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Item 1
Source of
Macromolecules
original article
33, No.6, 21st March 2000, p.2171-83
Title EFFECT OF THERMAL HISTORY ON THE RHEOLOGICAL
BEHAVIOR OF THERMOPLASTIC POLYURETHANES
Authors and
Pil Joong Yoon; Chang Dae Han afÀliation
Akron,University
The effect of thermal history on the rheological behaviour of ester- and ether-
based commercial thermoplastic PUs (Estane 5701, 5707 and 5714 from
B.F.Goodrich) was investigated. It was found that the injection moulding
temp. used for specimen preparation had a marked effect on the variations
of dynamic storage and loss moduli of specimens with time observed
during isothermal annealing. Analysis of FTIR spectra indicated that
variations in hydrogen bonding with time during isothermal annealing very Abstract
much resembled variations of dynamic storage modulus with time during
isothermal annealing. Isochronal dynamic temp. sweep experiments indicated
that the thermoplastic PUs exhibited a hysteresis effect in the heating and
cooling processes. It was concluded that the microphase separation transition
or order-disorder transition in thermoplastic PUs could not be determined
from the isochronal dynamic temp. sweep experiment. The plots of log
dynamic storage modulus versus log loss modulus varied with temp. over
the entire range of temps. (110-190C) investigated. 57 refs. Companies or
GOODRICH B.F. organisations
Location USA mentioned
Accession no.771897
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ISBN 1-85957-494-7
Polymer Processing with Supercritical Fluids
Contents
1 Supercritical Fluids ..................................................................................................................................3
1.1 What is a Supercritical Fluid? ..........................................................................................................3
1.2 Solvent Strength ...............................................................................................................................3
1.3 Advantages of Supercritical Fluids ..................................................................................................5
1.4 Polymers in Supercritical Carbon Dioxide (scCO2) .........................................................................5
1.4.1 Amorphous and Semi-Crystalline Polymers ........................................................................6
1.5 Supercritical Water (SCW) ...............................................................................................................6
1.5.1 Properties: Dielectric Constant ............................................................................................6
1.5.2 Properties: Ion Product ........................................................................................................7
1.6 Supercritical Methanol .....................................................................................................................9
1.7 Supercritical Nitrogen ......................................................................................................................9
2 Polymer Applications of Supercritical Fluids ........................................................................................9
2.1 Extraction and PuriÀcation ...............................................................................................................9
2.2 The Basic Principles of SCF Extraction of Polymers ....................................................................10
2.2.1 Choosing Solvent(s) for Supercritical Fluid Extraction (SFE) ..........................................11
2.2.2 Applications of SFE ...........................................................................................................11
2.3 Use of SCFs in Polymerisation ......................................................................................................11
2.3.1 Introduction ........................................................................................................................11
2.4 Impregnation ..................................................................................................................................13
2.5 Supercritical Fluid Dyeing (SFD) .................................................................................................14
2.6 Rapid Expansion of Supercritical Fluid Solutions (RESS Process) ...............................................15
2.7 Supercritical Anti-Solvents Precipitation (SASP) ..........................................................................15
3 Processing Applications of SCF Technology ........................................................................................16
3.1 Plasticisation of Polymers ..............................................................................................................16
3.2 Extrusion ........................................................................................................................................17
3.2.1 Microcellular Foams ..........................................................................................................17
3.2.2 MuCell Extrusion Technology ...........................................................................................19
3.3 Injection Moulding .........................................................................................................................19
3.3.1 Trexel: The MuCellTM System............................................................................................20
3.3.2 Ergocell ..............................................................................................................................20
3.3.3 Optifoam Process ...............................................................................................................22
3.3.4 Foamold .............................................................................................................................22
3.3.5 Applications and Properties of Microcellular Foams ........................................................23
3.4 Microcellular Blow Moulding ........................................................................................................23
3.5 Blending .........................................................................................................................................23
4 Hardening of Polymers ..........................................................................................................................24
5 Recycling and Recovery .........................................................................................................................24
5.1 Mechanical Recycling ....................................................................................................................24
5.2 Chemical Recycling .......................................................................................................................24
1
Polymer Processing with Supercritical Fluids
6 Conclusions .............................................................................................................................................25
Additional References ....................................................................................................................................26
Subject Index ................................................................................................................................................125
Company Index ............................................................................................................................................135
The views and opinions expressed by authors in Rapra Review Reports do not necessarily reÁect those
of Rapra Technology Limited or the editor. The series is published on the basis that no responsibility or
liability of any nature shall attach to Rapra Technology Limited arising out of or in connection with any
utilisation in any form of any material contained therein.
2
Polymer Processing with Supercritiical Fluids
1 Supercritical Fluids from their use. This review will therefore begin with a
quick introduction to supercritical Áuids.
In the polymer industry supercritical Áuids are currently
the subjects of intense research and commercial interest.
They can be used for a variety of processes, for example 1.1 What is a Supercritical Fluid?
as solvents in polymer synthesis, as plasticising agents or
for chemical recycling. Supercritical Áuids of materials A supercritical Áuid (SCF) is a substance (liquid or gas)
such as carbon dioxide and water also offer a ‘green’ which is in a state above its critical temperature (Tc) and
solution, in that they do not harm the earth’s environment critical pressure (Pc). At this critical point liquids and
(181). gases coexist, and a supercritical Áuid shows unique
properties that are different from those of either liquids
The development and application of supercritical or gases under standard conditions. The relationship
Áuid (SCF) technology has actually been quite slow, between temperature, pressure and the formation of
however it is unlikely that the pioneering researchers a supercritical Áuid can be seen in Figure 1. This is a
into supercritical Áuid properties in the early 1900s phase diagram for carbon dioxide, a SCF of particular
envisioned the wide-ranging impact supercritical interest to polymer scientists, which will be discussed
materials would have later in the century, with in more detail later on in this review.
applications in a variety of industries. Interest really
began in the 1960s and 1970s with research into An unusually large compressibility means that the
extraction techniques. These experiments used mainly density can be manipulated by small changes in
supercritical carbon dioxide in their research and pressure. One enormous benefit being that a SCF
concentrated in the food industry for the extraction of exhibits a pressure-tuneable dissolving power that is
Áavours and essential oils from materials such as hops ideally suited for developing processes for extracting,
and herbs and for decaffeinating coffee and tea. purifying and recrystallising substances and producing
new product forms that at present cannot be obtained
The decaffeination of coffee is the process most by conventional processing technologies.
commonly associated with supercritical fluids and
was Àrst carried out on a large production scale, in A SCF gives unusual properties, for example a viscosity
Germany in 1978. Here, the combined properties of like that of a gas, a density like that of a liquid, and a
the supercritical Áuid carbon dioxide were realised in a diffusion coefÀcient that lies between that of gas and
cost competitive and environmentally superior process. liquid. In addition, it has the gaseous property of being
The major driver for the development of the SCF able to penetrate porous and Àbrous solids and the
process was in the elimination of residual solvents in liquid property of being able to dissolve materials into
the products, especially methylene chloride, which had their components. It possesses no surface tension hence
previously been used to decaffeinate coffee. Increasing no capillary forces will appear during extraction. The
regulatory attention to solvent residues in food products solvating power of the SCF follows the changes in the
drove this, which is also driving current research in density. The beneÀts accrued from using supercritical
many polymer Àelds today. Áuids (especially water and carbon dioxide) include but
are not limited to the following: (i) environmentally
However there were also other advantages in employing benign solvents, (ii) the ability to selectively tune
supercritical fluids in these fields. Extraction by chemical reactions and solvents, (iii) the ability to
supercritical Áuid also gave improved Áavour and aroma enhance reaction rates due to their low viscosities and
characteristics in comparison to standard extraction high diffusivities. The parameters of some commonly
practices. used supercritical Áuids are summarised in Table 1.
3
Polymer Processing with Supercritical Fluids
supercritical Áuid
Figure 1
Phase diagram for carbon dioxide
(NB: At the boiling curve: gas and liquid phases co-exist. At the triple point: all three phases co-exist)
strength can be manipulated to simulate (and replace) A supercritical Áuid exhibits physical and chemical
the properties of many organic solvents. For example properties intermediate between those of liquids and
they can replace solvents such as hexane, methanol, gases. Characteristics of a supercritical fluid are:
methylene chloride and chloroform. Even the non-polar (i) dense gas, (ii) solubilities approaching liquid phase,
nature of supercritical (sc) CO2 material can also be and (iii) diffusivities approaching gas phase. These
overcome by adding a modiÀer in the form of a polar Áuids have densities and diffusivities similar to liquids
organic co-solvent. Thus SCFs have the potential to and viscosities comparable to gases as outlined in
replace numerous chemicals in a variety of industries, Table 2.
apart from the polymer industry.
4
Polymer Processing with Supercritiical Fluids
Mass transfer with supercritical Áuids is usually fast. 3. The ability to add modiÀers to a SCF, for example
Their active viscosities are nearer to those found in to change the polarity, gives them more selective
normal gaseous states. In the zone of the critical point, separation power.
the diffusion coefÀcient is more than ten times that
of a liquid and both the viscosity and diffusivity are 4. Little harm is done to the environment in terms
dependent on temperature and pressure. Changes in of residues from processes using SCF compared
viscosity and diffusivity are more marked in the area of to volatile organic compounds (VOCs) and ozone
the critical point. Also at high pressures, viscosity and depleting substances (ODSs).
diffusivity are considerably less than that of a liquid.
Therefore, the properties of gas-like diffusivity, gas- 5. SCFs are generally cheap, safe to use and have
like viscosity, and liquid-like density combined with minimal disposal costs associated with their
pressure-dependent recovery control have provided operation in industrial processes.
the drive for applying supercritical Áuid technology to
a variety of problems. By far and away the most widely used SCF of interest
to polymer scientists is scCO2 which will now be
The ability to improve solubility by using a material in considered in greater detail.
a supercritical state has been known since the 1870s,
therefore supercritical Áuid technology is not entirely a
new technology. The unique properties of supercritical
Áuids were reported slightly over one hundred years ago 1.4 Polymers in Supercritical Carbon Dioxide
by the observation that at high pressures, gases such as (scCO2)
carbon dioxide and ethylene, dissolved complex organic
compounds and that this dissolving power of these Áuids Carbon dioxide (CO2) is the most commonly used
was a strong function of pressure. However, it was not supercritical Áuid because of its low critical temperature,
until the second half of the 1900s that the Àrst commercial low toxicity and high purity at a low cost. It is non-
scale supercritical processing of polymers was utilised to Áammable and its use does not contribute to the net
manufacture tonnes of LDPE per year using supercritical global warming effect. In addition, CO2 is the second
ethylene (a.1). As stated in the introduction, for many most abundant and the second least expensive solvent in
years, SCFs have been used in food processing industries the planet. Being a gas under ambient conditions favours
to extract compounds such as caffeine, and the ability to its easy removal from polymeric products, thus saving
purge polymer materials of unwanted contaminants is costs on other secondary operations such as drying and
a new application with growing interest in this area of solvent removal.
supercritical Áuid technology.
This material has a relatively low operating pressure
and temperature, which makes obtaining supercritical
conditions less expensive then many other SCF
1.3 Advantages of Supercritical Fluids
materials. For example it is supercritical in a range often
already experienced by polymers during manufacturing
The advantages of using a SCF can therefore be processes such as extrusion or injection moulding. It can
summarised as follows: also be easily removed by simply reducing the pressure.
It can be easily recovered for recycling and can be used
1. SCFs have similar solvating powers to liquid to replace harmful or toxic materials such as Freons. It is
organic solvents, but their higher diffusivities, lower miscible with a variety of organic solvents, and can also
viscosity and lower surface tension make them more be used to replace some organic solvents. With a few
effective in many cases. notable exceptions, most polymers with high molecular
weights are not soluble in this material, an exception is
2. Since their density is pressure-tuneable, separation Áuoropolymers which do dissolve. However, polymers
of substances from solvents is easy to achieve. can take up a signiÀcant quantity of the material in
5
Polymer Processing with Supercritical Fluids
a supercritical state. Amorphous polymers behave (ii) impregnation and extraction of impurities, (iii)
differently to semi-crystalline materials, this difference membrane conditioning, (iv) production of micro-
will now be discussed further. particles, foams, gels and Àbres and (v) polymerisation
reactions.
1.4.1 Amorphous and Semi-Crystalline Polymers Changes in the physical and mechanical properties of
polymers are readily observed through the sorption of
At near critical conditions amorphous materials absorb supercritical carbon dioxide, with the resultant effect of
CO2 to a greater extent than semi-crystalline polymers reduction of the glass-transition temperature. The major
and a greater amount of plasticisation is found to occur. effects of supercritical carbon dioxide on amorphous
This is because CO2 is absorbed only into amorphous polymers are summarised in Figure 2. Table 3
regions and not crystalline regions. As the concentration summarises the effects of scCO2 on both amorphous
of the fluid increases, sorption and swelling in and semi-crystalline polymers.
amorphous polymers (or amorphous regions of semi-
crystalline materials) can cause a phase transition from
glass to liquid. The glass transition temperature (Tg) of
1.5 Supercritical Water (SCW)
the polymer drops signiÀcantly, a property which can
be exploited in polymer processing. Quantities in the
region of 10-30% by weight can be absorbed by these Like carbon dioxide, water is readily available and
materials and treatment with just 8-10% can depress a hence of interest as a supercritical Áuid. It is now
Tg of 80 °C to below room temperature. The amount of widely acknowledged that SCW possesses a massive
absorption is increased by increases in temperature and capacity for the destruction of both toxic and hazardous
pressure, however the polarity of the polymer and the materials.
structure of the polymer also determine the solubility
of any particular polymer being used. Whilst this interest is currently focused mainly in
waste water treatment and the conversion of poorly
Plasticisation of the polymer also causes an increase in biodegradable substances to less toxic and more
crystallinity, which causes an increase in the melting degradable substances, it has also come to the attention
temperature and induces changes in the mechanical of chemists. This is as a potential medium for chemical
properties of the materials. synthesis and also as a means of polymer recycling.
This is because of its special pressure, volume and
The different response to scCO2 means that amorphous temperature (PVT) dependencies. As a supercritical
and semi-crystalline polymers may be more suited to Áuid it has a number of interesting and unique properties
some applications than others. Certainly within the which are related to its dielectric properties and the ion
scope of this review it is amorphous polymers that are product.
of most interest.
There have been numerous attempts to quantify the 1.5.1 Properties: Dielectric Constant
plasticisation effects of scCO2 on various polymers,
e.g., (72, 90, 94, 101, 113). However, it is difÀcult to It can be seen from Figure 3 that supercritical water
deÀnitively state exact levels of either Áuid uptake or is able to operate at a range of dielectric constants as
level of plasticisation effect for any given polymer, the temperature and pressure is changed. The dielectric
given the many different processes, conditions, and constant can be varied in a useful region from about 2 to
types of the same material which have been tested. All 30 (although higher values can be obtained) dependent
these factors make any comparison virtually impossible. on the pressure and/or temperature. The SCW can be
Despite this however, in the Àeld of polymer processing, controlled to give a dielectric constant representing polar
supercritical technology has already established its to non-polar properties across this range, mimicking
effectiveness. Due to their small size, supercritical the polarities of numerous common solvents which
Áuids penetrate into polymers more easily than do occur. In comparison to common solvents, hexane
larger liquid solvents. This property facilitates the (non-polar) is 1.8, carbon tetrachloride has a dielectric
controlled rapid sorption of SCF through the adjustment constant of 2.2 and methanol 32.6 (polar). It therefore
of pressure and temperature. Supercritical Áuid used for has a higher solubility for organic substrates than water
polymer plasticisation has signiÀcant effects on polymer under atmospheric conditions and can dissolve parafÀn,
processing activities which include: (i) separation and aromatics and gases. At the critical point, it will appear
fractionation of polymers for extraction of impurities, as a weak polar solvent.
6
Polymer Processing with Supercritiical Fluids
Figure 2
Effect of supercritical carbon dioxide on amorphous polymers
Table 3 Summary of the effects and applications of scCO2 on amorphous and semi-crystalline polymers
Semi-crystalline Amorphous
Gas absorption Low (only in amorphous regions) High
Plasticisation effect Low (only in amorphous regions) High
Crystallinity Small increases may be seen (only in Increased
amorphous regions)
Common examples Nylon 66, PVDF, PP, HDPE ABS, HIPS, PC, PMMA, PET
Potential applications Replacements for CFCS in cleaning Foaming and production of
applications (limited applications as microcellular structures, impregnation,
amorphous dependent on degree of surface modiÀcation, introduction of
crystallinity) crystallisation
1.5.2 Properties: Ion Product temperatures and pressures, the value of the ion product
will be considerably increased, giving the acid catalysis
The catalytic properties are also enhanced in the effect. The relationship to the dielectric constant at
supercritical state. The proton concentration increases 400 °C is shown in Figure 4.
greatly, by about 30 times, which allows the SCW to
replace other acid catalysts. This change in activity is It can be seen from the unique properties of SCW, that
represented by the ion product which is the product of the ability to vary the properties of the reaction medium
the hydrogen ion concentration and the hydroxy-ion over a wide range of conditions can be achieved simply
concentration. by changing the pressure and temperature. A reaction
can be optimised without changing the solvent, which
offers many advantages to chemists. This versatility can
This is deÀned as Kw = [H+][OH-] be clearly seen in the ability to vary the relative static
dielectric constant (¡) and the Kw value with changes
Under standard temperature and pressure, this has a to temperature and pressure, since these two physical
value of 1 x 10-7 mol/l for both molecules, the value properties have such a major impact on both the polarity
for Kw will therefore be 1 x 10-14 (mol/l)2. Under high and acid/base-catalytic properties.
7
Polymer Processing with Supercritical Fluids
Figure 3
The dielectric constant of water as a function of density and temperature
Figure 4
Changes in ion product and dielectric constant as pressure changes at 400 °C
8
Polymer Processing with Supercritiical Fluids
With supercritical water high reaction rates can be are certain process advantages with microcellular
achieved, due to the combined properties of high foaming which can make this the gas of choice (see
dissolving capacity and high transportability. This Section 3.2).
means that any mass transfer restrictions due to phase
boundaries do not apply with compounds highly soluble Whilst there are other supercritical Áuids as shown in
in SCW. This is because as a supercritical Áuid it has a Table 1, at the time of this review none has yet generated
high diffusivity and low viscosity to penetrate materials. any pertinent research or data to merit inclusion in this
As well as this, the reaction kinetics can also be varied review.
by pressure. Its pressure and temperature tunability
enables good control as a reaction-causing solvent, Now that supercritical Áuids themselves have been
and has been used for applications such as extraction, considered, discussion will now begin on how these
decomposition and removal of pollutants in waste water, materials can be applied to various aspects of polymer
sludge, coal and oil applications. It has also been the processing.
solvent of choice for recovery of waste plastics during
chemical recycling.
9
Polymer Processing with Supercritical Fluids
Generally extraction relies on the basic principle that the free volume in the polymer is increased, the SCF
the solubility of a given compound (solute) in a solvent can penetrate deeply into the matrix and the impurities
varies with both temperature and pressure. At ambient are dissolved by the supercritical Áuid. As any volatile
conditions (25 °C and 1 bar) the solubility of a solute in materials within the feed matrix will then partition
a gas is generally negligible (and is related directly to themselves within the supercritical phase, these are
the vapour pressure of the solute). In a SCF, however, removed with the SCF during the extraction from the
solute solubilities of up to 10 orders of magnitude feed system. In the de-pressurisation phase the pressure
greater than those predicted by ideal gas law behaviour is quickly reduced and the supercritical fluid and
have been reported. This is because in supercritical impurities diffuse out of the polymer. The SCF can then
Áuids the solubility of a solute is not just a function be removed by changes to temperature and/or pressure,
of pressure. Solute-solvent interaction as well as the leaving negligible SCF in the extracted material and the
vapour pressure, controls the dissolution reaction. SCF can be recycled by recompression. This system is
Therefore volatile solids have a much higher solubility shown in Figure 5.
in SCF in general, than for example in ideal gases.
There are both advantages and disadvantages of using
The ability to further increase the solubility within a SCFs when compared to conventional liquid solvents
SCF extraction process may also be desirable, in order for separations.
to reduce the amount of solvent required. This may be
achieved by adding another component to the mixture. Some of the advantages are:
This may be referred as a co-solvent or entrainer. This
material will generally have a volatility intermediate • The dissolving power of the SCF is easily controlled
to that of the SCF and the solute which enables the and manipulated by pressure and/or temperature,
reaction to be controlled more precisely and selectively.
However, use of extra materials may also change the • No harmful residue is left as solvents are non-
chemical nature of the SCF and the ability to remove it toxic,
after reactions must also be taken into account.
• The SCF is easily recovered and recycled from the
extract due to its volatility,
2.2 The Basic Principles of SCF Extraction of
Polymers • The ability to sometimes achieve separations that
are not possible by traditional processes,
The Áuid is compressed to elevated pressures above its
critical pressure, to make it supercritical. The polymer • Heat sensitive materials can be extracted as low
is then exposed to the supercritical Áuid and swells. As temperatures can be employed.
Figure 5
Basic principle of SCF extraction
10
Polymer Processing with Supercritiical Fluids
Some of the disadvantages are: (ii) puriÀcation and separation of substances such as
oil and grease and
• An elevated working pressure is required with
associated costs and hazards, (iii) removal of impurities in chemical materials (195).
• Whilst recycling and cost savings can be achieved Conventionally, the puriÀcation of polymers is carried
by a recompression of the solvent, equipment out by either vacuum, steam stripping or solvent
installation can be costly and complex, extraction. However, these methods are not always
adequate as they come short in reducing the residual
• A high capital investment is therefore necessary for contents to the required permissible levels. Alternatively,
equipment. devolatilisation with supercritical Áuids can improve
impurity removal due to an increased thermodynamic
driving force and improved molecular diffusivity. It is
2.2.1 Choosing Solvent(s) for Supercritical Fluid therefore more effective.
Extraction (SFE)
This method can also be used to remove additives, residual
solvents, catalysts, and side reaction products which can
When choosing a solvent for SFE, many of the
have a detrimental effect on the end-use properties.
parameters are similar to those used in more traditional
extraction methods, namely: has good properties, is
inert to the Ànal material, can be easily separated and Since supercritical Áuids are ‘tuneable’, selective extractions
is economic to use. For SCF, this often means that the can be carried out providing the SCF has sufficient
critical parameters must be achievable without undue solubilising power with the product to be puriÀed.
cost or complexity.
For this reason carbon dioxide is the most commonly 2.2.2 Applications of SFE
used SCF in SFE, due primarily to its low critical
parameters, low-toxicity and low cost. Another Several applications for SFE outside the polymer
solvent with high potential is SCW, due to its ability industry have been commercialised, for example
to dissolve organic compounds whilst leaving behind in the food industry to decaffeinate tea and coffee,
inorganic salts. The opposite effect to its uncritical extraction of oils, hops and aromas. Tobacco can be
state. This enables the same solvent to be used for both denicotined with this process. A process called Residum
extractions. Oil Supercritical Extraction (ROSE) is used to remove
impurities in the treatment of used oils and lubricants.
Several other SCFs such as hexane and methylene The pharmaceutical industry uses SFE to extract
chloride have been used commercially and in research. ingredients from herbal plants, and also eliminate
For example, the petrochemical industry uses organic harmful residual solvents from their products. It can also
solvents. However, these materials require explosion be used to clean contaminated soil and remove residual
proof equipment, increasing the expense of these solvents from waste materials. Supercritical extraction
processes. Other restrictions on solvent choice may also in polymer applications is not widely used yet, but the
apply, for example the use of one set of highly effective potential seems high for the polymer industry. One
supercritical solvents (chloroÁuorohydrocarbons, CFCs) potential application may come in the mechanical
is limited due to their effect on the ozone layer. recycling Àeld where supercritical Áuids could be used
to remove low molecular weight contaminants from
recyclate before re-processing. (It is these that often
Use of carbon dioxide or water in the form of supercritical
give recyclate such a distinctive smell.)
Áuids is used as a substitute for organic solvents in both
the food and medical industries. SCFs are used as safe
alternative solvents in the food processing industry.
They are also used in the rapid extraction of spirits and 2.3 Use of SCFs in Polymerisation
other components at room temperature. Other areas of
application include:
2.3.1 Introduction
(i) puriÀcation and fractionation of polymers such
as the removal of unaffected monomers from The many attributes of scCO 2 which have been
polymers discussed earlier, have made it a viable alternative
11
Polymer Processing with Supercritical Fluids
solvent in a number of polymerisation reactions. It has Of all these processes it is the solution, suspension
been intensively researched in a wide range of reactions and emulsion type reactions that have attracted most
and used as the continuous phase for numerous step- attention for the application of SCF technology, because
growth and chain-growth reactions. This includes free- of the possibility to reduce waste water and/or solvent
radical, ionic- and metal-catalysed process routes. during polymerisation and to improve properties.
However, the long-term future of its use as a solvent It should be noted that bulk polymerisation is by its
will be limited by the poor solubility of most long- nature (solvent-free), of no interest to SCF technology,
chain polymers. Its application is likely to be limited since the objective is to replace solvents that are
to speciÀc special applications and materials such as toxic or reduce waste. However the use of a solvent,
Áuorinated polymers, polysiloxanes, and where the as in solution polymerisation, often offers a number
reaction involves soluble polymers such as those with of advantages (and some disadvantages too) to a
a low molecular weight. polymerisation process as summarised in Table 4.
Where SCFs have been used successfully, the ability to A summary of various techniques covered in the
tailor the properties with scCO2 has enabled the synthesis abstracts accompanying this review is given in Table 5.
of polymers with precise control of molecular weight It should be noted that all monomers could in theory
and polydispersity, but with minimal contamination, be processed by any one of the routes highlighted here.
and at acceptable levels. The morphology can also be However, there are often economic reasons why one or
controlled in some cases. ScCO2 also offers a potential two processes are favoured above others.
process route to extremely low residue polymers by
acting as a solvent in a number of polymerisation Fluoropolymers are already produced commercially
reactions. using scCO2. The polymerisation reaction is carried out
using the emulsion process. The use of SCF enabled the
In order to fully comprehend the application of SCFs replacement of water and was termed ‘Process G’ by the
in polymerisation, a quick revision of the various manufacturers, DuPont. The materials produced were a
polymerisation routes is now provided. range of melt processable PTFE resins (151, 153).
Commercial polymer materials are made by a variety of Due to the higher solubility of materials in SCF
techniques depending on the required properties and the compared to some conventional solvents, the range
type of Ànal product. Polymerisation mechanisms can of polymers that can be produced by techniques like
be simply classiÀed into two classes: step and chain. solution polymerisation can be expanded somewhat.
However with this technique there is a requirement for
• Step polymerisation proceeds with an increase of the materials to be soluble in the solvent, which still
one species at a time in any given chain. During means many polymers are not suitable for this route.
the reaction, any of the various sized polymer Generally, this means applications are limited to silicone
species present can react with another. The and Áuoropolymers. For example, DuPont has produced
production of polyamides and polyurethane are Áuorinated ethylene-propylene with scCO2 as a solvent
examples of commercially used step polymerisation using the solution polymerisation technique.
processes.
With dispersion polymerisation, SCF can be applied
• With chain polymerisation an initiator is used to for synthesis of polymers from monomers such as
produce a reactive species such as a free radical, acrylate and methacrylate (59, 67). Homogeneous
cation or anion. Monomer then reacts with the polymerisation with supercritical Áuids has also been
reactive species. Polystyrene and polyethylene are studied for Áuoroacrylates.
two examples of materials that can be made by
undergoing chain polymerisation.
Table 4. Use of solvents in polymerisation
Radical polymerisation can be split into homogeneous reactions
and heterogeneous types based on the initial mixture. Advantages Disadvantages
Mass and solution polymerisation are homogeneous; Diluent Purity (residues)
suspension and emulsion polymerisation are
Aids heat transfer Chain transfer to solvent
heterogeneous processes. A further type of radical chain
Allows mixing
polymerisation is emulsion polymerisation, which uses
monomers in the form of colloidal dispersions. Better thermal control
12
Polymer Processing with Supercritiical Fluids
13
Polymer Processing with Supercritical Fluids
solvent recovery can be made relatively easily, when using styrene (224), again using the scCO2 to swell
compared to the cost of other solvent recovery options. the LDPE substrate. After further treatment to induce
The process steps are illustrated in Figure 6. polymerisation some entanglement between the LDPE/
PS blends could be seen.
Materials that are both miscible and immiscible can
become dispersed. A material with little afÀnity for the This technology has numerous possibilities, e.g., (55,
matrix is dispersed and then trapped when it comes out 61), outside the range of melt mixing and with thermally
of solution, but has no molecular attraction with the unstable materials. For example it is possible to take a
matrix. The scCO2 appears not to aid compatibility in hydrophobic material such as PVC and generate a water-
these cases, in contrast to the effect seen in blending by soluble polymethacrylic acid (PMAA) within it.
extrusion for example. A material with afÀnity for the
matrix has potential in a variety of applications such as
a drug delivery mechanism, for dye impregnation and
2.5 Supercritical Fluid Dyeing (SFD)
to produce polymer blends. In all cases it is necessary
that the matrix species is able to swell under scCO2. A further application for SCF impregnation is to use
The ability to replace current aqueous dying solvents it as an aid to the dyeing of polymers (212, 214). It
with an environmentally benign material could reduce offers a number of advantages when compared to the
textile waste streams considerably. This will be further current water processes that require water, surfactants
discussed in Section 2.5. or dispersing aids and need a drying stage. With SFD
the production of waste water, which contains remnants
scCO2 can be used to obtain modifications to the of all the additives and unused dye, can be eliminated,
polymer molecules, by acting as a carrier for a second as can the necessary drying stage. PP fibres dyed
impregnated material. By impregnating one material using scCO2 also have a higher dye uptake than with
with a monomer and an initiator, the matrix swollen conventional water-based dying systems. Aramid, PE
under the effects of the scCO2 is modiÀed, without and PET (227) can also all be successfully dyed. Dye
producing thermal stresses. This allows materials to be molecules tend to be relatively large with slow diffusion
manufactured that may be difÀcult to obtain by more rates and they penetrate only into amorphous regions
common methods. of the polymer. In PP the plastication effect makes the
polymer molecules more mobile and this, combined
For example Lui and co-workers (107) have reported with the high diffusivity of scCO2, leads to higher
the polymerisation of styrene monomer within a dye diffusion into the polymer. There has also been
polypropylene (PP) matrix. This was carried out by considerable success in the dyeing of polyester (179,
impregnating a swollen PP matrix with the monomer 200). The high initial investment for this technology
and an initiator using scCO2 as the solvent. There has means it is the harder to dye materials that will most
been a similar study with the impregnation of LDPE likely utilise this technology Àrst.
Figure 6
The impregnation process
14
Polymer Processing with Supercritiical Fluids
2.6 Rapid Expansion of Supercritical Fluid The powder size produced can be manipulated by
Solutions (RESS Process) changes to parameters such as pressure, temperature
and concentration. The advantages of carbon dioxide
In the 1980s when a whole number of SCF applications are the same as in other processes. It is cheap, non-toxic
were being explored, one such technology was an exciting and leaves no residue.
new method to produce ultraÀne particles. Even today, this
is still an area of intense development by pharmaceutical The rapid expansion stage causes a sudden drop in the
companies and researchers in the US, Japan (70) and in dissolving capacity of the solvent as the Áuid comes out
Europe. This is because the recrystallisation of materials of its supercritical state, causing nucleation and growth
by supercritical Áuid processing enables the manufacture of any low vapour pressure solute species that were
of specially structured products of signiÀcantly high present in the solution prior to expansion. This rapid
quality and function that simply cannot be produced with crystallisation of the solute results in homogeneous
conventional manufacturing methods. This is because submicrometre particles. In many ways the process relies
some pharmaceutical materials are too unstable to on exploiting pressure drops, similar to the pressure
micronise by methods such as simple grinding or milling, drops employed in a number of SCF technologies such
as they either may form as amorphous materials or just as in extrusion to produce foaming (which will be
smear. This makes control of the particle size extremely discussed in the plastic processing section). However,
difÀcult. the products here can have a number of different forms
dependant on the process settings employed.
Two methods have been developed to overcome this
problem: As in many current SCF applications, the solvent
of choice is carbon dioxide; however as in other
• Rapid expansion of supercritical Áuid solutions technologies it may be necessary to modify the
(RESS) and properties of the solvent to improve solubility. Therefore
modiÀers may be required especially to improve the
• Supercritical anti-solvent precipitation (SASP) solubility of polar molecules (e.g., MeOH), since
carbon dioxide is non-polar, (but does have a limited
The RESS process can be used to produce thin Àlm afÀnity to polar materials). Co-solvents may also be
coating, polymer Àbres and Àne graining, by using employed to enhance solubility. A further approach is
this process to manufacture whisker-shaped fine to add polarity with Áuorinated substituents. However,
particles of a submicrometre size. There is a wide this can add expense to the process and also make
range of different materials that can be processed using recycling necessary.
RESS technologies including organic and inorganic
compounds and pharmaceutical materials. There are also a number of practical advantages
associated with the use of supercritical carbon dioxide
The RESS process is unique, as RESS products are as a solvent such as the Ànal dryness achieved by
generated ‘dry’, meaning little or no residual solvent. evaporation. This could be essential where residual
This is because the solvent changes phase during the solvents are problematic such as in pharmaceutical
expansion phase, leaving the deposited supercritical manufacture. This technique is currently employed in
Áuid-soluble materials behind. the pharmaceutical industry to produce materials such
as antibiotics, steroids and controlled release drugs.
The process works by exploiting property changes bought
about by density changes. By passing supercritical Áuid It is also possible to use supercritical carbon dioxide
solutions through a small oriÀce, a rapid expansion where there is no solubility, in a complimentary process
occurs, hence the acronym RESS. to RESS called SASP.
15
Polymer Processing with Supercritical Fluids
supercritical carbon dioxide can still be employed in a • a lower rigidity at room temperature,
powder forming reaction. The SASP process involves
Àrst dissolving the material in a suitable solvent. This • increased elongation and Áexibility of individual
is then sprayed into the supercritical carbon dioxide, chains in the polymer,
contained in a high-pressure chamber. Droplets are
formed and the original solvent dissolves in the carbon • increased toughness.
dioxide, leaving the insoluble material in powder
form. The size of the powder depends on the reaction Amorphous materials and amorphous regions in semi-
conditions such as temperature, pressure, and the crystalline materials are more easily penetrated than
concentrations of the constituent reaction materials. crystalline regions in semi-crystalline polymers. The
Like RESS this technique is currently employed in the degree of crosslinking also affects the ability of the
pharmaceutical industry (106). plasticiser to penetrate. This can be observed when
considering that elastomers (with a less dense network
A further advantage of both the RESS and SASP of crosslinks) may swell in a solvent but a thermoset
processes are the extremely fast process times. Gas and (highly crosslinked) neither swells nor dissolves.
solution mixing and pressure reductions can take place
in times well below a second. Market opportunity is
During polymer synthesis, plasticisation can generally
likely to increase for these technologies and this should
be achieved either during synthesis by adding a small
also therefore enhance the economics of the process.
amount of co-monomer (to disturb the subsequent
crystallinity and chain packing), or by adding a low
molecular weight compound into a higher molecular
weight polymer. In both techniques the result is an
3 Processing Applications of SCF increase in the free volume leading to the described
changes in physical properties.
Technology
A further method to induce plasticisation is to include
a high-pressure gas, a process called gas-induced
3.1 Plasticisation of Polymers plasticisation. When scCO2 is dissolved into a polymer
melt the viscosity is observed to decrease. This is
Since it is the plasticisation of polymers using scCO2 which obviously of great interest in trying to process high
is of major interest in processing, a quick discussion on viscosity melts. It also enables temperature-sensitive
the effects of plasticisation will now follow. polymers to be processed at lower temperatures, as
well as lower processing temperatures for materials
Plasticisers are additives sometimes mixed with with high glass transition temperatures. As previously
polymers to change the rheology and/or the mechanical described, amorphous polymers swell under the
properties of the Ànal product. Perhaps the best-known inÁuence of scCO2 and can absorb carbon dioxide to a
use of plasticisers is in PVC where plasticisers can be greater extent than crystalline polymers, and therefore
used to reduce stiffness and lower the glass transition amorphous polymers have an increased potential
temperature. The effect of this addition depends on the for both plasticisation and foaming (which will be
nature of the additive and the structure of the polymer. If discussed later).
the additive is soluble in the plasticiser, then absorption
will cause swelling and eventually it will dissolve. For materials with high viscosities, a lowering of
viscosity during processing can be achieved by an
The behaviour of molten thermoplastic polymers with increase in the processing temperature. However an
supercritical Áuids is of great interest as a substitute for increase in temperature can also cause heat degradation,
plasticising agents in processing. This is particularly if this requires temperatures above the normal processing
of importance for thermally labile polymers with high range. Therefore an alternative method that could reduce
glass transition temperatures (Tg) and for materials that the viscosity of polymers is extremely attractive. This is
are highly viscous. not only in terms of the drop in viscosity and therefore
improvements in processability, but also the ability
Plasticisation is generally characterised by changes in to reduce the processing temperatures. This allows a
the polymer system that result in: drop in energy consumption and therefore leads to cost
reductions. Obviously therefore, this is a very attractive
• a lowering of the glass transition temperature, proposition to material processors.
16
Polymer Processing with Supercritiical Fluids
The high pressures required for the containment of (CO2) is the most common blowing agent but nitrogen
SCF within the polymers, are similar to those already (N2) is also used. This can be injected directly into the
encountered in processing operations such as injection molten polymer in the extruder. By using these gases in
moulding and extrusion. Therefore, it is not a great supercritical states both a higher diffusivity and a higher
problem to modify these systems for use with a SCF solubility in the polymer can be achieved. A variety of
such as scCO2. Also the gas can be easily removed by injector systems are available, the main prerequisite
simply reducing the pressure. Processes developed for being that they can deliver a controlled dose of the Áuid,
use with supercritical Áuids will now be discussed, to the barrel of the machine.
whilst they are primarily focused on foam applications,
the other major beneÀt of using supercritical Áuids The second step requires the saturation, mixing and
(for energy savings) should also be borne in mind dissolving of the SCF into the molten polymer to create
throughout. a single-phase homogeneous polymer/gas solution. A
number of different methods of mixing the polymer
and gas have been studied. For example Rapra has done
work on dispersing the SCF in the polymer, using both
3.2 Extrusion
a static mixer and a cavity transfer mixer (CTM) (228).
The work proved to be successful and was later applied to
Standard extruders generally need little modiÀcation injection moulding for the Foamold process (see Section
to incorporate scCO 2 as this can be introduced 3.3.4). Research has also been carried out to assess the
through a venting port (114, 118, 228). The scCO2 is feasibility of making compounds of gas encapsulated
injected downstream after the plastic undergoes initial polymers, providing a gas/polymer ‘pre-mix’ to enable
plastication. The two materials then create a single processing/foaming to be carried out without the need for
phase through the action of the screw and mixers. The further gas additions. The permeability of the polymer
rapid pressure drop at the die initiates cell nucleation. and hence gas diffusion and potential shelf-life of these
compounds is obviously a limitation here.
The use of supercritical Áuids in extrusion has focused
on two distinct applications: In terms of the extrusion processing itself, it has been
found that the gas diffusion process depends on solubility,
1. Insulation foams, low density (< 0.4 g/cm3). diffusion rate and extrusion parameters such as foaming
temperature and saturation pressure (in order to promote
2. Microcellular foams, high density (approximately the development of a microcellular structure).
0.7 g/cm3).
The Ànal step is the foaming as the material exits the
The basic steps to foaming remain the same; the die. The die has a dual function as it must maintain an
differences are in the pressure drop requirements, adequate pressure in the extruder barrel to keep the
which control the Ànal cell sizes. For standard foams, blowing agent from coming out of solution. It must
conventional equipment can generally be used providing also provide the appropriate rapid pressure drop rate to
supercritical Áuid is introduced and adequately mixed bring the SCF back out of solution. At this stage there is
prior to foaming. Under these conditions a standard nucleation, and gas nuclei form throughout the polymer
extruder would generally be expected to produce matrix as the materials are split back into two phases.
low quality foam with large irregular cell sizes. This is followed by a cell growth phase that relates to the
These extrusions would have the same drawbacks growth and development of the cells. This is controlled
as conventionally produced cellular materials using by a combination of mass transfer and Áuid dynamics
chemical-blowing agents, i.e., poor and irregular surface which is beyond the scope of this review. Depending on
Ànish. the parameters employed during processing, a variety of
conventional size cells or microcellular cells will result.
For microcellular production, the pressure drop is more Some of the important parameters in SCF foaming are
tightly controlled, by design and modiÀcations to both highlighted in Figure 7.
the screw and die. This enables maintenance of an
adequate pressure within the system and ensures that
a sufÀcient pressure drop is present when the material 3.2.1 Microcellular Foams
exits through the die.
Since microcellular foams are of such high commercial
The Àrst step in extrusion is the injection of the physical interest, further discussion on their unique properties
blowing agents in a supercritical state. Carbon dioxide will now follow.
17
Polymer Processing with Supercritical Fluids
Figure 7
Important parameters in the extrusion foaming process
A microcellular foam is characterised by its cell size sized, microscopic cells than characterise microcellular
(smaller than 10 μm) and the cell density (density >109 moulding.
cells/cm3). These materials have a more consistent and
homogeneous cell structure compared to the cell size There is little data available on the critical pressure drop
and structure of standard foam. These bring a number required for microcellular foaming. For high impact
of advantages, including better physical properties such polystyrene (HIPS), it is reported as being around
as improved impact strength and toughness. This means 109 Pa/s. However such critical pressures are likely
that when compared to common structural foams these to be highly material dependant due to factors such
materials have a higher weight to mechanical strength as crystallinity, branching and additives which can all
ratio. They also beneÀt from an improved surface affect the number of available nucleation sites.
appearance, low dielectric constant and improved
thermal insulation. Another important beneÀt of this The pressure drop in a system can be calculated as
process is the ability to replace unfoamed applications follows:
which do not require the full mechanical properties
dp 32μD4V2
achieved with unfoamed materials. This allows =
manufactures to achieve both material and weight dt d6
savings. where D = screw diameter, μ = material viscosity, d =
nozzle oriÀce diameter, V = extrusion speed/injection
In order for microcellular foaming to be achieved, the speed.
supercritical Áuid and polymer must Àrst create a single-
phase solution. For this, the CO2 needs to be dissolved As the screw speed is increased the pressure drop
with the polymer at high pressure, the solubility being also increases. The critical pressure required to create
pressure dependent. Lowering the pressure to below the microcellular foams is however also related to the
saturation point will bring the CO2 out of solution. gate size (in injection moulding), the material, the
gas percentage and the melt temperature. In injection
To create microcellular foams it is necessary for a large moulding, which will be further discussed later in this
number of cells to be created before any increase in the review, there is a clear link between injection speed and
size of those cells occurs. This can only be produced potential weight reduction. Higher speeds lead to more
with a cell nucleation rate that is extremely high and foaming as there are considerably more cells produced
higher than the diffusion rate of the blowing agent into at a higher injection speed. This is due to an increased
cells (i.e., cell creation as opposed to cell growth). With pressure drop in the tool at a faster speed. At a further
a large number of nucleation sites in place, growth can increased injection speed the pressure drop would
then occur simultaneously and at the same rate. It is this continue to rise and more cells would be achieved until
relationship that gives the evenly distributed, uniformly a saturation point was reached. It is the rate of pressure
18
Polymer Processing with Supercritiical Fluids
reduction which controls the time period for nucleation 2. A proprietary screw design is used to disperse
and growth. Under unsaturated process conditions, a and intimately mix the SCF and the polymer to
higher pressure drop may be required to increase the form a single-phase solution. A pressure proÀle is
nucleation rate. This can be achieved with the design required to keep the SCF in solution and to ensure
of the nozzle and with consideration of factors such the availability of sufÀcient nucleation sites when
as tooling. the material exits the die.
In terms of service strength, the compressive strength of 3. A suitably designed die will ensure there is control
the foams depends on the cell size, as it has been found of the microcellular foaming when the material exits
that the compressive strength increases with increasing the die.
cell size. The compressive force causes progressive
buckling of the microcellular cells (319). A diagram of a potential setup is shown in Figure 8.
Microcellular foaming was Àrst offered for extrusion Trexel along with others, have also successfully
commercially by Trexel under the trade name MuCell commercialised microcellular moulding in injection
Extrusion Technology. This system provides both the moulding. As in extrusion, all the systems represented
equipment and processing technologies for producing here assume the creation of a single-phase of polymer
microcellular foams using thermoplastic materials and and gas with a solubility gradient.
can currently only be used under license. It can be
installed in both new and existing extrusion equipment. scCO2 and supercritical nitrogen are currently used
As in conventional foaming, the MuCell Extrusion as foaming agents in injection moulding to produce
Technology is based on three stages, but the process lightweight components with high mechanical strength.
requires the purchase and modiÀcation of several pieces The higher solubility of scCO2 is advantageous, however
of proprietary equipment: supercritical nitrogen can sometimes be used to produce a
better surface Ànish and smaller cells. As with extrusion,
1. A Trexel SCF System provides the Áuid pumping to produce microcellular foams a higher pressure drop
and a MuCell® Injector Kit is used to inject the is required than with conventional foaming. This is to
supercritical Áuid directly into the extruder barrel. increase the number of nucleation sites.
Figure 8
Design for a MuCellTM system
19
Polymer Processing with Supercritical Fluids
3.3.1 Trexel: The MuCellTM System (166, 167) • Software and system modiÀcations to create and
maintain the uniformity required of the single-phase
An injection moulding system using scCO 2 is solution through the injection moulding cycle.
commercially available by licence from Trexel Inc.,
Woburn, MA. The technology is known as MuCellTM. The screws are usually 22:1 or 24:1 L/D with the barrel
Àtted with injector systems designed to match the screw
There are numerous claims made for this process, length. A shut-off nozzle and screw position control
for example it is claimed that this technology can modiÀcations are used to help maintain the pressure for
lower the viscosity of the melt, allowing temperature a single phase solution and prevent decompression. A
reductions of up to 78 °C (especially useful if processing system is shown in Figure 9.
heat sensitive materials such as PVC leading to both
As with the Trexel extrusion technology, this system
reduced energy consumption and less chance of material
also requires the purchase of both a licence for the
degradation). There is also an associated reduction in
technology and any necessary machine modiÀcations.
the cavity pressure that is produced in the tool. This can
allow an increase in the number of cavities, and hence
The next system attempts to introduce the material into
improved manufacturing efÀciency.
the nozzle rather than the barrel, making the change to
foaming much simpler and cheaper. It is much newer
The MuCell TM process configuration includes a and therefore less established than the Trexel system,
speciÀcally conÀgured screw and feed system designed but also enables further understanding of the basic
to optimise the thermodynamic instability necessary to requirements for microcellular moulding.
achieve rapid foaming. Carbon dioxide is introduced
into the injection barrel to form a single-phase solution
with the polymer melt. 3.3.2 Ergocell
The following equipment is required to run In 2001, Demag Ergotech Àrst showed its new Ergocell
MuCellTM: process for moulding microcellular foamed products.
To overcome any possible patent conÁicts, they made
• metering system for the supercritical Áuid (SCF) to an agreement with Trexel that makes it necessary for
ensure the Áuid is at the appropriate pressure and Ergocell customers to purchase a MuCell licence,
volume. however these are offered at reduced cost. As part of
the agreement Demag also offer customers injection
• A Trexel designed screw and possibly new barrel. presses with a MuCell option.
Figure 9
MuCellTM system
20
Polymer Processing with Supercritiical Fluids
Unlike MuCell, which injects the gas part way along a opposite each other. The mixer external geometry is
specially modiÀed screw, the Ergocell process injects splined to the plunger. A schematic of the module is
gas downstream of the plastication screw into an already shown in Figure 10.
fully homogenised melt. This process works by splitting
the plasticising, gas mixing and injection stages into As the polymer is passed down the screw, gas delivery
separate functions. Plasticising proceeds as normal but takes place simultaneously with plasticising of the
a mixing chamber is added on at the end of the screw next shot. Gas is fed from the metering station into the
to inject the gas and blend the gas/polymer mixture. A melt as the screw draws feed material in, and is pushed
melt accumulator then holds the material under pressure back by the back pressure. This feeding of material
until it is injected. This is achieved using conventional pushes existing material into the mixer and injection
equipment: a standard injection cylinder and screw, and module. The melt here is intimately mixed with the
a non-return valve. This is because all the necessary CO2. The melt accumulator then holds the mixture
work is carried out in a bolt-on unit Àtted to the end of under pressure until the nozzle valve is opened and the
existing machinery. plunger injects the melt into the mould. scCO2 is the
recommended blowing agent with this process, due to
Ergocell technology equipment is made up of: its high sorption capacity in polymers. Whilst nitrogen
can be used, lesser weight savings are obtainable. The
• A module for gas metering and mixing (including microcellular structure produced has realised material
a mixer, injection module and non-return valve). savings of up to 40 percent. Also, as in other injection
moulding supercritical applications the gas reduces the
• An injection accumulator. viscosity of the material enabling reductions in injection
pressure and clamping forces.
• A gas station (a source of gas, carbon dioxide or
nitrogen is also required by the user). The main differences in the Ergocell and MuCell
systems are in the point of gas injection. Because of
• A gas metering and mixing module. the design of Ergocell, it can be retroÀtted to Ergotech
machines and also removed when necessary to use the
The function of the module is to ensure effective machine in its standard conÀguration. The hardware
homogenising of the melt/gas mixture independent to itself does not require a licence as the MuCell system
the plasticising stage. It consists of an injection plunger does. There is also the likelihood of less shear damage
which is attached to the existing plasticising screw. This to the material, due to the nature of the mixing system,
then leads to a mixer where the gas nozzles are arranged as the melt is not mixed in the screw but by a mixer.
injection
spine
piston screw
melt
polymer gas
(single phase)
gas injection
nozzle
Figure 10
Ergocell module
21
Polymer Processing with Supercritical Fluids
This also allows a wider processing window for many In order to produce a homogeneous distribution of gas in
material applications. As summarised in Table 6, the the melt a ring shape die design and a torpedo is used at
other advantages of this process are the same as for the centre of the melt Áow channel to enlarge the mixing
MuCell technology. area. This is manufactured using sintered metal which is
permeable to the gas. Static mixers downstream of the
Áuid entrance point ensure intimate polymer/gas mixing
3.3.3 Optifoam Process is achieved. The results reported so far by IKV Aachen,
Germany who initially developed the process, relate
to the importance of the relative injection moulding
A further bolt-on system has been commercialised by
parameters. Injection speeds, melt temperature and the
Sulzer Chemtech Ltd. In this system gas is introduced
concentration of the blowing agent are considered the
in a specially designed injection nozzle rather than
key machine settings with this system.
the barrel as in the MuCell system. This nozzle is
shown schematically in Figure 11 and is mounted
between the plasticising unit and the shut-off nozzle With an 8 mm wall thickness a density reduction of up to
of a conventional machine in a similar manner to the 66% was achieved using this system with polystyrene.
Ergocell system. (However, generally with all foaming methods, larger
weight reductions can be achieved with thicker cavities.
This correlation seems independent of the material
type.)
Table 6. Advantages of microcellular mouldings A further application for the Optifoam process achieved
over standard injection mouldings a 63% density reduction. This was on a thermoplastic
Process Reduction in part weight polyurethane shoe sole (a.2). Like the Ergocell design,
advantages Elimination of sink marks this can be retroÀtted to all injection moulding machines
Control of warpage but unlike any of the processes so far, is license free.
Lower internal stresses
Improved insulation (thermal and
acoustical) 3.3.4 Foamold
Dimensional stability
Specially suited for decorating The Foamold system by Rapra Technology Limited
techniques claims to be the world’s Àrst portable injection moulding
Cost advantages Material savings machine with scCO2 foaming capability(188). The gas
injection unit can be used either for foaming or as a
Reduction in clamping force
means of lowering the viscosity of the molten material
Reduction in cycle time to allow easier mould Àlling and improved product
Figure 11
Optifoam gas injection nozzle schematic
22
Polymer Processing with Supercritiical Fluids
quality. Unlike other systems, the Foamold system a lesser dependency on the supercritical Áuid level
uses both a cavity transfer mixer (CTM) and an internal employed in processing.
static mixer to disperse the gas in the melt. Previous
research carried out by Rapra on extrusion had shown
the necessity to maintain uniform processing conditions.
3.4 Microcellular Blow Moulding
This was achieved by separation of the screw pre-
plasticiser and the ram injection pot. The system, known
as Foamold includes a cavity transfer mixer (designed Microcellular blow moulding has also been proposed
and developed at Rapra) and a static internal mixer, to by Trexel Inc. (196). Like the injection moulding and
ensure near perfect dispersion of the gas in the melt. The extrusion processes already commercialised by Trexel,
small machine can deal in sample weights in the range the SCF is injected into the extruder. The process
0.02-12 g. Lower processing temperatures (meaning is preformed in the normal sequence and foaming
less thermal degradation), lower injection pressures and controlled by modiÀcations to the die and screw.
shorter cycling times means there is a great potential
for energy savings.
3.5 Blending
3.3.5 Applications and Properties of Microcellular Blends are extremely important materials, which can
Foams provide materials with properties not available from
using a single material. Blends are produced by mixing
Most materials can be produced with a microcellular or blending polymers together. Examples of common
structure, including amorphous, semi-crystalline and commercial blends are PVC-ABS or PC-ABS. These
thermoplastic elastomer (TPE) materials (64). Therefore materials are not to be confused with copolymers,
there are numerous applications reported for this which are polymeric materials composed of one or
technology of which some now follow: automotive more monomers in the same chain, e.g., high impact
fasteners and door latches, automotive interior trim, air polystyrene (HIPS) or ABS which is a terpolymer
distribution manifold, engine intake manifold gasket, (three different monomer groups), made up of a blend
automotive fuse box, rear air blower base connector, fan of acrylonitrile, butadiene and styrene. These types of
motor housing, printer components, electrical switches, materials would be produced by polymerisation routes
electrical box, electrical connector, cable ties, child gate as dealt with in Section 2.
panel, thin-wall container, bottle cap, and thermoplastic
vulcanisate weatherstrips (82). Successful polymer blending often depends on the very
different viscosities of the polymers. For example a low
For the same reasons as stated in Section 1.4.1, it is viscosity polymer with a small quantity of high viscosity
difÀcult to deÀnitively give the properties of microcellular polymer can improve a number of properties such as
materials as they are so dependent on the particular the impact strength or the tear strength. Blends can be
process and material combination. However, Table 7 is of two types: miscible (one phase) and have a single
a guide to the potential for the change of properties with glass transition temperature or immiscible (two phases)
microcellular processing when compared to standard with two glass transition temperatures.
techniques.
Most useful blends of two polymers are immiscible
The weld-line properties of injection moulded and hence form two phase systems (one phase rich
microcellular materials are affected by processing with one material and another phase rich in the other
conditions similar to conventional injection moulding material). The blend may be made up predominately
(129), that is increased strength with increasing melt of one of these materials, whilst the second component
temperature, injection speed and shot size. The weld- is dispersed within it. The level of dispersion plays an
line strength of microcellular materials also showed important part in determining the blend properties,
23
Polymer Processing with Supercritical Fluids
particularly the particle size of the dispersed material. The process details have yet to be published, subject
This is determined by the shearing action at blending but to patent applications. From reports that are available
also depends on the surface tension of the material. it appears they are using SCF as a plasticiser and are
using scCO2 and methane as solvents in a process
Additives can be used to improve the stability of the to ultimately deposit a ceramic on the surface of the
material interface, they are called compatibilisers. polymer via a sol-gel process. Whilst the creation of
They work by reducing the surface tension and hence a polymer-ceramic matrix is not new, incorporation of
the particle size between the dominant phase and the SCF into the process would suggest that a large process
dispersed phase. They also help to prevent the particles and hardness improvement should be achievable.
from coalescing.
A further application for supercritical Áuids has been Unlike mechanical recycling, which collects and uses
reported by Rosti Medical Plastics (25). They have waste plastics without any further chemical treatment,
announced a new product called Hard-Plas. This aims to chemical recycling uses the waste products to turn
replace traditional metal materials, primarily in medical them into their monomers (or other useful chemicals)
applications, by producing disposable polymer scalpels by means of chemical reactions. Common examples
to replace metal ones. This would remove the current of chemical recycling processes include cracking and
contamination problem. It is reported that a hardness hydrogenation. Thermal conversion technologies on
equivalent to quartz has been achieved. the other hand generate conversion products and heat.
24
Polymer Processing with Supercritiical Fluids
These are used for both a volume reduction in the waste can be considerably improved, also no additive or
and for energy recovery. There are three common types compatibilisers are required with SCW. This should lead
of categories of reactions, distinguished by their air to a process that is more efÀcient than the conventional
requirements: process for PET decomposition. Recently the effect of
supercritical ammonia on polycarbonates has also been
• Pyrolysis: thermal processing in the absence of studied (52).
oxygen. (Pyrolysis conditions have found few
commercial applications because of high viscosities Polyamide (161) has also been decomposed with
and low heat transfer rates.) SCW, as have flame retardant additive containing
epoxy materials (162). In this case the SCW enabled
• Hydrogenation: as pyrolysis but in a high hydrogen accelerated bromine abstraction for the plastic to be
or carbon monoxide environment. achieved.
25
Polymer Processing with Supercritical Fluids
Additional References
a.1 K.M. Scholsky, Process Polymers with
Supercritical Fluids, Chemtech, 1987.
26
References and Abstracts
Item 1 Item 3
GPEC 2004: Plastics - Helping Grow A Greener Polymer Science Series A
Environment. Proceedings of a conference held Detroit, 46, No.4, April 2004, p.377-80
Mi., 18th-19th Feb.2004. SYNTHESIS OF POLYIMIDES IN
BrookÀeld, Ct., SPE, 2004, Paper 27, pp.6, CD-ROM, SUPERCRITICAL CARBON DIOXIDE
012 Said-Galiyev E E; Vygodskii Y S; Nikitin L N; Vinokur
AROMATIC HYDROCARBON CONTENT OF R A; Khokhlov A R; Potoskaya I V; Kireev V V;
COMMON PLASTIC PACKAGING MATERIALS Schaumburg K
Ezrin M; Lavigne G Russian Academy of Sciences; Mendeleev University of
Connecticut,University Chemical Technology; Roskilde,University
(SPE,Environmental Div.)
High molecular-mass polyimides are synthesised in
Various plastics packaging materials containing readily supercritical carbon dioxide by the one-step polycyclisation
detected levels of aromatic hydrocarbons were subjected to of diamines and tetracarboxylic dianhydrides under batch
supercritical Áuid extraction with carbon dioxide to remove and Áow regimes. The effect of various reaction parameters
the hydrocarbons and then exposed to atmosphere to allow (including the content of water in the reaction system)
them to reabsorb hydrocarbons from the air either in a Áask on the structure, molecular mass and yield of polymers
or garage. The plastics packaging materials were analysed is studied. It is shown that the solubility of monomers
before extraction, after extraction and after exposure to in supercritical CO2 is indecisive for polymer growth.
hydrocarbons in the atmosphere by thermal desorption gas It is hypothesised that CO2 exhibits catalytic activity
chromatography/mass spectroscopy using heat to evolve when polyimides are prepared in the presence of water.
volatile compounds onto the chromatography column. 11 refs.
The materials were found to absorb hydrocarbons from DENMARK; EU; EUROPEAN COMMUNITY; EUROPEAN
the atmosphere. The most likely source of the absorbed UNION; RUSSIA; SCANDINAVIA; WESTERN EUROPE;
WESTERN EUROPE-GENERAL
hydrocarbons was identiÀed as gasoline vapours.
USA Accession no.922515
Accession no.923279
Item 4
Item 2 Journal of Cellular Plastics
GPEC 2004: Plastics - Helping Grow A Greener 40, No.5, Sept.2004, p.371-82
Environment. Proceedings of a conference held Detroit, CELL DEVELOPMENT IN MICROCELLULAR
Mi., 18th-19th Feb.2004. INJECTION MOLDED POLYAMIDE-6
BrookÀeld, Ct., SPE, 2004, Paper 49, pp.10, CD-ROM, NANOCOMPOSITE AND NEAT RESIN
012 Chandra A; Gong S; Turng L-S; Gramann P
DEVULCANIZATION OF RECYCLED TIRE Wisconsin-Madison,University; Madison Group
RUBBER USING SUPERCRITICAL CARBON The effects of processing parameters and nanofillers
DIOXIDE (nanoclay) on cell nucleation and cell growth during
Tzoganakis C; Zhang Q the injection moulding of microcellular polyamide-
Waterloo,University 6 nanocomposites were investigated using various
(SPE,Environmental Div.) techniques. A fractional four-factorial, three level, L9
An investigation was carried out into the devulcanisation Taguchi design of experiments was performed to minimise
of crumb rubber from recycled truck tyres in a twin- the number of trials and facilitate the analysis of the
screw extruder into which supercritical carbon dioxide results and morphology development of cell structure was
was injected to swell the crumb rubber. The effects of the analysed by scanning electron microscopy. Processing
supercritical carbon dioxide on extrusion and of processing parameters studied included melt temperature, injection
conditions (Áow rate, carbon dioxide concentration, screw speed, supercritical Áuid concentration and shot size.
speed and conÀguration and temperature) on the viscosity (ANTEC 2004, Chicago, Illinois, 16th-20th May) 8 refs.
USA
and degree of devulcanisation of the rubber were examined
and chemical changes occurring during devulcanisation Accession no.922671
assessed using FTIR spectroscopy. 14 refs.
CANADA
Accession no.923300
Item 5 Item 7
Macromolecules Journal of Applied Polymer Science
37, No.11, 1st June 2004, p.4241-6 93, No.2, 15th July 2004, p.545-9
CHARACTERIZATION OF POLYETHYLENES NEW PDMS MACROMONOMER STABILIZER
PRODUCED IN SUPERCRITICAL CARBON FOR DISPERSION POLYMERIZATION OF
DIOXIDE BY A LATE-TRANSITION-METAL STYRENE IN SUPERCRITICAL CARBON
CATALYST DIOXIDE
de Vries T J; Kemmere M F; Keurentjes J T F Ruolei Wang; Cheung H M
Eindhoven,University of Technology Akron,University
Polymerisation of ethylene in a supercritical carbon dioxide A polydimethylsiloxane(PDMS) macromonomer was used
(scCO2) medium, using a palladium based catalyst, was as a stabiliser for free radical dispersion polymerisation
studied over a range of temperatures, pressures and of PS in supercritical carbon dioxide. The reactions were
ethylene concentrations. Polymers were characterised conducted in a 225 mL stainless steel autoclave over the
using gel permeation chromatography, differential scanning temperature range 60 to 80C and under pressures of 1500
calorimetry, and nuclear magnetic resonance spectroscopy. to 3000 psi. The effects of the stabiliser concentration
High molecular weight amorphous polymers with narrow on conversion, molec.wt. and product morphology
molecular weight distribution and a high degree of were investigated. After 2 to 12 h of polymerisation, the
branching were obtained, similar to those obtained from conversion determined by the gravimetric method was
solution polymerisation in dichloromethane. Degree of between 20 and 80%. These preliminary results indicated
short chain branching was higher when sc CO2 was used, that the macromonomer provided satisfactory stabilisation
and evidence of a new branch-on-branch structure was for the styrene system. 14 refs.
observed. Molecular weight, but not short chain branching USA
were affected by polymerisation temperature and ethylene Accession no.920957
concentration. 22 refs.
EUROPEAN COMMUNITY; EUROPEAN UNION;
NETHERLANDS; WESTERN EUROPE Item 8
Accession no.921548 E-Polymers
No.2, 2004, p.1-7
SOLVATION OF POLY(METHYL ACRYLATE)
Item 6 AND POLY(VINYL ACETATE) BY CO2 STUDIED
ANTEC 2003. Proceedings of the 61st SPE Annual VIA ATOMISTIC MONTE CARLO SIMULATION
Conference held Nashville, Tn., 4th-8th May 2003. TECHNIQUES
BrookÀeld, Ct., SPE, 2003, Volume 1-Processing Beuermann S; Buback M; Drache M; Nelke D;
Session M13-Recycling, p.2811-5, CD-ROM, 012 Schmidt-Naake G
MELT PROCESSING OF THERMALLY Clausthal,Technical University; Gottingen,Georg-
UNSTABLE POLYMERS PLASTICIZED WITH August-Universitat
CO2
Bortner M J; Wilding M D; Baird D G The differences in solubility of PVAc and polymethyl
Virginia,Polytechnic Institute & State University acrylate(PMA) were studied by using atomistic Monte
(SPE) Carlo simulation techniques. Polymer segments consisting
of nine monomer units served as model compounds
An acrylonitrile copolymer was plasticised using for polymer chains. As a measure of intermolecular
supercritical carbon dioxide, so as to reduce the melt interactions with the solvent environment, cohesion
viscosity and allow melt spinning at temperatures below energies of the polymer segments embedded in either
those at which signiÀcant crosslinking occurred. The the corresponding monomer or in carbon dioxide were
copolymer (65 mol% acrylonitrile, 25 mol% methyl calculated. SpeciÀc interactions between polymer segments
acrylate and 10 mol% rubber), in pellet form, was exposed were identiÀed only in the case of PMA segments in carbon
to carbon dioxide at 11 MPa and 120 C for various dioxide environment. This result was in agreement with
time periods and characterised by differential scanning experimental results on phase behaviour and propagation
calorimetry and capillary rheometer measurements. A kinetics. 15 refs.
plasticising effect was observed, with a nonlinear pressure EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
dependence, indicating that further plasticisation would WESTERN EUROPE
occur at higher pressures. 14 refs. Accession no.920167
USA
Accession no.920541
Item 9 Item 11
E-Polymers ANTEC 2003. Proceedings of the 61st SPE Annual
No.3, 2004, p.1-14 Conference held Nashville, Tn., 4th-8th May 2003.
REVERSIBLE ADDITION FRAGMENTATION BrookÀeld, Ct., SPE, 2003, Volume 1-Processing
CHAIN TRANSFER(RAFT) POLYMERIZATION Session M16-Interface and Compatibilization, p.2271-5,
OF STYRENE IN FLUID CO2 CD-ROM, 012
Arita T; Beuermann S; Buback M; Vana P EFFECTS OF SUPERCRITICAL CO2
Gottingen,Georg-August-Universitat ON THE INTERFACIAL REACTION OF
MALEIC ANHYDRIDE FUNCTIONALIZED
RAFT polymerisations of styrene in liquid carbon
POLYETHYLENE AND POLYAMIDE-6
dioxide were carried out at 80C and 300 bar using cumyl
Xue A; Tzoganakis C
dithiobenzoate as the controlling agent in the concentration
Waterloo,University
range 0.0035 to 0.021 mol/L. The polymerisation rates
(SPE)
were retarded, depending on the concentration of added
RAFT agent, with no significant difference between Blends of maleic anhydride-functionalised polyethylene and
the RAFT polymerisation performed in liquid carbon polyamide-6 (PA-6) were prepared by reactive extrusion
dioxide and in toluene. Full chain length distributions using a co-rotating twin-screw extruder, with injections of 1-4
were analysed with respect to peak molec.wts., indicating wt% carbon dioxide. Nonreactive low density polyethylene
the successful control of radical polymerisation in liquid was added to some blends to reduced the maleic anhydride
carbon dioxide. A characterisation of the peak widths (MA) concentration. The degree of interfacial reaction was
indicated a minor inÁuence of liquid carbon dioxide on the determined by measuring the amount of unreacted MA by
addition reaction of macroradicals on the dithiobenzoate Fourier transform infrared spectroscopy. The MA conversion
group. 29 refs. increased with increasing carbon dioxide concentration. This
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; was attributed to interfacial reactions between the two melt
WESTERN EUROPE phases. It is proposed that dissolution of carbon dioxide into
Accession no.920168 the polymer melt increased the free volume, which enhanced
segmental chain mobility and promoted reorientation of
the chain conÀguration, so facilitating contact of reactive
Item 10 functional groups. The inÁuence of carbon dioxide on the
Macromolecules MA conversion was less pronounced with increasing PA-6
37, No.12, 15th June 2004, p.4580-9 content in the blend. At high PA-6 concentrations (70%), MA
GRAFTING OF MALEIC ANHYDRIDE ONTO conversions as high as 80% were achieved without the use
ISOTACTIC POLYPROPYLENE IN THE of carbon dioxide. This was attributed to the development
PRESENCE OF SUPERCRITICAL CARBON of a crosslinked interfacial region, or to the saturation of
DIOXIDE AS A SOLVENT AND SWELLING FLUID copolymers at the interface. 19 refs.
Galia A; De Gregorio R; Spadaro G; Scialdone O; CANADA
Filardo G
Accession no.919057
Palermo,University
Grafting of maleic anhydride(MA) onto isotactic PP(iPP) Item 12
was carried out by thermal decomposition of dicumyl Asian Plastics News
peroxide(DCP) using supercritical carbon dioxide (scCO2) July-Aug.2004, p.13-4
as a solvent and swelling Áuid. As long as the initial NEW TECHNOLOGIES FROM JAPAN
concentration of anhydride dissolved in scCO2 was higher
than 1% w/w, the grafting occurred without signiÀcant Japanese Àrms have been working on processes to improve
molec.wt. modiÀcation of the polymer and, with proper the surface Ànish of plastics parts and obviate the need
selection of the operative conditions, a grafting level for coating. Munekata employs supercritical CO2 in a
higher than 0.5% w/w with respect to the polymer mass process to improve the surface Ànish of moulded products.
was obtained. The amount of grafted MA was determined Supercritical CO2 is also being used in microcellular
by FTIR spectroscopy and polymer degradation was foam extrusion. For parts that have been coated, various
monitored by dynamic mechanical tests in the melt state. recycling technologies are available to enable the reuse
The effect of MA and DCP concentration, of scCO2 density of plastics. Idemitsu TechnoÀne has developed a system
and of the reaction time on the grafting yield and on the to recycle plated parts by employing a magnetic force to
melt Áow behaviour was studied. MA homopolymerisation remove metals from recycled plastics after it has been
during the grafting was indicated by the FTIR spectra. The finely powdered. Nanotechnology is another active
maleated iPP synthesised was an effective compatibilising research area in Japan. Unitika has applied nanotechnology
agent in the preparation of iPP/nylon-6 blends. 42 refs. to realise a biodegradable polylactic acid compound with
EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; mechanical properties superior to PS, PP and ABS.
WESTERN EUROPE JAPAN
Accession no.920303 Accession no.917826
Item 16
Item 14 Macromolecules
Polymer Materials Science and Engineering 37, No.10, 18th May 2004, p.3564-8
20, No.2, March 2004, p.155-7 EFFECTS OF PRESSURE AND TEMPERATURE
Chinese ON THE KINETICS OF L-LACTIDE
INVESTIGATION OF SORPTION AND POLYMERIZATION IN SUPERCRITICAL
DESORPTION OF SUPERCRITICAL CARBON CHLORODIFLUOROMETHANE
DIOXIDE INTO POLYSTYRENE Pack J W; Kim S H; Park S Y; Lee Y-W; Kim Y H
Chen Cun-she; Xu Hui; Li Xiao-juan Korea,Institute of Science & Technology;
Beijing,University of Technology & Business Seoul,National University
The interaction of supercritical carbon dioxide with PS The ring-opening polymerisation of L-lactide initiated
was investigated systematically. PS Àlms of 0.67 mm by stannous 2-ethylhexanoate in the presence or absence
thickness were treated with carbon dioxide at pressures of 1-dodecanol in supercritical chlorodiÁuoromethane
between 15 MPa and 30 MPa, at temperatures between 40 was studied at a range of pressures and temperatures, and
and 80C and for soaking times between 6 and 10 h. During the polymers characterised by GPC (molecular weight,
carbon dioxide sorption, the formerly transparent PS polydispersity). The effects of pressure and temperature
samples became opaque. The gravimetric desorption data on polymerisation kinetics are discussed. 37 refs.
were kinetically evaluated, assuming Fickian diffusion. KOREA
The sorbed amount of carbon dioxide ranged from 9.7% Accession no.917051
(80C, 15 MPa) to 13.5% (40C, 25 MPa). The desorption
diffusivities decreased with decreasing concentrations of
carbon dioxide inside the polymer. 7 refs. Item 17
CHINA Journal of Applied Polymer Science
92, No.4, 15th May 2004, p.2363-8
Accession no.918236
DEPOLYMERIZATION OF
POLY(TRIMETHYLENE TEREPHTHALATE) IN
Item 15 SUPERCRITICAL METHANOL
Journal of Materials Chemistry Hao-Hong Zhang; Hong-Wei Xiang; Yong Yang; Yuan-
14, No.11, 7th June 2004, p.1663-78 Yuan Xu; Yong-Wang Li
MATERIALS PROCESSING IN SUPERCRITICAL Chinese Academy of Sciences
CARBON DIOXIDE: SURFACTANTS, The depolymerisation of poly(trimethylene terephthalate)
POLYMERS AND BIOMATERIALS (PTT) was carried out in supercritical methanol in a batch
Woods H M; Silva M M C G; Nouvel C; Shakesheff K reactor at temperatures between 280 and 340C, at pressures
M; Howdle S M between 2.0 and 14.0 MPa and a reaction time of up to
Nottingham,University 60 min. The degradation products of PTT were dimethyl
Supercritical carbon dioxide (scCO2) is a unique solvent terephthalate (DMT) and 1,3-propane diol (PDO). The
with a wide range of interesting properties. Recent yields of DMT and PDO increased greatly with increasing
advances in the use of scCO2 in materials synthesis temperature and the monomer yields increased with
and materials processing are reviewed. In particular, the increasing pressure up to 10 MPa and then levelled off at
higher pressures. PTT seemed to completely depolymerise California; ANTEC 2003, Nashville, Tennessee, 4-8 May,
to monomers at 320C after 30 min or more. The Ànal 2003)
yields of DMT and PDO at 320C and 10.0 MPa with a USA
10:1 weight ratio of methanol to PTT reached 98.2%. A Accession no.916790
kinetic model for the simulation of the depolymerisation
reaction agreed well with the experimental data. In this
model, the scission of one PTT ester linkage by a methanol Item 20
molecule resulted in the formation of one carboxymethyl Polymer Science Series B
group and one hydroxyl group. 29 refs. 46, No.3-4, March-April 2004, p.61-5
CHINA
COPOLYMERIZATION OF PROPYLENE
OXIDE AND CARBON DIOXIDE UNDER
Accession no.917303 SUPERCRITICAL CONDITIONS
Rakhimov T V; Said-Galiev E E; Vinokur R A;
Item 18 Nikitin L N; Khokhlov A R; Il’in V V; Nysenko Z N;
Macromolecules Sakharov A M; Schaumberg K
37, No.7, 6th April 2004, p.2450-3 Moscow,Institute of Organoelement Compounds;
ENZYME-CATALYZED RING-OPENING Moscow,Institute of Organic Chemistry;
POLYMERIZATION OF EPSILON- Roskilde,University
CAPROLACTONE IN SUPERCRITICAL
The copolymerisation of propylene oxide with supercritical
CARBON DIOXIDE
carbon dioxide using zinc adipate as catalyst was
Loeker F C; Duxbury C J; Kumar R; Wei Gao;
investigated at different comonomer ratios. The product
Gross R A; Howdle S M
poly(propylene carbonate) was characterised by proton
Nottingham,University; Brooklyn,Polytechnic
NMR (copolymer structure) and GPC (molecular
University
weight), and the effects of carbon dioxide concentration
The ring-opening polymerisation of epsilon-caprolactone on copolymer yield and polydispersity are discussed. 21
was carried out in supercritical carbon dioxide using an refs.
enzyme catalyst (Novozym-435, which is lipase B from DENMARK; EU; EUROPEAN COMMUNITY; EUROPEAN
Candida antarctica supported on macroporous beads). UNION; RUSSIA; SCANDINAVIA; WESTERN EUROPE;
WESTERN EUROPE-GENERAL
The molecular weights of the poly(epsilon-caprolactone)
obtained were very similar to those obtained using toluene Accession no.915631
but in supercritical carbon dioxide, the polydispersity of
the polymer was lower and the yields were higher. The Item 21
enzyme catalyst could be cleaned and recycled using ANTEC 2003. Proceedings of the 61st SPE Annual
supercritical carbon dioxide while still producing a high Conference held Nashville, Tn., 4th-8th May 2003.
molecular weight polymer. Thus, it was not necessary to BrookÀeld, Ct., SPE, 2003, Volume 1-Processing
use organic solvents. 34 refs. Session T7-Polymerisation Catalysis and Application of
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA; New Polymers, p.1794-8, CD-ROM, 012
WESTERN EUROPE
KINETIC STUDY OF THE POLYMERIZATION
Accession no.917368 OF METHYL METHACRYLATE UNDER
SUPERCRITICAL FLUID CO2
Item 19 Lu S; Zhang Z; Nawaby A V; Day M
Journal of Cellular Plastics Canada,National Research Council
40, No.3, May 2004, p.229-41 (SPE)
SUPERCRITICAL CO2 PROCESSED High pressure differential scanning calorimetry was
POLYSTYRENE NANOCOMPOSITE FOAMS used to study the kinetics of the in-situ polymerisation of
Strauss W; D’Souza N A methyl methacrylate using supercritical carbon dioxide as
North Texas,University solvent and benzoyl peroxide as initiator. The steady state
The preparation of cellular PS nanocomposites containing polymerisation obeyed Àrst-order reaction kinetics, with
various amounts of montmorillonite-layered silicate using rates similar to those observed for polymerisation in air, but
carbon dioxide supercritical Áuid, as a solvent and blowing the molecular weight 34% was higher. The polymerisation
agent, is reported. The characterisation of compression kinetics increased and the induction time decreased with
moulded laminates based on the foams by scanning increasing initiator concentration. 14 refs.
electron microscopy, DSC and X-ray diffraction is also CANADA
reported. The effects of the silicate on foam nucleation, Accession no.915676
growth and microstructure are assessed and the thermal
properties of the nanocomposite foams before and after
processing tabulated. 24 refs. (SAMPE 2003, Long Beach,
Item 22 Item 24
ANTEC 2003. Proceedings of the 61st SPE Annual Polyurethanes Expo 2003. Proceedings of a conference
Conference held Nashville, Tn., 4th-8th May 2003. held Orlando, Florida, 1st-3rd Oct.2003.
BrookÀeld, Ct., SPE, 2003, Volume 1-Processing Arlington, VA, Alliance for the Polyurethanes Industry,
Session W7-Thermoplastic Foams Applications Part I, 2003, p.61-6, 28 cm, 012
p.1812-6, CD-ROM, 012 SUPERCRITICAL OR SUBCRITICAL CO2
EFFECT OF MONTMORILLONITE ON ASSISTED WATER BLOWN SPRAY FOAMS
FORMATION OF POLYSTYRENE FOAMS Ohnuma Y; Mori J
USING SUPERCRITICAL CO2 Achilles Corp.
Strauss W; Ranade A; D’Souza N A; Reidy R F; (American Plastics Council; Alliance for the
Paceley M Polyurethanes Industry)
North Texas,University
In Japan, spray foams occupy about 40 % of the rigid
(SPE)
PU (PUR) foam market. HCFC-141b used as a blowing
Styrene monomer, benzoyl peroxide initiator and agent in this segment is scheduled to be phased out by
various concentrations of montmorillonite clay were the end of 2003. Potential substitutes include HFC-245fa,
mixed and heated to initiate in-situ polymerisation. The HCF-365mfc and water. The Ministry of Economy,
nanocomposites were compression moulded into sheets Trade & Industry commenced research on recovery and
of 1.1 mm thickness, which were immersed in liquid processing technology of CFCs from thermal insulations
carbon dioxide at temperatures in the range 60-85 C at for building in 2001. The bank of CFCs in existing rigid
pressures of 7.6-12.0 MPa. After soaking for a set time, PUR foams has been estimated at 29,000 to 36,000
the pressure was reduced to atmospheric and the samples tonnes; there is greater interest in all water or hydrocarbon
cooled at a rate of 1 C/min to room temperature. Rapid blown foams. Japanese spray foams are mostly used in
carbon dioxide absorption rates were observed, compared the building envelope area where thermal conductivity is
with polystyrene, and foams were successfully prepared not the most critical requirement, so water is considered
at temperatures in the range 75-85 C, at pressures of 8-12 to be the preferred blowing agent. All water blown PUR
MPa. The key process parameters were temperature and foams suffer from poor dimensional stability and poor
depressurisation rate. The cell morphology was strongly adhesion to substrates besides high thermal conductivity.
dependent upon the clay concentration and dispersion, Rigid polyisocyanurate (PIR) spray foams using aromatic
and preferred orientation was observed round the foam polyester polyol are widely used in Japan. In this case, if
cells. 24 refs. water is used, B-component degradation occurs in a short
USA period. An attempt is made to solve these difÀculties using
Accession no.915679 supercritical or subcritical CO2. With some equipment
modification, proprietary water blown spray systems
are developed. Adding 1.5% of CO2, isotropic cells are
Item 23 obtained which lead to dimensionally stable foams at the
Journal of Applied Polymer Science density comparable to HCFC-141b blown foams. Not
92, No.3, 5th May 2004, p.2008-12 only is a conventional foam system developed, but also
EFFECT OF SUPERCRITICAL CARBON an aromatic polyester polyol-based Áame-retardant foam
DIOXIDE DYEING CONDITIONS ON THE system in which water is added as a separate stream.
CHEMICAL AND MORPHOLOGICAL CHANGES These foams can be processed as well as HCFC-141b
OF POLY(ETHYLENE TEREPHTHALATE) blown foams and good adhesion is shown even at low
FIBERS temperature. 4 refs.
Hou A; Xie K; Dai J JAPAN
Shanghai,Donghua University
Accession no.914048
The effects of supercritical carbon dioxide dyeing
conditions at various temperatures on the chemical and
Item 25
morphological properties of poly(ethylene terephthalate)
Materials World
Àbres were investigated using FTIR, x-ray diffraction,
12, No.7, July 2004, p.9-10
DSC and SEM. The results are discussed in terms of
ROSTI MEDICAL PLASTICS ANNOUNCES
changes in crystal size, melting temperature, crystallinity
CUTTING EDGE POLYMER ENGINEERING
and surface morphology. 14 refs.
Wilkes S
CHINA
Accession no.914028 Hard-Plas is a unique polymer hardening process
developed by Rosti that looks set to take on products
that are traditionally manufactured from metals in a wide
variety of Àelds. It is the medical area that will probably be
the Àrst to beneÀt from the process, as disposable polymer
scalpels hardened using the technique would overcome
problems of possible contamination faced by multiple- using GPC. Characterisation was also undertaken using
use stainless steel scalpels. The process itself is carried proton NMR and SEM. 20 refs.
out within a pressure vessel that can withstand pressures KOREA
exceeding 20 bar and temperatures above 120C. The Hard- Accession no.912715
Plas process can achieve a surface hardness of at least 7
Mohs or 178 Brinell, equivalent to quartz.
Item 28
Rosti Medical Plastics
EUROPEAN COMMUNITY; EUROPEAN UNION;
Colloid and Polymer Science
NETHERLANDS; WESTERN EUROPE 282, No.6, April 2004, p.569-74
Accession no.914369 PRODUCTION OF POLY(METHYL
METHACRYLATE) PARTICLES BY DISPERSION
POLYMERIZATION WITH MERCAPTOPROPYL
Item 26 TERMINATED POLY(DIMETHYLSILOXANE)
ANTEC 2003. Proceedings of the 61st SPE Annual STABILIZER IN SUPERCRITICAL CARBON
Conference held Nashville, Tn., 4th-8th May 2003. DIOXIDE
BrookÀeld, Ct., SPE, 2003, Volume 1-Processing Fujii S; Minami H; Okubo M
Session W5-Recent Advances in Polymer Structure, Kobe,University
Properties and Morphology, p.1610-4, CD-ROM, 012
PROCESSING OF INTRACTABLE POLYMERS PMMA particles were produced by dispersion
USING HIGH-PRESSURE CARBON DIOXIDE polymerisation of methyl methacrylate in the presence of
Garcia-Leiner M; Lesser A J mercaptopropyl-terminated polydimethylsiloxane(MP-
Massachusetts,University PDMS) in supercritical carbon dioxide with AIBN initiator
(SPE) at about 30 MPa for 24 h at 65C. The particle diameter
could be controlled in a size range of submicron to micron
To facilitate the processing of polymers with high by varying MP-PDMS concentration. The MP-PDMS was
melt viscosities such as Áuorinated ethylene-propylene shown to work not only as a chain transfer agent but also
copolymer, polytetrafluoroethylene and syndiotactic as a colloidal stabiliser. 26 refs.
polystyrene, the feed section of a single screw extruder JAPAN
was modiÀed so that the polymer could interact with
Accession no.912886
carbon dioxide (CO2) under conditions close to or in
the supercritical regime prior to extrusion. It was shown
that cell nucleation was controlled by the diffusion rate Item 29
of CO2 in the polymer melt, so that the provision of a International Polymer Processing
saturation time prior to extrusion facilitated foaming. Cell 19, No.1, March 2004, p.77-86
nucleation was also enhanced by operating with the die DEVELOPMENT OF A HYBRID SOLID-
temperature close to the polymer melting point. Increasing MICROCELLULAR CO-INJECTION MOLDING
the saturation pressure gave higher cell densities and PROCESS
lower average cell sizes. The enhanced processability was Turng L-S; Kharbas H
attributed to a plasticisation effect and to a hydrostatic Wisconsin-Madison,University
contribution. 23 refs. The development of a hybrid solid-microcellular co-
USA injection moulding process, which employs a modiÀed
Accession no.914651 two-colour injection moulding machine equipped with
an interfacial platen and a supercritical Áuid unit for
Item 27 co-injection moulding, is reported. The production of co-
Macromolecular Bioscience injection moulded PS parts having a microcellular core
4, No.3, 15th March 2004, p.340-5 encapsulated by a solid skin layer is demonstrated and
RING-OPENING POLYMERIZATION OF the effects of process conditions and core-skin volume
LACTIDE AND PREPARATION OF ITS ratios on penetration and morphology of the core are
MICROSPHERE IN SUPERCRITICAL FLUIDS examined. The cell structure and morphology of the
Pack J W; Kim S H; Park S Y; Lee Y-W; Kim Y H parts, as determined by scanning electron microscopy, are
Korea,Institute of Science & Technology; compared with microcellular injection moulded PS parts
Seoul,National University and the potential beneÀts of the process are discussed.
24 refs.
The ring-opening polymerisation of lactide initiated USA
by stannous octoate was carried out in supercritical
Accession no.911353
chlorodiÁuoromethane at various reaction conditions and
reactant concentrations. Polylactide microspheres were
prepared by using a continuous supercritical antisolvent
process. Molecular weights and MWDs were determined
Item 30 Item 32
ANTEC 2003. Proceedings of the 61st SPE Annual ANTEC 2003. Proceedings of the 61st SPE Annual
Conference held Nashville, Tn., 4th-8th May 2003. Conference held Nashville, Tn., 4th-8th May 2003.
BrookÀeld, Ct., SPE, 2003, Volume 1-Processing BrookÀeld, Ct., SPE, 2003, Volume 1-Processing
Session T34-Shear Rheology, p.986-90, CD-ROM, 012 Session W22-Microcellular Molding, p.691-5, CD-
RHEOLOGICAL CHANGES IN CO2 ROM, 012
IMPREGNATED POLYSTYRENE REINFORCED MICROCELLULAR NANOCOMPOSITE
WITH NANOCLAYS INJECTION MOLDING PROCESS
Wingert M J; Han X; Zeng C; Li H; Lee L J; Yuan M; Turng L-S; Spindler R; CaulÀeld D; Hunt C
Tomasko D L; Koelling K W Wisconsin-Madison,University; Kaysun Corp.;
Ohio,State University US,Dept.of Agriculture,Forest Products Laboratory
(SPE) (SPE)
The combined effects of montmorillonite and carbon Tensile and impact test bars of several polyamides
dioxide additions on the melt rheology of polystyrene (PS) and polyamide-clay nanocomposites were prepared by
was studied using an extrusion slit die rheometer. In the microcellular injection moulding using nitrogen as the
absence of carbon dioxide, the nanocomposite viscosity supercritical Áuid. The presence of the supercritical Áuid
increased with increasing clay content. However, the melt enhanced the clay exfoliation and dispersion during
viscosity of PS containing carbon dioxide decreased with moulding. Compared with the corresponding microcellular
increasing clay content. It was considered that this may polyamides, the microcellular nanocomposites exhibited
be due to the adsorption of carbon dioxide onto the clay superior mechanical properties, cell structures and cell
surface, so lubricating the Áow and creating a unique distributions. 4 refs.
particle layering structure. 21 refs. USA
USA Accession no.910803
Accession no.911397
Item 33
Item 31 ACS Polymeric Materials: Science and Engineering.
ANTEC 2003. Proceedings of the 61st SPE Annual Spring Meeting 2003. Volume 88. Proceedings of a
Conference held Nashville, Tn., 4th-8th May 2003. conference held New Orleans, La., 23rd-27th March
BrookÀeld, Ct., SPE, 2003, Volume 1-Processing 2003.
Session W22-Microcellular Molding, p.686-90, CD- Washington, D.C., ACS,Div.of Polymeric Materials
ROM, 012 Science & Engineering, 2003, p.92-3, CD-ROM, 012
MICROCELLULAR INJECTION MOLDING POLYMER-CLAY NANOCOMPOSITES
Turng L-S PREPARED IN SUPERCRITICAL CARBON
Wisconsin-Madison,University DIOXIDE
(SPE) Garcia-Leiner M; Lesser A J
Massachusetts,University
In the microcellular injection moulding process,
(ACS,Div.of Polymeric Materials Science & Engng.)
supercritical nitrogen or carbon dioxide is introduced
into the polymer melt in the machine barrel. The gas The preparation of nanocomposites based on either
and polymer phases separate during moulding to HDPE or polytrimethylene terephthalate and modiÀed
form microcells. The beneÀts include lower operating or unmodified montmorillonite nanoparticles in the
temperatures and pressures, the ability to mould thin walls, presence of supercritical carbon dioxide is described. The
reduced cycle times and improved dimensional stability. effects of the clay nanoparticles on the morphology and
Samples of a variety of polymers and Àller systems were crystallisation of the polymers and on the foaming process
prepared by microcellular injection moulding using are discussed and the inÁuence of supercritical carbon
nitrogen gas and a range of processing parameters. The dioxide on melt intercalation is assessed. 10 refs.
samples were characterised by microstructural studies USA
and by measurements of mechanical properties. The cell Accession no.909399
size decreased with increasing supercritical gas content,
injection speed and melt plastication pressure. The cell size
was signiÀcantly reduced by the presence of exfoliated Item 34
nanoclay. The microcellular structure generally resulted Polymer Preprints. Volume 44. Number 1. March
in reductions in tensile, impact and weld line strength. 2003. Papers presented at the ACS meeting held New
10 refs. Orleans,Lo., 23rd-27th March 2003.
USA
Washington, DC, ACS, Div.of Polymer Chemistry,
2003, p.1216-7, 28CM, 012
Accession no.910802 DEGRADATION OF PET UNDER
SUPERCRITICAL METHANOL
initiator, monomer and at different reaction mixture polymerisation conditions was determined by comparing
densities. The Hildebrand parameter of the Áuid phase the activation energies for chemical reaction and phenol
suggests that vinyl pyrrolidone acts as a cosolvent for the diffusion. 9 refs.
polysiloxane chains. Analysis of the kinetics suggested USA
that, for this system, a nucleation mechanism different to Accession no.901299
that proposed for pure dispersion polymerisation processes
was involved. 33 refs.
EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;
Item 52
WESTERN EUROPE Polymer Preprints. Volume 44. Number 1. March 2003.
Accession no.904133 Papers presented at the ACS meeting held New Orleans,
La., 23rd-27th March 2003.
Washington, D.C., ACS,Division of Polymer Chemistry,
Item 50 2003, p.738-9, 28cm, 012
Journal of Materials Chemistry CHEMICAL RECYCLING OF
13, No.11, Nov.2003, p.2838-44 POLYCARBONATES WITH (SUPERCRITICAL)
THE PREPARATION OF NOVEL NANO- AMMONIA
STRUCTURED POLYMER BLENDS OF ULTRA Mormann W; Spitzer D
HIGH MOLECULAR WEIGHT POLYETHYLENE Siegen,Universitat
WITH POLYMETHACRYLATES USING (ACS,Div.of Polymer Chemistry)
SUPERCRITICAL CARBON DIOXIDE
Busby A J; Zhang J; Naylor A; Roberts C J; The behaviour of aliphatic and aromatic polycarbonates
Davies M C; Tendler S J B; Howdle S M towards liquid and supercritical ammonia was investigated.
Nottingham,University The use of ammonolysis for the chemical recycling of
bisphenol-A polycarbonate-containing composites such as
Several methacrylates were polymerised in an ultrahigh compact disks or car windows is discussed. 5 refs.
molec.wt. PE matrix using supercritical carbon dioxide EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
and the inÁuence of side chain length on the loading WESTERN EUROPE
of the methacrylate phase and the morphology of the Accession no.901296
resulting polymer blends investigated. It was found that the
methacrylates were located in nanoscalar phase separated
domains within the PE and that these blends could not Item 53
be fabricated in the absence of the supercritical carbon Macromolecules
dioxide. 35 refs. 36, No.19, 23rd Sept.2003, p.6967-9
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
SUPERCRITICAL CARBON DIOXIDE-
EUROPE MEDIATED INTERCALATION OF PEO IN CLAY
Accession no.901742 Qian Zhao; Samulski E T
North Carolina,University
Kobe,University Item 57
Macromolecules
Polyacrylonitrile particles were produced by precipitation
36, No.16, 12th Aug.2003, p.5908-11
polymerisation of acrylonitrile in supercritical carbon
SUSPENSION POLYMERIZATION OF L-
dioxide. The effects of initiation rate of the polymerisation
LACTIDE IN SUPERCRITICAL CARBON
and acrylonitrile concentration on the conversion, the
DIOXIDE IN THE PRESENCE OF A TRIBLOCK
Áuidity of powder, the degree of coagulation, the viscosity-
COPOLYMER STABILIZER
average molecular weight and the crystallinity were
Bratton D; Brown M; Howdle S M
examined in detail. 41 refs.
Nottingham,University; Smith & Nephew
JAPAN
Accession no.900163 Details are given of the preparation of a well-deÀned
Áuorinated triblock copolymer surfactant for suspension
polymerisation of polylactide in supercritical carbon
Item 55 dioxide. Data concerning the ether-caprolactone copolymer
Journal of Applied Polymer Science and their interaction with polylactide particles in suspension
90, No.8, 21st Nov.2003, p.2040-4 polymerisation are discussed. Molecular structures and
SUPERCRITICAL CO2-ASSISTED SYNTHESIS morphological properties were determined. 27 refs.
OF POLY(ACRYLIC ACID)/NYLON1212 BLEND EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
Chang Y; Xu Q; Liu M; Wang Y; Zhao Q EUROPE
Zhengzhou,University Accession no.898508
Blends of polyacrylic acid and polyamide-12,12 were
prepared by the infusion of acrylic acid into and radical Item 58
polymerisation within the polyamide-12,12 using Journal of Applied Polymer Science
supercritical carbon dioxide as a substrate-swelling agent 90, No.4, 24th Oct.2003, p.1113-6
and monomer/initiator carrier and characterised by DSC, PREPARATION OF CONDUCTING
FTIR spectroscopy and scanning electron microscopy. The COMPOSITES OF POLYPYRROLE USING
sorption of carbon dioxide into the polyamide-12,12 and SUPERCRITICAL CARBON DIOXIDE
effects of impregnation conditions on the preparation of Abbett K F; Teja A S; Kowalik J; Tolbert L
the blends investigated. 24 refs. Georgia,Institute of Technology
CHINA
Pyrrole was polymerised in several host polymers (PCTFE,
Accession no.899792
crosslinked PDMS, PMMA and porous crosslinked PS)
using supercritical carbon dioxide as the transport medium
Item 56 and reaction medium for in-situ polymerisation and the
Modern Plastics International morphology and electrical conductivity of the resulting
33, No.11, Nov.2003, p.18 composites determined. It was found that conductive
NEW WAY TO RECYCLE AUTO PLASTICS composites were formed using PMMA and porous
A group of seven industrial Àrms led by the Fraunhofer crosslinked PS as host polymers, the level of pyrrole
Institute for Chemical Technology has developed an polymerised on the surface or in the pores of the host
economical and safer way to recycle PE fuel tanks from polymer being sufÀcient to produce the interconnected
end-of-life vehicles. Over the course of their working conducting polymer networks. 17 refs.
lives, the tanks absorb up to 5% of their weight in gasoline USA
or diesel. The research group is studying the use of Accession no.898131
supercritical carbon dioxide to separate fuel from plastic,
it is brieÁy reported. The shredded fuel tanks are placed Item 59
in pressurised vessels and diffused with CO2 gas. At a Macromolecules
speciÀc pressure and temperature, the gas acts as a highly 36, No.13, 1st July 2003, p.4779-85
efÀcient solvent, extracting the fuel that has inÀltrated DISPERSION POLYMERIZATION OF MMA
the plastic. IN SUPERCOOLED CARBON DIOXIDE
FRAUNHOFER-INSTITUT FUER CHEMISCHE TECHNOLOGIE IN THE PRESENCE OF COPOLYMERS
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; OF PERFLUOROOCTYLETHYLENE
WESTERN EUROPE
METHACRYLATE AND POLY(PROPYLENE
Accession no.898687 GLYCOL) METHACRYLATE
Lunhan Ding; Olesik S V
Ohio,State University
Radical copolymerisation was used to prepare a
series of random copolymer dispersants based on
perfluorooctylethylene methacrylate and propylene
proÀtable subjects for future research. 126 refs. Tests were carried out to determine the Áexural and tensile
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN properties of the composites and an analysis was made of
EUROPE the evolution of damage and energy dissipation using a
Accession no.895234 combination of cyclic loading and optical microscopy of
post-stressed composite cross-sections. The relationship
between the structure and properties of the composites was
Item 64
also analysed to provide a better understanding of the overall
Blowing Agents and Foaming Processes 2003.
performance of the composites. 16 refs.
Proceedings of a conference held Munich, Germany,
USA
19th-20th May 2003.
Shawbury, Rapra Technology Ltd., 2003, Paper 11, Accession no.894131
p.101-25, 29 cm, 012
NEW DEVELOPMENTS IN MUCELL MARKETS Item 66
Traut H Macromolecules
Trexel 36, No.9, 6th May 2003, p.3380-5
(Rapra Technology Ltd.) QUANTIFYING PLASTICIZATION AND
The latest developments and commercial applications MELTING BEHAVIOR OF POLY(VINYLIDENE
of the MuCell microcellular foam injection moulding FLUORIDE) IN SUPERCRITICAL CARBON
process are presented. In particular, advancements in the DIOXIDE UTILIZING A LINEAR VARIABLE
MuCell screw design combined with the simple ability to DIFFERENTIAL TRANSFORMER
upgrade a standard electric or hydraulic injection moulding Shenoy S L; Fujiwara T; Wynne K J
machine into a fully capable MuCell moulding machine Virginia,Commonwealth University
are described. The MuCell process has been adopted as a The plasticisation and melting behaviour of PVDF in
core plastics manufacturing technology to achieve higher supercritical carbon dioxide were studied by measuring
productivity weight reduction, quality improvement and linear dilation as a function of temperature (75-130C) and
cost savings. The microcellular foam injection moulding pressure (138-670 bar) using a linear variable differential
process results in plastic components that are lighter, transformer. In constant temperature experiments at 75
Áatter, straighter and more dimensionally stable at extreme and 99C, the carbon dioxide density or solvent quality
operating temperatures compared to conventionally determined the degree of swelling. At lower pressures,
moulded parts. The MuCell process can be applied to a the rate of change of dilation with pressure increased
wide variety of Àlled and unÀlled materials, including many rapidly up to 414 bar and then attenuated. At 117 and
high temperature engineering resins and thermoplastic 130C, the rate of change of dilation with pressure was
elastomers (TPEs). Today there are MuCell products in almost linear. Reasons for the higher swelling of PVDF
various markets, including automotive, business equipment, above 100C were discussed. PVDF swelling was measured
electric/electronic, consumer and medical industries. The as a function of temperature at constant pressure. With
MuCell process uses supercritical Áuids (SCF) of inert gases, increasing pressure, the melting temperature decreased to
typically nitrogen or carbon dioxide, to evenly distributed a minimum of 135C at 483 bar. Above 483 bar, hydrostatic
and uniformly sized microscopic cells throughout a polymer. effects predominated over plasticisation and the melting
In injection moulding the microcellular foam process temperature increased. 54 refs.
enhances product design, improves processing efÀciency USA
and reduces costs.
Accession no.893374
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
WESTERN EUROPE
Accession no.895001 Item 67
Polymer
44, No.14, June 2003, p.3803-9
Item 65 HOMO AND COPOLYMERISATION OF 2-
Polymer Composites (DIMETHYLAMINO)ETHYL METHACRYLATE
24, No.4, Aug.2003, p.545-54 IN SUPERCRITICAL CARBON DIOXIDE
EVALUATING THE MECHANICAL Wenxin Wang; Giles M R; Bratton D; Irvine D J; Armes
PERFORMANCE OF SUPERCRITICAL CO2 S P; Weaver J V W; Howdle S M
FABRICATED POLYAMIDE 6,6/PMMA, FIBER Nottingham,University; Uniqema; Sussex,University
REINFORCED COMPOSITES
Caskey T C; Lesser A J; McCarthy T J The free-radical dispersion homopolymerisation of
Massachusetts,University 2-(dimethylamino)ethyl methacrylate(DMA) and
copolymerisation of DMA with methyl methacrylate(MMA)
The mechanical properties of a polyamide-6,6 Àbre/PMMA in supercritical carbon dioxide were studied. The
composite made by a novel supercritical carbon dioxide polymerisations were performed in the presence of two
assisted process under compressive force were investigated. commercially-available stabilisers, poly(dimethylsiloxane)
Item 72
Item 70
Journal of Polymer Engineering
Journal of Applied Polymer Science
23, No.1, Jan.-Feb.2003, p.1-22
89, No.3, 18th July 2003, p.742-52
RHEOLOGICAL PROPERTIES OF
FORMATION OF MICROCAPSULES OF
POLYSTYRENE/SUPERCRITICAL CO2
MEDICINES BY THE RAPID EXPANSION
SOLUTIONS FROM AN EXTRUSION SLIT DIE
OF A SUPERCRITICAL SOLUTION WITH A
Xue A; Tzoganakis C
NONSOLVENT
Waterloo,University
properties. Processing behaviour as a function of The preparation and SEM characterisation of microcellular
temperature and pressure has been studied by various foams from high-Tg fluorinated aromatic PEEK are
methods. However, there are few studies on the post- described. These foams, produced using supercritical
plasticised morphologies. The conformation change of carbon dioxide, as blowing agent, are closed-cell foams
syndiotactic PS after SCCO2 plasticisation by using X- with low dielectric constants and better thermal insulation
ray technique has been reported. Recently, a programme properties than their matrix. A SEM micrograph of the
to study plasticisation of semicrystalline polymers as a microcellular polymer is illustrated. 4 refs.
function of pressure and temperature approaching melting CHINA
point (Tm) has been initiated. Unique post-plasticised Accession no.886331
thermal behaviour is described and the morphologies
of PVDF and PVDF copolymer, vinylidene Áuoride-
co-5 mol.% hexafluoropropylene (PVDF-HFP), are Item 84
investigated. 9 refs. Polymer
USA
44, No.8, 2003, p2201-11
CARBOXYLIC ACID END GROUP
Accession no.887894 MODIFICATION OF POLY(BUTYLENE
TEREPHTHALATE) IN SUPERCRITICAL
Item 82 FLUIDS
Plastics and Rubber Weekly de Gooijer J M; Scheltus M; Jansen M A G; Koning C E
2nd May 2003, p.9 Eindhoven,University of Technology; DSM Research
JYCO SEALING USES MUCELL PROCESS FOR
ModiÀcation of polybutylene terephthalate carboxylic end
AUTOMOTIVE FOAM SEALS
groups by 1,2-epoxybutane was carried out at different
Proving that the MuCell microcellular foaming technology temperatures and pressures in supercritical carbon dioxide,
is not just for injection moulders, US-based Jyco Sealing and mixtures of this with an added 10 mol percent of
Technologies is using the process to manufacture dioxane. Highest modiÀcation was achieved in the mixed
foamed thermoplastic vulcanisate (TPV) weatherstrips solvent at the highest experimental temperature, resulting
for the automotive sector. According to chief executive in much improved hydrolytic stability of the polymer as
ofÀcer Sam Jyawook, the foaming process is critical in observed by molecular weight measurements and intrinsic
the production of weather seals because an open-cell viscosity change with respect to hydrolysis time. An
structure will not meet the demanding automotive industry increase in crystallinity was observed, using differential
standards. The MuCell technique, which uses supercritical scanning calorimetry, due to the plasticising effect of the
Áuids to create the foam structure, has proved to give mixed solvents. 27 refs.
good control of cell structure, reducing surface porosity EUROPEAN COMMUNITY; EUROPEAN UNION;
and preventing moisture uptake. MuCell developer Trexel NETHERLANDS; WESTERN EUROPE
now has a commercial TPV foaming process. TPVs are Accession no.885760
predicted to continue replacing EPDM in weather-seal
applications, where they are claimed to provide easier
Item 85
recyclability, colourability and improved design Áexibility.
Journal of Applied Polymer Science
The company claims its process is consistent in high-
88, No.9, 31st May 2003, p2189-93
output manufacturing processes with a range of material
PLASTICISATION OF POLYMERS WITH
formulations.
SUPERCRITICAL CARBON DIOXIDE:
JYCO SEALING TECHNOLOGIES; TREXELL INC. EXPERIMENTAL DETERMINATION OF GLASS
USA TRANSITION TEMPERATURES
Alessi P; Cortesi A; Kikic I; Vecchione F
Accession no.887869
Trieste,University
A method for the study of the plasticisation effect of
Item 83
supercritical carbon dioxide on polymers, including
Polymer Preprints. Volume 43. Number 2. Fall 2002.
polymethyl methacrylate, polystyrene and polycarbonate,
Papers presented at the ACS Meeting held Boston, Ma.,
and its effect on glass transition temperature was shown to
18th-22nd Aug.2002.
be high-pressure partition chromatography, a modiÀcation
Washington, DC, ACS,Div.of Polymer Chemistry, 2002,
to inverse gas chromatography. Experimental results were
p.1338, 28cm, 012
compared with published Àgures for each polymer, and
MICROCELLULAR FOAMING OF AMORPHOUS
shown to be in good agreement. 14 refs.
HIGH-TG POLYMER USING CARBON DIOXIDE
EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;
Wang D; Jin Y; Jiang Z; Wu Z WESTERN EUROPE
Jilin,University
(ACS,Div.of Polymer Chemistry) Accession no.885711
Item 86 Item 89
European Polymer Journal Polymer Preprints. Volume 43. Number 2. Fall 2002.
39, No.3, March 2003, p.423-8 Papers presented at the ACS Meeting held Boston, Ma.,
MONITORING DISPERSION 18th-22nd Aug.2002.
POLYMERISATIONS OF METHYL Washington, D.C., ACS,Div.of Polymer Chemistry,
METHACRYLATE IN SUPERCRITICAL 2002, p.889, 28cm, 012
CARBON DIOXIDE POLYMERIZATION OF VINYLIDENE
Wang W; GrifÀths R M T; Giles M R; Williams P; FLUORIDE IN DENSE CARBON DIOXIDE
Howdle S M Wojcinski L M; Saraf M K; Charpentier P;
Nottingham,University; UK,Health and Safety DeSimone J M; Roberts G W
Laboratory North Carolina,State University; North Carolina,Chapel
Hill University
Details are given of the development of power compensation
(ACS,Div.of Polymer Chemistry)
calorimetry equipment to monitor the dispersion
polymerisation of methyl methacrylate in supercritical Vinylidene Áuoride was polymerised via free radical
carbon dioxide. The effect of initiator concentration and precipitation polymerisation in supercritical carbon
stabiliser on the reaction was studied and the enthalpy of dioxide in a continuous stirred tank reactor. The initiator
polymerisation obtained from the apparatus was found to was diethyl peroxydicarbonate. The resulting PVDF was
correlate with other reported data. 21 refs. highly porous with a novel bimodal molecular weight
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN distribution which varied with reaction conditions such
EUROPE as monomer concentration, temperature and pressure.
Accession no.884200 No refs.
USA
Item 91 Item 93
Polymer Preprints. Volume 43. Number 2. Fall 2002. Polymer Preprints, Volume 43. Number 2. Fall 2002.
Papers presented at the ACS Meeting held Boston, Ma., Papers presented at the ACS Meeting held Boston, Ma.,
18th-22nd Aug.2002. 18th-22nd Aug. 2002.
Washington, D.C., ACS,Div.of Polymer Chemistry, Washington, DC, ACS,Div. of Polymer Chemistry,
2002, p.887, 28cm, 012 2002, p.938-9, 28 cm, 012
PLASTICIZATION AND MELTING BEHAVIOR ELECTROCHEMICAL SYNTHESIS AND
OF PVDF AND PVDF COPOLYMERS IN CHARACTERIZATION OF CONDUCTING
SUPERCRITICAL CARBON DIOXIDE POLYPYRROLE FILMS IN SUPERCRITICAL
Shenoy S L; Fujiwara T; Wynne K J CARBON DIOXIDE
Virginia,Commonwealth University Badlani R N; Mayer J L; Anderson P E; Mabrouk P A
(ACS,Div.of Polymer Chemistry) Northeastern University
(ACS,Div.of Polymer Chemistry)
PVDF and poly(vinylidene fluoride-co-4.9 mol%
hexaÁuoropropylene) were plasticised by supercritical Pyrrole polymers were synthesised by the electrochemical
carbon dioxide. The degree of plasticisation depended polymerisation of pyrrole in supercritical carbon dioxide on
strongly on the temperature and the pressure. The gold disks and indium tin oxide/glass working electrodes.
hexaÁuoropropylene groups resulted in a much larger They were characterised by cyclic voltammetry, four-point
swelling of the copolymer. The melting temperatures of probe conductivity, scanning electron microscopy and
both the homopolymer and the copolymer were lowered UV vis spectroscopy and found to exhibit relatively high
by polymer-supercritical carbon dioxide interactions. conductivity and distinct surface morphology. 21 refs.
However, above about 540 bar, there was a modest increase USA
in the melting temperature due to the hydrostatic pressure. Accession no.883668
Thus, the melting behaviour was a balance between the
lowering of the melting temperature due to plasticisation
and increasing it due to the hydrostatic pressure. 12 refs. Item 94
USA
ANTEC 2002. Proceedings of the 60th SPE Annual
Technical Conference held San Francisco, Ca., 5th-9th
Accession no.883971 May 2002.
BrookÀeld, Ct., SPE, 2002, Paper 611, Session
Item 92 W17-Applied Rheology. Wall Slip, Instabilities and
Journal of Applied Polymer Science Processing Aids, pp.5, CD-ROM, 012
88, No.2, 11th April 2003, p.522-30 RHEOLOGY AND EXTRUSION OF CO2
SURFACE MODIFICATION OF PLASTICIZED ACRYLIC COPOLYMERS
POLYBUTADIENE FACILITATED BY Bortner M J; Baird D G
SUPERCRITICAL CARBON DIOXIDE Virginia,Polytechnic Institute & State University
Ngo T T; McCarney J; Brown J S; Lazzaroni M J; (SPE)
Counts K; Liotta C L; Eckert C A
The reduction of the glass transition temperature (Tg)
Georgia,Institute of Technology
and hence the melt viscosity of poly(acrylonitrile-co-
The hydrophilicity of polybutadiene was increased by methyl acrylate) (10 mol% methyl acrylate) by the
treating the polymer surface with hydrophilic monomers addition of carbon dioxide, to facilitate melt spinning,
(such as 3-vinylbenzoic acid and crotonic acid) in the was investigated. Copolymer pellets were saturated with
presence of a photoinitiator in a supercritical carbon carbon dioxide in a sealed pressure vessel for various
dioxide environment. The carbon dioxide acted as the time periods. Following depressurisation, dynamic and
swelling agent for the polymer and the transport medium steady shear measurements were made using a torsional
for solutes to diffuse on to the polymer surface. The rheometer, and a modiÀed capillary rheometer, pressurised
carbon dioxide pressure had a substantial effect on the using nitrogen, was used to study both saturated and
partitioning of the solute between the polymer and the unsaturated copolymer. Tg was determined by differential
Áuid phase and a smaller effect on the diffusivity of the scanning calorimetry. A reduction of approximately 40%
solute onto the polymer surface. Based on these results, in melt viscosity was obtained on saturating the copolymer
the operating conditions of the process could be optimised with carbon dioxide, leading to a reduction in processing
to obtain the required surface properties. The dimerisation temperature of up to 20 C. 7 refs.
kinetics of carboxylic acids in carbon dioxide solution USA
were examined. This dimerisation behaviour signiÀcantly Accession no.883569
affected the solubility and diffusivity of the acids in
solution. 15 refs.
USA
Accession no.883780
Item 95 Item 97
Journal of Polymer Science: Polymer Physics Edition Polymer Engineering and Science
41, No.4, 15th Feb.2003, p.368-77 43, No.1, Jan.2003, p.157-68
PREPARATION AND CHARACTERIZATION EFFECT OF PROCESS CONDITIONS
OF MICROCELLULAR POLYSTYRENE/ ON THE WELD-LINE STRENGTH AND
POLYSTYRENE IONOMER BLENDS WITH MICROSTRUCTURE OF MICROCELLULAR
SUPERCRITICAL CARBON DIOXIDE INJECTION MOLDED PARTS
Jin Wang; Xingguo Cheng; Xuejing Zheng; Lih-Sheng Turng; Kharbas H
Mingjun Yuan; Jiasong He Wisconsin-Madison,University
Beijing,Institute of Chemistry
The way in which the process conditions affected the weld-
Preparation of microcellular PS, lightly sulphonated line strength and microstructure of injection-moulded
PS(SPS), zinc-neutralised lightly sulphonated PS(ZnSPS) microcellular parts was investigated. Experimental design
and blends of PS/SPS and PS/ZnSPS via supercritical was used and polycarbonate tensile test specimens were
carbon dioxide was carried out using the pressure-quench produced for tensile tests and microscopic analysis.
process. Both higher foaming temperature and lower Injection moulding trials were performed by systematically
pressure resulted in larger cell sizes, lower cell densities adjusting four process parameters, i.e. melt temp., shot size,
and lower relative density for microcellular ionomers and supercritical Áuid level and injection speed. Conventional
blends than for microcellular PS. The difference between solid specimens were also produced for comparison. The
the various microcellular samples was the change of cell TS was measured at the weld line and away from the
size with the sample composition. The cell size decreased weld line. The weld-line strength of injection moulded
in the sequence from SPS, through PS/SPS blends, PS and microcellular parts was lower than that of its solid
PS/ZnSPS blends, to ZnSPS. The diffusivity of carbon counterparts. It increased with increasing shot size, melt
dioxide in samples also decreased in the sequence from temp. and injection speed and was weakly dependent
SPS, through PS/SPS blends, PS and PS/ZnSPS blends, on the supercritical Áuid level. The microstructures of
to ZnSPS. For this series of samples with similar structure the moulded specimens at various cross-sections were
and identical solubility of carbon dioxide, the varying examined using SEM and optical microscopy in order to
diffusivity was responsible for the difference of cell sizes. study the variation of cell size and density with different
36 refs. process conditions. 21 refs.
CHINA USA
Accession no.882238 Accession no.881046
Item 96 Item 98
Industrial and Engineering Chemistry Research Journal of Applied Polymer Science
42, No.3, 5th Feb.2003, p.448-55 87, No.7, 14th Feb.2003, p.116-22
DISPERSION COPOLYMERIZATION OF VINYL REACTIVE EXTRUSION OF POLYPROPYLENE
MONOMERS IN SUPERCRITICAL CARBON WITH SUPERCRITICAL CARBON DIOXIDE:
DIOXIDE FREE RADICAL GRAFTING OF MALEIC
Galia A; Muratore A; Filardo G ANHYDRIDE
Palermo,University Dorscht B M; Tzoganakis C
Waterloo,University
An investigation was carried out into the free-radical
copolymerisation of methyl methacrylate and N,N- Supercritical carbon dioxide was used in a reactive extrusion
dimethylacrylamide initiated by the thermal decomposition process for the peroxide-initiated functionalisation of PP
of AIBN in supercritical carbon dioxide in the presence with maleic anhydride. The use of supercritical carbon
of polysiloxane surfactants. The phase behaviour of the dioxide led to improved free radical grafting of maleic
reaction mixture was examined by combining visual anhydride on to PP when high levels of maleic anhydride
observation of the mixture to the recording of the pressure were used. There was no evidence of improvement
trend inside a Àxed-volume view cell during slow heating in the homogeneity of the product and melt Áow rate
and cooling of the reaction mixture. The effects of the measurements showed a reduction in the degradation of
nature of the surfactant, feed composition and surfactant PP during the grafting reaction when low levels of maleic
concentration on dispersion copolymerisation were studied anhydride were used. 26 refs.
and the end-use properties of the copolymers evaluated. CANADA
24 refs. Accession no.880727
EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;
WESTERN EUROPE
Accession no.881794
Tang M; Wen T-Y; Du T-B; Chen Y-P The degradation kinetics of polycarbonate (poly(bisphenol
Chinese Culture University; Taipei,National Taiwan A carbonate)) in supercritical and subcritical benzene is
University studied at various temperatures (523-618 K) at 50 atm.
The degradation is also investigated in other solvents at
A polymer composite was produced by impregnating a
573 K and 50 atm. The time evolution of molecular weight
pyrrole monomer within a PS substrate in supercritical
distribution is obtained by gel permeation chromatography
carbon dioxide followed by soaking the resulting composite
and modelled with continuous distribution kinetics to
in a solution of a metal salt to form an electrically conductive
obtain the degradation rate coefÀcients. The activation
composite. The effects of doping solvent (acetonitrile or
energy, determined from the temperature dependence of
water), doping temperature and nature of the oxidants
the rate coefÀcient, increases from 16.7 to 20.4 kcal/mol
(iron chloride, iron sulphate, iron perchlorate or iron
from the subcritical region to the supercritical region of the
nitrate) on the electrical conductivity of the composites
solvent. The degradation rate coefÀcients at the supercritical
were investigated and the heat stability of the composites
conditions are an order higher than the rate coefÀcients at
determined by thermogravimetry. 18 refs.
subcritical conditions, indicating enhanced degradation at
TAIWAN
supercritical conditions. The Arrhenius plot shows a break at
Accession no.875416 the supercritical transition point, while the semilogarithmic
plot of rate coefÀcients with the density of the reaction
Item 109 mixture shows a continuous linear variation. 17 refs.
Industrial and Engineering Chemistry Research INDIA
41, No.22, 30th Oct.2002, p.5393-400 Accession no.875148
HYDROTHERMAL DECHLORINATION AND
DENITROGENATION OF MUNICIPAL-WASTE-
Item 111
PLASTICS-DERIVED FUEL OIL UNDER SUB-
Polymer
AND SUPERCRITICAL CONDITIONS
43, No.25, 2002, p.6653-9
Akimoto M; Ninomiya K; Takami S; Ishikawa M; Sato
PREPARATION OF CROSS-LINKED
M; Washio K
MICROPARTICLES OF POLY(GLYCIDYL
Niigata,University
METHACRYLATE) BY DISPERSION
The hydrothermal processing of municipal-waste-plastics- POLYMERIZATION OF GLYCIDYL
derived fuel oil (kerosene fraction; Cl content = 62 ppm, METHACRYLATE USING A PDMS
N content = 1150 ppm) under sub- and supercritical MACROMONOMER AS STABILIZER IN
conditions is investigated so as to demonstrate the possible SUPERCRITICAL CARBON DIOXIDE
use of water and aqueous solutions of metal salts and Wenxin Wang; GrifÀths R M T; Naylor A; Giles M R;
hydroxides for the dechlorination and denitrogenation Irvine D J; Howdle S M
of the fuel oil. The hydrothermal processing is carried Nottingham,University; Uniqema
out in a small SUS316 stainless steel batch reactor under
The dispersion polymerisation of glycidyl methacrylate was
nitrogen atmosphere. Although the two reactions take place
carried out using poly(dimethylsiloxane) monomethacrylate
in water, they proceed much more readily under basic
macromonomer as the stabiliser in supercritical carbon
conditions, especially in aqueous solutions of alkaline
dioxide. Under optimised conditions, discrete crosslinked
metal hydroxides. That is, the nitrogen content in the
polymer particles were produced with high monomer
product oil decreases to 297 ppm upon processing with
conversion during a very short reaction time of less than
water for 15 min at 425 deg.C, whereas it decreases to
4 h. The reaction pressure and stabiliser concentration
49 ppm when 0.10 mol/L NaOH is used instead of water
affected the morphology of the Ànal product. 18 refs.
at 375 deg.C. Under these hydrothermal conditions, the
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
chlorine content in the product oil is always nearly 0 ppm. EUROPE
Organic acids such as benzoic acid and phthalic acid in
the fuel oil can also be removed. 37 refs. Accession no.874632
JAPAN
Accession no.875151 Item 112
Macromolecules
35, No.23, 5th Nov.2002, p.8869-77
Item 110 PREPARATION OF A POLYMETHYL
Industrial and Engineering Chemistry Research METHACRYLATE/ULTRAHIGH MOLECULAR
41, No.22, 30th Oct.2002, p.533-40 WEIGHT POLYETHYLENE BLEND USING
KINETICS OF DEGRADATION OF SUPERCRITICAL CARBON DIOXIDE
POLYCARBONATE IN SUPERCRITICAL AND AND THE IDENTIFICATION OF A THREE-
SUBCRITICAL BENZENE PHASE STRUCTURE. AN ATOMIC FORCE
Silvalingam G; Madras G MICROSCOPY STUDY
Indian Institute of Science Zhang J; Busby A J; Roberts C J; Chen X; Davies M C;
Item 117 New chemical blowing agents (CBAs) are making dramatic
ACS Polymeric Materials: Science and Engineering. strides in achieving reproducible cell distributions and cell
Spring Meeting. Volume 84. Proceedings of a size in microcellular foaming. New applications include
conference held San Diego, Ca., 1st-5th April 2001. automotive mouldings, such as foamed bumpers and fascia.
Washington, D.C., ACS,Div.of Polymeric Materials CBAs now utilise microencapsulated small particle size
Science & Engng., 2001, Paper 343, p.625-6, 27cm, 012 components with very narrow distributions to achieve both
SUPERCRITICAL CARBON DIOXIDE signiÀcant weight reduction and cycle time improvement.
INTERACTION WITH POLYMERIC Trials show that these improvements can be achieved on
MATERIALS: SORPTION AND DESORPTION conventional equipment. 11 refs.
DIFFUSION COEFFICIENT USA
Shuely W J; Ince B S Accession no.871809
US,Research & Technology Directorate;
US,Army,Aberdeen Proving Ground
(ACS,Div.of Polymeric Materials Science & Engng.) Item 119
162nd ACS Rubber Division Meeting - Fall 2002.
Sorption and desorption diffusion coefÀcient measurements Proceedings of a conference held Pittsburgh, Pa., 8th-
by means of TGA were carried out to characterise the 11th Oct. 2002.
plasticisation of a range of polymers by supercritical Akron, Oh., ACS Rubber Division, 2002, Paper 116,
carbon dioxide, which is utilised as a cleaning Áuid for pp.17, 28cm, 012
sensitive equipment. Polymers tested included PVC, DEVULCANIZATION OF UNFILLED NATURAL
PPO, polycarbonate, PMMA and polydimethylsiloxane. RUBBER IN SUPERCRITICAL CARBON
The time required to return to the unplasticised state DIOXIDE
was estimated using diffusion coefÀcient equations and Kojima M; Tosaka M; Kohjiya S; Ikeda Y
continuous desorption curve measurements permitted Kyoto,University; Kyoto,Institute of Technology
adjustment and correction for extractables and zero-time (ACS,Rubber Div.)
sorption measurement lag after decompression. 3 refs.
USA
Sulphur cured unÀlled NR was devulcanised in supercritical
carbon dioxide using diphenyl disulphide, as devulcanising
Accession no.872806 agent, and the product fractionated into sol and gel
fractions. The structure and properties of the devulcanised
Item 118 rubber were determined by rheometry, viscometry,
Foams 2002. Proceedings of a conference held Houston, swelling measurements, NMR spectroscopy, GPC and
Tx., 22nd-23rd Oct.2002. DSC. The dependence of devulcanisation on the amount
BrookÀeld, Ct., 2002, Session VII, p.163-8, 27cm, 012 of devulcanising agent, pressure and time was examined
INNOVATIVE FOAMING TECHNOLOGIES and the effect of crosslink distribution in the vulcanisate
Reedy M E on devulcanisation evaluated. 20 refs.
Reedy International Corp. JAPAN; USA
(SPE,Thermoplastic Materials & Foams Div.; Accession no.871413
SPE,South Texas Section)
Many new innovative technologies are now being Item 120
introduced and reintroduced for foamed injection moulding Journal of Applied Polymer Science
processing. Often called microcellular foaming, the new 86, No.9, 28th Nov.2002, p.2338-41
technologies utilise a number of approaches to achieve MOLECULAR WEIGHT DISTRIBUTION
Àne cellular structures with double-digit weight and cycle OF POLYACRYLONITRILE PRODUCED IN
time reductions. The key to the innovative technologies is SUPERCRITICAL CARBON DIOXIDE
computerised process control, good tool design including Xin-rong Teng; Hui-li Shao; Xue-chao Hu
counter pressure, static melt mixing and new chemical Shanghai,Donghua University
blowing agents. These technologies have subtle differences,
which are very important for optimum part performance. An effectively linear molec.wt. calibration curve of
Technologies include a microcellular injection moulding PAN was obtained using a copolymer standard with a
process using supercritical gas and polymer mixtures, which single broad MWD. The molec.wts. and MWDs of PAN
reduce part weight while creating a swirled surface Ànish. obtained from precipitation polymerisation of acrylonitrile
A class A surface is obtained with the use of Textron’s in supercritical carbon dioxide were quantiÀed by the
IntelliMould, a process control system that decreases part calibration curve. The effects of monomer concentration,
weight and cycle time while eliminating surface irregularities. initiator concentration, carbon dioxide pressure and total
In addition, new compact gas counter pressure modules are reaction time on the molec.wt. and MWD were studied
providing signiÀcantly improved structural foam processing. in detail. 28 refs.
Processors are also using new tailored static mixers to create CHINA
highly uniform melt components at constant temperatures. Accession no.871260
polydimethyl siloxane with dissolved carbon dioxide, and carbon dioxide-assisted extrusion and as a blowing agent
polystyrene with the refrigerant gases 1,1-diÁuoroethane in the microcellular foaming process. 7 refs.
(R152a) and 1,1,1,2-tetraÁuoroethane (R134a). For each USA
system, conventional viscoelastic scaling techniques were Accession no.855568
used to reduce the composition-dependent viscosity versus
shear rate relationships to master curves identical to the
Item 143
viscosity curve for the pure polymer. The dependence of
Modern Plastics International
the viscoelastic scaling factors on dissolved gas content is
32, No.5, May 2002, p.35
correlated by a simple free volume theory, combined with
NEW SOLVENT PROVES CRITICAL TO
an equation-of-state model for the polymer-gas mixture. Also
MAKING IMPROVED FLUOROPOLYMERS
considered is the effect of dissolved gas on the glass transition
Rosenzweig M
temperature of the polymer-gas mixture.
USA DuPont Fluoropolymers is introducing what it claims
Accession no.855569 are the first commercial fluoropolymers made using
supercritical carbon dioxide. The nine grades now debuting
globally are similar to Áuorinated ethylene propylene
Item 142 polymers, but are terpolymers containing some vinyl ether.
ACS POLYMERIC MATERIALS SCIENCE AND The materials, designated TeÁon G, are much tougher than
ENGINEERING. SPRING MEETING 2001. VOLUME FEP. Toughness at 100C is 4.6 kJ/m3 versus 1.7 kJ/m3
84. Proceedings of a conference in San Diego, Ca.. for TeÁon FEP. Tensile strength retention with increasing
Washington, D.C., 2001, p.276-8, 012 temperature exceeds all current FEP polymers, while
CO2-ASSISTED POLYMER PROCESSING: ultimate elongation also is much higher. The new polymers
ACCESSING NEW PROCESSING WINDOWS are particularly suitable for extrusion. Initial applications
AND NOVEL MORPHOLOGIES will focus on heat-shrink tubing, wire and cable insulation
Royer J R; Siripurapu S; DeSimone J M; Spontak R J; and industrial Àlm.
Khan S A
North Carolina,State University; North DUPONT FLUOROPOLYMERS
Carolina,University USA
Accession no.855046
A detailed rheological investigation to help elucidate the
advantages of carbon dioxide-induced plasticisation is
presented. Several example cases, speciÀcally microcellular Item 144
foaming and extrusion technology are discussed to Blowing Agents and Foaming Processes 2002.
demonstrate the utilisation of supercritical carbon Proceedings of a conference held Heidelberg, 27th-28th
dioxide as a plasticiser. Experimental measurements of May 2002.
viscosity as a function of shear rate, pressure, temperature Shawbury, Rapra Technology Ltd., 2002, Paper 8, p.79-
and carbon dioxide concentration were carried out for 85, 29cm, 012
various commercial polymer resins using an extrusion NEW DEVELOPMENTS IN MUCELL
slit die rheometer. Carbon dioxide was demonstrated MICROCELLULAR FOAM MOULDING
to be an excellent plasticiser for all samples measured, TECHNOLOGY AND COMMERCIAL
lowering the viscosity of the polymer melts by 25-80% APPLICATIONS
depending on pressure, temperature and carbon dioxide Janisch R
concentration. A free-volume model was developed to Trexel USA
predict the effects of carbon dioxide on melt rheology, (Rapra Technology Ltd.)
using existing theories for viscoelastic scaling of polymer The MuCell microcellular foam injection moulding
melts and the prediction of glass transition temperature process, which provides plastics components that
depression by a diluent. Conventional viscoelastic scaling are lighter, Áatter, straighter and more dimensionally
and data corrections were formed using the predictive stable at extreme operating temperatures compared to
free-volume model developed. Utilising only the free- conventionally moulded components, and the hardware
volume theory, the experimental data was collapsed to a necessary to adapt the process are brieÁy described. The
single master curve independent of pressure and carbon cost beneÀts of the process are indicated and a range
dioxide concentration for each of the three polymer resins. of products manufactured using the process, which
A predictive tool to quantify the viscosity reduction of employs supercritical fluids of inert gases to create
polymer melts due to plasticisation by carbon dioxide or evenly distributed and uniformly sized microscopic cells
other diluents is therefore possible from the combination throughout the polymer, by companies from as far aÀeld
of conventional viscoelastic scaling and free volume theory as Australia and Singapore are illustrated. 5 refs.
with thermodynamic models. This prediction assists in the EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA;
design of novel extrusion processes and in understanding WESTERN EUROPE
the ability of carbon dioxide to act as a processing aid for Accession no.854592
vinylidene Áuoride(VDF)) with VAc was possible and and synthesise novel materials with both strongly polar
that P(TFE-VAc) was linear. All the TFE-VAc copolymers groups and highly CO2-philic segments. Synthetic
had high yields and high molec.wts., suggesting good polymers with pendent carbohydrate moieties and a stable
solubility in carbon dioxide. CTFE-VAc copolymers C-C backbone are referred to as glycopolymers, which
were synthesised in high yield when less than 50 mol are water-soluble and have many potential applications
% CTFE was in the feed. At higher concentrations of in biochemical and biomedical Àelds. Novel amphiphilic
CTFE, the gradual consumption of VAc resulted in lower block copolymers with well-defined glycopolymer
polymer yields and molec.wts., suggesting that CTFE and fluoropolymer blocks are reported using living
was less soluble than TFE in carbon dioxide. VDF-VAc anionic polymerisation. Both protected (hydrophobic/
copolymers were synthesised with the lowest yields of the CO2-philic) and deprotected (hydrophilic/CO2-philic)
three Áuorocarbons studied due to the decreased reactivity copolymers are CO2 amphiphiles and their solubility in
(and probably carbon dioxide solubility) of VDF relative CO2 is heavily inÁuenced by the amphiphilic structure.
to VAc. 35 refs. The emulsion polymerisation of N-ethylacrylamide in
CANADA CO2 is successfully performed by using the hydrophilic
Accession no.853379 deprotected block copolymer. 7 refs.
USA
Accession no.849822
Item 149
Macromolecules
35, No.9, 23rd April 2002, p.3325-7 Item 151
RIGID PORE STRUCTURE FROM HIGHLY Plastics and Rubber Weekly
SWOLLEN POLYMER GELS 5th April 2002, p.9
Winter H H; Gappert G; Ito H SUPERCRITICAL DEBUT
Massachusetts,University Smith C
A crosslinked PE specimen, when exposed to a suitable DuPont has launched a range of six high-performance
pressure-temp. cycle in the presence of supercritical melt processable PTFE resins, the first commercial
propane, was shown to increase its size several fold and to products to be manufactured using its supercritical CO2
develop an open-pore structure. The process was genuine polymerisation technology. Process G uses supercritical
and was expected to be applicable to other semicrystalline CO2 in place of water used in traditional emulsion
polymers which could be crosslinked and swollen. It polymerisation of Áuoropolymers. The Àrst Process G
provided a relatively simple method for obtaining high resins are targeted at heat shrink tubing, high-performance
value-added materials from commodity polymers such Àlms and high temperature cable sleeving. Property data
as PE or from approved biopolymers. When supercritical are presented.
Áuids were used as the swelling Áuid, the process was DUPONT CO.
capable of producing extremely high-purity materials with USA
zero emissions. 15 refs. Accession no.849679
USA
Accession no.853346 Item 152
Macromolecules
Item 150 35, No.3, 29th Jan.2002, p.934-40
Polymer Preprints. Volume 42, Number 2, Fall 2001. POLY(METHYL METHACRYLATE) AND
Proceedings of a conference held Chicago, Il., 26th-30th POLY(BUTYL METHACRYLATE) SWELLING IN
August 2001. SUPERCRITICAL CARBON DIOXIDE
Washington D.C., ACS,Div.of Polymer Chemistry, Nikitin L N; Said-Galiyev E E; Vinokur R A;
2001, p.340-1 Khokhlov A R; Gallyamov M O; Schaumburg K
LIVING ANIONIC POLYMERISATIONS OF Russian Academy of Sciences; Moscow,Lomonosov
WELL-DEFINED SUGAR-CONTAINING University; Copenhagen,University
DIBLOCK FLUOROCOPOLYMER AND
The swelling of PMMA and poly(butyl methacrylate) in
ITS APPLICATION IN CO2 EMULSION
supercritical carbon dioxide was studied by means of direct
POLYMERISATIONS
optical observation. The diffusion coefÀcients of carbon
Ye W; DeSimone D M
dioxide molecules in the polymers were determined by
North Carolina,University
analysing the diffusion front propagation in the polymers
(ACS,Div.of Polymer Chemistry)
and by volumetric measurements of the swelling kinetics
Carbon dioxide as a useful processing Áuid is limited for different temperatures and pressures. The results from
by its inability to solubilise highly polar compounds. the two methods were in good agreement. A difference in
This problem can be alleviated by the addition of CO2- the appearance of diffusion fronts in these polymers with
philic amphiphiles. The primary objective is to design different glass transition temperatures was observed. The
Item 170
Item 168 ACS Polymeric Materials Science and Engineering.
ACS Polymeric Materials Science and Engineering. Spring Meeting 2001. Volume 84. Proceedings of a
Spring Meeting 2001. Volume 84. Proceedings of a conference in San Diego, Ca..
conference in San Diego, Ca.. Washington, D.C., 2001, p.37-8. 012
Washington, D.C., 2001, p.45-6. 012 OPEN-PORE MORPHOLOGIES BY
FREE-RADICAL COPOLYMERIZATIONS CRYSTALLIZATION OF CROSSLINKED,
OF STYRENE AND METHACRYLIC ACID POLYETHYLENE GELS SWOLLEN WITH
ESTERS IN HOMOGENEOUS PHASE OF SUPERCRITICAL PROPANE
SUPERCRITICAL CARBON DIOXIDE Gappert G; Ito H; Winter H H
Beuermann S; Buback M; Jurgens M Massachusetts,University
Gottingen,Georg-August-Universitat
Crosslinked polyethylene was crystallised from supercritical
Phase behaviour measurements and copolymer syntheses propane to create open-pore structures in pre-shaped
show that free-radical binary and ternary copolymerisations samples. A metallocene LLDPE was moulded from pellet
of styrene with functional methacrylates such as, for example, into a Áat sheet and then radiation crosslinked in an inert
glycidyl methacrylate, 2-hydroxypropyl methacrylate or i- atmosphere. The shaped, crosslinked sample was then
bornyl methacrylate might be carried out in homogeneous swollen with its critical point to prevent the formation
phase in the presence of supercritical carbon dioxide up to of a liquid phase during pore evacuation. Samples which
high degrees of monomer conversion. Terpolymerisations of contained a fraction of uncrosslinked chains were partially
styrene with methyl methacrylate and glycidyl methacrylate extracted during the swelling step. All samples displayed
were modelled using the software program PREDICI. a rise in volume and decrease in density and maintained
Currently developed are strategies either for a batch or a their original moulded shape. Scanning electron microscopy
continuous polymerisation process leading to a uniform reveals pore sizes ranging from about 0.25 microns to 10
copolymer composition. 7 refs. microns. Propane is recovered completely in high purity and
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; leaves no residue in the porous polyethylene. 10 refs.
WESTERN EUROPE
USA
Accession no.841552
Accession no.841550
supercritical carbon dioxide Áuid. At lower temp. and Pressure was measured using transducers before and after
pressure, the high-speed spun Àbres, which had inherently the die contraction. The introduction of CO2 into the
larger crystallite sizes and lower birefringence, showed polystyrene melt reduced the entrance pressure drop, and
a larger dye uptake than the other fibres. When the the shear and extensional viscosities. The entrance pressure
supercritical conditions were elevated to 125C and 230 drops as a function of wall shear stress Àtted a master curve
bar, the dye uptake of both types increased markedly for different CO2 contents and pressure levels. 10 refs.
and the difference in dye uptake between the fibres CANADA
became small. This indicated that the swelling of Àbres Accession no.823411
in supercritical carbon dioxide Áuid exceeded a certain
level and the diffusion of dye molecules was then
Item 203
promoted. The swelling also promoted the rearrangement
Blowing Agents ‘99. Proceedings of a conference
of molecular chains and permitted cold crystallisation to
held at the conference centre UMIST, UK, 9th.-10th
occur. The modiÀcation of Àbre structure through dyeing
December 1999..
in supercritical carbon dioxide fluid was significant,
Shawbury, 1999, Paper 11, p.59-63. 012
particularly for the Àbres whose inherent structure was
MICROCELLULAR FOAM MOLDING
not so well developed. 20 refs.
TECHNOLOGY
JAPAN
Pierick D; Janisch R
Accession no.825008 Trexel Inc.
(Rapra Technology Ltd.)
Item 201 The MuCell foam moulding technology, invented by
Antec 2001.Conference proceedings. the Massachusetts Institute of Technology’s Mechanical
Dallas, Texas, 6th-10th May, 2001, paper 200 Engineering Department, and licenced exclusively by Trexel
SUPERCRITICAL FLUID ASSISTED POLYMER Inc., is described. The proprietary process uses supercritical
PROCESSING Áuids of atmospheric gases to create evenly distributed and
Matthews S O; Hornsby P R uniformly sized microscopic cells throughout a polymer.
Brunel University The process is suitable for injection moulding, blow
(SPE) moulding and extrusion, providing advantages in product
A single screw extruder with a direct injection port for design, processing efÀciency and cost reduction. The use of
supercritical carbon dioxide was used to study the inÁuence MuCell technology permits moulders to reduce raw material
of CO2 additions on the processing of polyethylene (PE) consumption and cycle time whilst producing strong, lighter
and PE containing silicon nitride. The extruder was Àtted weight products, the ability to foam thin-walled parts,
with a slit die for in-line rheometry. The injection of CO2 reduce processing temperatures, injection pressure and
gave an average reduction in viscosity of 25%. Negligible clamp tonnage. In addition, the process enables moulders
foaming was observed, and was dependent upon screw to foam materials that previously could not be foamed
speed, temperature, and the rate of CO2 injection and successfully using conventional foaming technologies,
pressure. Removal of the PE from the composite materials such as high temperature polysulphone, polyetherimide,
by thermal treatment yielded ceramics of controlled liquid crystalline polymers and thermoplastic elastomers.
porosity which could be successfully sintered. 8 refs. These advantages and features of the MuCell technology
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN are further discussed, and examples of applications are
EUROPE described.
Accession no.823412 EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA;
WESTERN EUROPE
Accession no.818864
Item 202
Antec 2001.Conference proceedings.
Item 204
Dallas, Texas, 6th-10th May, 2001, paper 199
Blowing Agents ‘99. Proceedings of a conference
MEASUREMENT OF ENTRANCE PRESSURE
held at the conference centre UMIST, UK, 9th.-10th
DROP OF POLYSTYRENE/SUPERCRITICAL
December 1999..
CO2 SOLUTIONS
Shawbury, 1999, Paper 10, p.53-57. 012
Xue A; Tzoganakis C
CARBON DIOXIDE AS BLOWING AGENT
Waterloo,University
IN THE EXTRUSION OF THERMOPLASTIC
(SPE)
FOAMS
The inÁuence of pressure and supercritical carbon dioxide Gale M
content on the entrance pressure drop and rheological Rapra Technology Ltd.
properties of polystyrene/CO2 solutions was investigated (Rapra Technology Ltd.)
using a twin screw extruder Àtted with 180 degree entrance
The use is discussed of carbon dioxide as a blowing agent
angle slit dies with contraction ratios of 4:1 and 18:1.
in the extrusion of thermoplastic foams, in particular,
polyoleÀns and polystyrene. The paper summarises some London,Imperial College of Science,Technology &
of the work carried out at Rapra Technology Ltd., into Medicine
the use of carbon dioxide with a conventional single
Supercritical Áuids have a unique and valuable potential
screw extruder, retroÀtted with a Cavity Transfer Mixer
for the enhanced processing of many materials. Research
and a static mixer heat exchanger. Estimates are included
in the applications of supercritical fluids to polymer
of potential cost savings for a proposed commercial
processing are reviewed. The ability of supercritical
applications, and an indication of the type of equipment
carbon dioxide to swell and plasticise polymers is crucial
which will probably be used. 9 refs.
to impregnation, extraction and modiÀcation of polymeric
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
EUROPE
materials. This plasticisation also reduces viscosity and
facilitates the processing of polymers due to lower shear
Accession no.818863 stresses. Spectroscopy plays an important role in probing
these interactions at a molecular level and to follow in
Item 205 situ the processes of CO2-induced plasticisation and
Industrial and Engineering Chemistry Research the crystallisation of polymers. Opportunities exist for
40, No.3, 7th Feb.2001, p.756-67 improving the processing of many polymeric-based
DEPOLYMERISATION OF STYRENE- materials ranging from textile to food and biomaterials.
BUTADIENE COPOLYMER IN NEAR-CRITICAL The implications of interactions between supercritical
AND SUPERCRITICAL WATER carbon dioxide and polymers for drying, dyeing, foaming
Park Y; Hool J N; Curtis C W; Roberts C B and extrusion are also discussed with an outlook for
Auburn,University further opportunities in this and related areas of polymer
processing. 312 refs.
Many conventional solvents do not sufÀciently dissolve
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
crosslinked polymers such as SBR to allow efÀcient EUROPE
polymerisation. Supercritical and near-critical water
Accession no.809650
provides an alternative benign solvent for this application.
Supercritical water oxidation and thermal gradation
under supercritical water conditions provide a means to Item 207
break down rubbery materials into organic compounds Macromolecules
that can then be recovered as a chemical feedstock. 34, No.4, 13th Feb.2001, p.775-81
Depolymerisation reactions of SBR are examined in RING-OPENING POLYMERIZATION
a semi-continuous reactor. A statistical experimental OF EPSILON-CAPROLACTONE IN
analysis technique is used to investigate the effect of SUPERCRITICAL CARBON DIOXIDE
various operating conditions: temperature, pressure and the Stasssin F; Halleux O; Jerome R
presence of hydrogen peroxide as an oxidant. The results Liege,University
demonstrate the ability of supercritical and near-critical
The ring-opening polymerisation of epsilon-caprolactone
water to break down the SBR into a range lower molecular
was investigated in supercritical carbon dioxide at 40 C
weight organic compounds for potential recovery. Analysis
and 210-215 bar, with dibutyltin dimethoxide initiator.
of variance shows that the temperature and oxidant
The polymer molecular weight was dependent upon
concentration are signiÀcant at the 1% level for destruction
the monomer:tin alkoxide molar ratio and the degree of
efficiency. Benzene, toluene, ethylbenzene, styrene,
monomer conversion. First-order reaction kinetics were
phenol, acetophenone, benzaldehyde and benzoic acid are
observed, the kinetics being lower than for polymerisation
identiÀed as liquid products using gas chromatography in
in toluene and in bulk. This was attributed to the
both and semi-continuous reactors. The gas products are
competitive coordination of CO2 onto tin. 21 refs.
comprised of carbon monoxide, carbon dioxide and water
BELGIUM; EUROPEAN COMMUNITY; EUROPEAN UNION;
as determined by Fourier transform IR spectroscopy. The WESTERN EUROPE
efÀciency and a semi-quantitative analysis of the liquid
Accession no.808638
products show that both pyrolysis and oxidation products
are observed, and low molecular weight oxidation products
are to be primary. 7 refs. Item 208
USA Polymer Engineering and Science
Accession no.810172 41, No.2, Feb.2001, p.135-44
DRAWING IN HIGH PRESSURE CARBON
DIOXIDE - A NEW ROUTE TO HIGH
Item 206 PERFORMANCE FIBERS
Polymer Science Series C Hobbs T; Lesser A J
42, No.1, 2000, p.78-101 Massachusetts,University
POLYMER PROCESSING WITH
SUPERCRITICAL FLUIDS A new draw technique for polymer orientation was
Kararian S G developed and applied to different polymer Àbres (PETP,
nylon-66 and UHMWPE). In this technique, a polymer EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
was drawn uniaxially in supercritical carbon dioxide EUROPE
using a custom high-pressure apparatus. This technique Accession no.807333
could be used as a replacement for the traditional drawing
process or as a post-treatment process. With PETP, Item 211
the technique was not effective at temps. at or below Industrial and Engineering Chemistry Research
130C. In contrast, the process was highly effective for 40, No.2, 24th Jan.2001, p.536-43
nylon-66, where carbon dioxide drawn Àbres showed LATEXES FORMED BY RAPID EXPANSION OF
signiÀcantly higher crystallinity and orientation, together POLYMER/CARBON DIOXIDE SUSPENSIONS
with improved mechanical properties. While the Àbres INTO WATER. I. HYDROPHILIC SURFACTANT
were plasticised, the drawability of the Àbres was only IN SUPERCRITICAL CARBON DIOXIDE
slightly dependent on temp. High pressure carbon dioxide Jae-Jin Shim; Yates M Z; Johnston K P
drawing of UHMWPE fibres was equally effective. Texas,University
Commercial high performance Àbres could be drawn
up to a ratio of 1.9 in a second stage, resulting in large The rapid expansion of poly-2-ethylhexyl acrylate
increases in tensile modulus and small improvements in suspensions in supercritical carbon dioxide containing a
TS. 40 refs. hydrophilic as well as a carbon dioxide-philic surfactant
USA produced stable aqueous latices. The hydrophilic
surfactants were soluble in both carbon dioxide and
Accession no.807502
water. The aqueous latices could also be formed after
depressurisation and resuspension of the polymer
Item 209 dispersion in carbon dioxide. Latices in basic buffer
Journal of the Textile Institute - Part 3: Textile solutions were stable for a few weeks for concentrations
Design: Technology, Management and Marketing up to 15.6% and for several months after sonication. The
Vol.91, 2000, p.166-7 synthesis of water-dispersible polymer particles in carbon
NOTES ON FUTURE DEVELOPMENTS FOR dioxide, which could be transferred to water without the
TEXTILE FINISHING PROCESSES need for organic solvents, could be used for preparation
Knittel D; Schollmeyer E of new environmentally-benign coatings and adhesives.
German Textile Research Institute North-West eV 28 refs.
A brief description is presented of textile Ànishing processes USA
that are liable to gain broad technical application in the Accession no.807153
near future and on other processes that require intensive
research work but promise beneÀcial new ecological Item 212
and economical treatment procedures. The processes Journal of Polymer Research
discussed include supercritical Áuid dyeing of synthetic 7, No.3, Sept.2000, p.155-9
Àbres (particularly PETP), electric dyeing, liquid ammonia ANALYSIS ON THE DYEING OF
treatment of cellulosic Àbres, enzymatic processes, and POLYPROPYLENE FIBERS IN SUPERCRITICAL
processes for conductive Àbres, liquid crystal Àbres and CARBON DIOXIDE
Àbres derived from new bioresources. Liao S K; Chang P S; Lin Y C
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; Feng Chia,University
WESTERN EUROPE
Accession no.807440 PP Àbres were dyed in a supercritical carbon dioxide
system and the results were compared with those for
Àbres dyed in water system. Dye uptake value calculated
Item 210 by UV spectroscopy indicated that PP Àbre dyeing was
Chemical and Engineering News much better in carbon dioxide than in water. Optical
79, No.5, 29th Jan.2001, p.34-5 microscopic analysis showed that dye molecules had
ONE STEP TO BIOACTIVE POLYMERS diffused thoroughly into Àbre in carbon dioxide because
Brennan M B of the good compatibility between the dye and the carbon
A report is presented on studies led by S.M.Howdle at the dioxide. X-ray and birefringence analysis demonstrated
University of Nottingham in which supercritical carbon that plasticisation caused by the introduction of carbon
dioxide is used to incorporate inorganic materials and dioxide made the molecular chain more mobile and led
enzymes into the biodegradable polymers poly(lactide- to an increase in the dyeing of PP Àbres. Furthermore, a
co-glycolide) and poly(DL-lactide). Particular attention mechanical test and DSC analysis indicated that the Àbre
is paid to the incorporation of hydroxyapatite in order to structure was not damaged when the fabric was dyed at
create artiÀcial bone and to the incorporation of catalase, 100C. 23 refs.
ribonuclease A and beta-D-galactosidase. TAIWAN
interesting family of silicone polymers are the silicone of supercritical carbon dioxide is in the direct formation
rubbers - ready for curing compounds, that overcome of microcellular thermoplastic parts, in which the direct
the poor mechanical properties of raw silicones after addition of supercritical Áuid is done in an extruder to
intermolecular net formation. Siloxane based polymers are produce foamed plastic parts. 6 refs.
known to be soluble in supercritical carbon dioxide over INDIA
a wide range of concentrations. The main disadvantage Accession no.801405
of raw siloxanes in sensor applications is the loss of
surface integrity over time due to inadequate viscosity.
Item 219
A new approach is described combining RESS and room
Industrial and Engineering Chemistry Research
temperature gas-phase curing to produce siloxane based,
39, No.12, Dec.2000, p.4891-6
chemically active and physically stable polymer particles
NEW CHELATE COMPLEXES OF COPPER AND
with a wide range of morphologies. 5 refs.
IRON: SYNTHESIS AND IMPREGNATION INTO
USA
A POLYMER MATRIX FROM SOLUTION IN
Accession no.802377 SUPERCRITICAL CARBON DIOXIDE
Said-Galiyev E; Nikitin L; Vinokur R; Gallyamov M;
Item 217 Kurykin M; Petrova O; Lokshin B; Volkov I;
Antec 2000.Conference proceedings. Khokhlov A; Schaumburg K
Orlando, Fl., 7th-11th May, 2000, paper 488 Nesmeyanov Institute of Organo-Element Compounds;
SUPERCRITICAL CARBON DIOXIDE Copenhagen,University
ASSISTED POLYMER BLENDING IN Chelate complexes of copper diiminate and iron diiminate
TWIN-SCREW EXTRUSION: RELATIONS were synthesised and their physical characteristics were
BETWEEN MORPHOLOGY EVOLUTION AND studied. The diffusion of supercritical(SC) carbon dioxide
MECHANICAL PROPERTIES into polyarylate(PAR) Àlms and their impregnation with
Elkovitch M D; Lee L J; Tomasko D L diiminates were investigated. The equilibrium degree
Ohio,State University of PAR swelling in SC carbon dioxide was about 10%.
(SPE) The conditions of impregnation were determined. The
The inÁuence of additions of 0.5-3.0 wt% of supercritical impregnation was conÀrmed by the FTIR spectroscopic
carbon dioxide to blends of polystyrene (PS) and data. Thermal reduction of metal ions was investigated.
poly(methyl methacrylate) (PMMA) was investigated Transformations of the chelate complexes on the polymer-
during compounding using a twin screw extruder. Àlm surface were studied by ESCA. The value of the Auger
Viscosity reductions of up to 80% and 70% were observed factor indicated that, after thermal reduction, the copper
for PMMA and PS, respectively. The dispersed phase ion was in a nearly univalent state. The copper content in
exhibited a sharp decrease in size adjacent to the injection Àlms was as large as 6.3 wt % and the iron content was 4.5
point, but further compounding resulted in its coalescence, wt %. The FTIR and ESCA spectroscopic studies showed
and demixing occurred when the CO2 was vented. The that, in the course of impregnation, chelate complexes
Ànal morphology was similar to that observed without the interacted with functional groups of the polymer.
addition of CO2. Small additions of Àllers slowed down Subsequent thermal reduction of metal in air resulted in
the demixing on release of the CO2. 12 refs. diiminate evaporation and thermooxidative degradation
USA with ligand decomposition and enrichment of the surface
with metal atoms. According to the SAXS data, the size
Accession no.802018
distribution of metal-containing particles ranged from 20
to 60 nm with a maximum at 34 nm. 23 refs.
Item 218 DENMARK; EUROPEAN COMMUNITY; EUROPEAN UNION;
Popular Plastics and Packaging RUSSIA; SCANDINAVIA; WESTERN EUROPE
46, No.1, Jan. 2001, p.77-9 Accession no.800608
REVIEW ON THE APPLICATIONS OF
SUPERCRITICAL FLUIDS IN POLYMER Item 220
PROCESSING Industrial and Engineering Chemistry Research
Tipnis S J 39, No.12, Dec.2000, p.4707-13
The use of supercritical Áuids and in particular supercritical COMPARISON OF DYE DIFFUSION IN
carbon dioxide is examined with respect to the beneÀts it POLY(ETHYLENE TEREPHTHALATE) FILMS
provides in polymer processing and polymerisation. The IN THE PRESENCE OF A SUPERCRITICAL OR
viability of using supercritical carbon dioxide as a solvent AQUEOUS SOLVENT
medium for homogeneous solution of polymerisation in Sicardi S; Manna L; Banchero M
place of ecologically dangerous solvents such as CFC Torino,Politecnico
was demonstrated in the homogeneous synthesis of The diffusion coefficients of a solute (a dyestuff)
Áuorinated telomers. A further development in the use permeating a PETP Àlm in a supercritical impregnating
system were measured for different working conditions The kinetics of the surfactant-free precipitation
and the results were compared with similar data obtained polymerisation of vinylidene Áuoride(VDF) in supercritical
with the same solute in the same material but in a carbon dioxide were studied in a continuous stirred
traditional aqueous system. The experimental technique autoclave. Diethyl peroxydicarbonate was used as the
used was that of the ‘Àlm roll method’ for the experiments free-radical initiator. The stirring rate and agitator design
conducted in the supercritical system. For the aqueous had no effect on the rate of polymerisation(Rp) or on the
system, the sorption kinetics of the dyestuff on plane PETP weight-average molec.wt.(Mw) of the PVDF formed. The
sheets were measured. The results conÀrmed the high gain fractional conversion of VDF ranged from 7 to 26% and Rp
in the rate of diffusion obtained with the supercritical was as high as 0.000027 mol/L.s at 75C and at a VDF feed
impregnating system, related to the high plasticising concentration of 2.5 mol/L. The PVDF was collected as a
power of supercritical carbon dioxide towards synthetic dry, free-Áowing powder and had Mws up to 150 kg/mol
polymers. Comparison was made with the data obtained and melt Áow indices as low as 3.0 at 230C. Homogeneous,
by operating with supercritical carbon dioxide at different free-radical kinetics provided a reasonable basis for
working pressures and temps. and in the presence of a describing the Rp, despite the heterogeneous nature of
proper modiÀed (ethanol). 25 refs. the system. The order of the reaction with respect to the
EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; monomer was found to be 1.0 and the order with respect
WESTERN EUROPE to the initiator was 0.5. The experimental data suggested
Accession no.800602 that an inhibitor was present in the monomer or that the
monomer itself acted as an inhibitor. 31 refs.
USA
Item 221
Industrial and Engineering Chemistry Research Accession no.800595
39, No.12, Dec.2000, p.4622-6
PRODUCTION OF ENGINEERING PLASTICS Item 223
FOAMS BY SUPERCRITICAL CARBON Industrial and Engineering Chemistry Research
DIOXIDE 39, No.12, Dec.2000, p.4564-6
Ming-Tsai Liang; Chang-Ming Wang SYNTHESIS OF SUGAR-CONTAINING
I-Shou,University AMPHIPHILES FOR LIQUID AND
Foams of PETP and polycarbonate(PC) were prepared SUPERCRITICAL CARBON DIOXIDE
by rapid depressurisation of carbon dioxide-saturated Weijun Ye; DeSimone J M
molten resin. It was found that the attainable expansion North Carolina,University
ratio of the foam produced was generally less than 10. The The use of liquid and/or supercritical carbon dioxide as a
effect of saturation temp. on the nucleation was mainly a processing Áuid is limited by its inability to solubilise highly
result of the competition between the viscosity effect and polar compounds. This problem can be alleviated by the
the solubility effect. The effect of saturation pressure on addition of carbon dioxide-philic amphiphiles. The main
the nucleation was, however, two-fold, i.e. the degree of aim of this study was to design and synthesise materials that
supersaturation and the rate of depressurisation. The effect had both strong polar moieties and highly carbon dioxide-
of lowering the depressurisation rate and changing the philic segments. Sugar-containing hydrophobic/hydrophilic
depressurisation pattern on the polymeric foams was also Áuorinated copolymers were synthesised by free-radical
investigated. By careful observation of the microstructure, polymerisation. The degree of solubility of the amphiphiles
it was concluded that the foaming process was dominated in carbon dioxide was found to be strongly inÁuenced by
by the nucleation kinetics. This study provided several the amphiphilic structure, including the polarity of the sugar
alternative techniques for controlling the microstructure head (acetal protected and deprotected) and the fraction of
and the expansion ratio of PETP and PC foams. 12 refs. carbon dioxide-philic groups. It was also found that the
TAIWAN presence of water in the carbon dioxide phase could decrease
Accession no.800596 the solubility of the hydrophilic copolymer. The dispersion
polymerisation of 2-hydroxyethyl methacrylate in carbon
dioxide was tested by using the hydrophilic amphiphile as
Item 222
a stabiliser. Spherical particles in the submicron size range
Industrial and Engineering Chemistry Research
were obtained. 14 refs.
39, No.12, Dec.2000, p.4588-96
USA
CONTINUOUS PRECIPITATION
POLYMERIZATION OF VINYLIDENE Accession no.800594
FLUORIDE IN SUPERCRITICAL CARBON
DIOXIDE: MODELING THE RATE OF Item 224
POLYMERIZATION Industrial and Engineering Chemistry Research
Charpentier P A; DeSimone J M; Roberts G W 39, No.12, Dec.2000, p.4506-9
North Carolina,State University IMPREGNATION OF POLYETHYLENE(PE)
WITH STYRENE USING SUPERCRITICAL water mixture solvent under heating to thereby recover a
CARBON DIOXIDE AS THE SWELLING AGENT non-crosslinked silicone or silicone oil-like product from
AND PREPARATION OF PE/POLYSTYRENE the waste.
COMPOSITES EUROPEAN COMMUNITY; EUROPEAN UNION; JAPAN;
Dan Li; Buxing Han WESTERN EUROPE-GENERAL
Beijing,Institute of Chemistry Accession no.800456
The impregnation of LDPE with styrene using
supercritical(SC) carbon dioxide as the swelling agent Item 227
was studied at 35C in the pressure range from 90 to 160 International Journal of Polymeric Materials
bar. The concentration of styrene in the Áuid phase ranged 47, No.4, 2000, p.657-65
from 0 to 1.668 mol/l. The soaking time varied from 4 to 36 EFFECT OF PRESSURE AND TEMPERATURE
h. In the presence of AIBN initiator, styrene polymerised ON SUPERCRITICAL CO2 DYEING OF PET-
to some extent in the soaking process, which resulted in DYEING WITH MIXTURES OF DYES
an increase in the mass uptake. LDPE/PS composites were Tusek L; Golob V; Knez Z
prepared by the further polymerisation of styrene in SC Maribor,University
carbon dioxide-swollen LDPE substrates at higher temp.
A study was made of the effects of pressure and
Using this method, the composition of the composites
temperature on the dyeing of PETP in supercritical carbon
could be controlled by the soaking time, pressure and
dioxide. The PETP was dyed with either one dye or with
styrene concentration in the Áuid phase. Some of the PS
mixtures of two or three dyes and the dyed samples studied
molecules in LDPE/PS blends entangled with the PE
by colorimetry and extraction of the dyes from the fabric.
molecules, which caused signiÀcant improvement in the
It was found that variations in pressure and temperature
impact strength, the TS and the EB. 23 refs.
gave rise to differences in colour, especially when mixed
CHINA
dyes were employed, and that the amount of dye on the
Accession no.800592 fabrics increased with increasing temperature as a result
of more rapid molecular motion of the chains and free
Item 225 volume formation in the Àbres. 12 refs.
Industrial and Engineering Chemistry Research SLOVENIA
39, No.12, Dec.2000, p.4445-9 Accession no.800194
POLYMER DEPOSITION FROM
SUPERCRITICAL SOLUTIONS FOR SENSING
Item 228
APPLICATIONS
Antec 2000.Conference proceedings.
Tepper G; Levit N
Orlando, Fl., 7th-11th May, 2000, paper 417
Virginia,Commonwealth University
CARBON DIOXIDE EXTRUSION FOAMING OF
The feasibility and potential advantages of using ENGINEERING THERMOPLASTICS
supercritical Áuid technology for the development of Gale M
advanced coatings for chemical sensor applications was Rapra Technology Ltd.
demonstrated. Polydimethylsiloxane microspheres were (SPE)
deposited onto the sensing surface of a surface acoustic
The direct injection of supercritical Áuid carbon dioxide
wave device using rapid expansion of supercritical
was evaluated for the extrusion foaming of a number
solutions. The sensor output was monitored during
of engineering thermoplastics (polyether-etherketone,
repetitive exposure to dilute hexane vapour and was found
polyphenylsulphone, styrene-maleic anhydride terpolymer,
to exhibit fast reversible behaviour. 16 refs.
high temperature polycarbonate, polyphenylene oxide and
USA
linear polypropylene). A cavity transfer mixer and a static
Accession no.800589 mixer were attached to an extruder to mix and homogenise
the liquid carbon dioxide into the molten polymer, and to
Item 226 cool the polymer to the required foaming temperature. A
Patent Number: EP 1057855 A1 20001206 simple measuring system for melt strength measurement
METHOD OF RECYCLING CROSSLINKED was also evaluated. 8 refs.
SILICONE COMPOUND WASTE EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
EUROPE
Kawamoto T
Yazaki Corp. Accession no.799932
This involves hydrolysing crosslinked silicone compound
waste by bringing the waste into contact with a solvent
having a hydroxyl group in a molecule under a supercritical
state or by bringing the waste into contact with an alcohol/
presence dramatically changes resultant foam structure. SUPERCRITICAL FLUIDS AND SILICONES:
Varying the concentration of this oligomer allows control OVER A DECADE OF APPLICATIONS
of cell size in foams. 8 refs. Wetmore P M; Krukonis V
USA Phasex Corp.
Accession no.797474 (Paint Research Association)
Supercritical Áuids (SCFs) achieve improved processing
Item 233 results that are difÀcult, if not impossible, to attain using
Polymer Preprints. Volume 40. Number 2. August 1999. traditional methods. Motivated by demands for product
Conference proceedings. and process improvements and by increasingly stringent
New Orleans, La., August 1999, p.829-30 restrictions on liquid organic solvent use, SCFs have
SYNTHESIS OF TWO-STAGE COMPOSITE been applied for over a decade to address and solve
LATEX PARTICLES BY DISPERSION scores of silicone-containing polymer problems. The
POLYMERISATION IN CARBON DIOXIDE unique combination of gas-like and liquid-like properties
Young J L; Spontak R J; DeSimone J M of SCFs is exploited for carrying out operations such as
North Carolina,Chapel Hill University; North extraction, fractionation, impregnation/deposition and
Carolina,State University recrystallisation. A broad spectrum of applications with
(ACS,Div.of Polymer Chemistry) silicone and siloxane polymers is examined and described,
including extraction of residual monomers and cyclics
The synthesis of two-stage latex particles builds on earlier from medical tubing and speciality lubricants, fractionation
research on dispersion polymerisations in supercritical of silicone adhesives and functional siloxane polymers for
CO2. In this Àrst example of a two-stage latex synthesis in improved performance, fractionation of copolymers for
CO2, composite particles containing PS and PMMA were chemical composition elucidation, and impregnation of
prepared and characterised. Two-stage latex particles are polycarbosilane polymers into composites for improving
prepared by sequential polymerisation of two monomers. oxidation resistance. 49 refs.
There are numerous possible particle morphologies, USA
or distributions of the two polymer phases in the Ànal
particles. For example, in a core-shell particle, the second- Accession no.795777
stage polymer forms a shell around the Àrst polymer core.
Other morphologies include inverted, sandwich, raspberry Item 235
and half-moon. The notation ‘PS/PMMA’ indicates that Silicones in Coatings II. Conference proceedings.
styrene was polymerised Àrst, followed by MMA. This Florida, USA, 24th-26th March 1998, paper 12
notation does not necessarily mean that PS will form SUPERCRITICAL FLUIDS:
the core and PMMA will form the shell of the particles. ENVIRONMENTALLY ACCEPTABLE
A balance between thermodynamic and kinetic factors REPLACEMENTS FOR ORGANIC SOLVENTS
determines the morphology of the resulting particles. In - THE WAY AHEAD
considering the particle morphology produced in CO2, a Howdle S
non-polar solvent, it can be predicted that the more polar Nottingham,University
PMMA should form the core with a PS shell. However, (Paint Research Association)
there are other factors to be taken into account. PMMA
Supercritical Áuids are becoming increasingly attractive
has been shown by FTIR to have speciÀc interactions with
as environmentally acceptable replacements for organic
CO2, and PMMA absorbs twice as much CO2 as PS under
solvents in chemical reactions and material processing. The
the same conditions. While PMMA’s polarity should be a
properties of supercritical Áuids are highlighted, especially
driving force to form the core, the interactions with CO2
those of supercritical CO2, which offers particular
may be a driving force to form a PMMA shell. However,
advantages for the handling of silicones; including small
both PMMA and PS are highly plasticised in CO2,
molecule reactants, polymers and stabilisers. 33 refs.
reducing the Tg of both polymers far below the typical
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
polymerisation conditions of 65 deg.C, 345 bar. As a result, EUROPE
the mobility of both polymers may allow for rearrangement
Accession no.795776
of particle morphology during the polymerisation. All of
these inÁuences make it difÀcult to predict the morphology
of these two-stage latex particles in CO2. 6 refs. Item 236
USA Silicones in Coatings II. Conference proceedings.
Accession no.797284 Florida, USA, 24th-26th March 1998, paper 11a
WHY SILICONES AND SUPERCRITICAL
FLUIDS?
Item 234 Johns K
Silicones in Coatings II. Conference proceedings. Chemical & Polymer
Florida, USA, 24th-26th March 1998, paper 13 (Paint Research Association)
Supercritical Áuid technology is an exciting but very much Details are given of the free radical polymerisation of
ignored route to new methods of surface modiÀcation. methyl methacrylate-ethyl methacrylate copolymers in
It is, however, a sister to the conventional alternatives supercritical carbon dioxide. Mention is made of the use
to hydrocarbon solvents such as radiation curing, high of polydimethyl siloxane methacrylate as a stabiliser.
solids, water-borne, powder coating. The technology can Characterisation was undertaken using NMR, SEM, DSC
be complementary to these as well as competitive. The and GPC. The effect of varying AIBN initiator on the
interest in SCF here arises from a previous need to develop composition and molecular weights of the copolymers
techniques to replace CFC solvents for the deposition of was also studied. 19 refs.
thin Àlms of Áuorinated liquids. 15 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE
EUROPE Accession no.793530
Accession no.795775
Item 240
Item 237 Journal of Polymer Science: Polymer Physics Edition
Modern Plastics International 38, No.21, 1st Nov.2000, p.2832-40
30, No.10, Oct.2000, p.25-7 SOLUBILITY OF VINYLIDENE FLUORIDE
CARBON DIOXIDE FOAMING IS EXPLORED POLYMERS IN SUPERCRITICAL CARBON
FOR THIN EXTRUSIONS DIOXIDE AND HALOGENATED SOLVENTS
Leaversuch R D Dinoia T P; Conway S E; Jong Sung Lim; McHugh M A
Johns Hopkins University; Korea,Institute of Science &
We are told that the use of carbon dioxide as a foaming
Technology; Virginia,Commonwealth University
agent in extruded products made with commodity resins
is gradually Ànding its market niche. This article discusses The cloud point behaviours of PVDF and vinylidene
carbon dioxide in foam extrusion in detail, with many Áuoride-22 mol % hexaÁuoropropylene copolymer were
examples. studied at temps. up to 250C and pressures up to 3000 bar
RAPRA TECHNOLOGY LTD.; TREXEL; ECLIPSE in supercritical carbon dioxide and halogenated solvents.
BLING SYSTEMS; ALUSUISSE COMPOSITES; Cloud point pressures for both polymers decreased as the
DUMAPLAST; POLYMER PROCESSING solvent polarisability, polar moment per molar volume and
INSTITUTE; TORONTO,UNIVERSITY density increased. It was, however, extremely difÀcult to
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA; dissolve either Áuoropolymer in chlorotriÁuoromethane,
WESTERN EUROPE which had a large polarisability and a small dipole
Accession no.795336 moment. Carbon dioxide was an effective solvent because
it complexed with the C-F dipole at low temps. where
energetic interactions Àxed the phase behaviour. Polymer
Item 238
structure also had a marked effect on the cloud point
Industrial and Engineering Chemistry Research
pressure. 47 refs.
39, No.11, Nov.2000, p.4020-3
KOREA; USA
CONTINUOUS DISTRIBUTION KINETICS FOR
THE DEGRADATION OF POLYSTYRENE IN Accession no.792538
SUPERCRITICAL BENZENE
Karmore V; Madras G Item 241
Indian Institute of Science Analytical Chemistry
The degradation kinetics of PS in supercritical benzene 72, No.17, 1st Sept.2000, p.4230-4
was studied at various temperatures. The time evolution POLYMER NMR CELL FOR THE STUDY OF
of the MWD was obtained by analysing the samples HIGH-PRESSURE AND SUPERCRITICAL FLUID
with GPC. Activation energies were determined from the SOLUTIONS
temperature dependence of the rate coefÀcients. 24 refs. Wallen S L; Schoenbachler L K; Blatchford M A
INDIA North Carolina,University
Accession no.794849 NMR offers researchers unique, highly localised
molecular information. The importance of this technique
is well established in studies using chemical shift, spin
Item 239
coupling, and relaxation times providing detailed structural
Macromolecular Rapid Communications
information, determining chemical equilibria and kinetics,
21, No.15, 23rd Oct.2000, p.1019-23
and understanding molecular dynamic processes. However,
COPOLYMERISATION OF METHYL AND
the widespread application of NMR spectroscopy to high-
ETHYL METHACRYLATE IN SUPERCRITICAL
pressure liquids and supercritical Áuids has been limited
CARBON DIOXIDE
due to the complexity of the necessary instrumentation.
Giles M R; Hay J N; Howdle S M
One approach to these studies is to build a dedicated
Nottingham,University; Surrey,University
that are best fulÀlled by blocked copolymers. A number by further cooling in a static mixer heat exchanger. Using
of lactide-co-glycolide polymers blocked distribution this arrangement, foams can be extruded from a number
of the co-monomers by NMR spectroscopy and powder of engineering polymers including polyaryletherketone.
diffraction. The molar ratios are determined by 1H NMR In addition to the ability to foam engineering polymers,
spectroscopy to verify the manufacturer’s declarations of carbon dioxide as blowing agent should give considerable
the purchased specimens. Additionally, the block length economic savings for commodity plastics foaming in
is determined by application of 13C NMR. Therefore, a comparison to chemical blowing agents. 5 refs.
method is modiÀed and evaluated in order to calculate EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
the length of lactide and glycolide sequences in the EUROPE
polymer. The impact of synthesis conditions on block Accession no.777093
length and crystallinity, and the impact of the blocking
on both crystallinity and solubility of the polymers, are
Item 261
examined. 11 refs.
Polymer Degradation and Stability
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
WESTERN EUROPE
65, No.3, 1999, p.373-86
CHARACTERISTICS OF POLYETHYLENE
Accession no.778044 CRACKING IN SUPERCRITICAL WATER
COMPARED TO THERMAL CRACKING
Item 259 Moriya T; Enomoto H
Patent Number: EP 1006143 A1 20000607 Tohoku Electric Power Co.Inc.; Tohoku,University
APPARATUS FOR DECOMPOSITION AND
PE cracking obtained from hydrothermal experiments with
RECOVERY OF POLYURETHANE RESIN
supercritical water was compared to water-free thermal
Kodama K; Murayama K; Kumaki T; Kasuya F;
cracking. The degradation mechanism of HDPE and the
Nagase Y; Nakata M; Nishida S
contribution of supercritical water to degradation were
Takeda Chemical Industries Ltd.; Kobe Seiko Sho KK
also considered by analysing the products in the aqueous
This includes a Áuidiser, which Áuidises the polyurethane phase after the reaction. 21 refs.
resin as a target compound of hydrolysis decomposition, JAPAN
a reactor, which hydrolyses the Áuidised target compound Accession no.776428
with either a supercritical water or high-temperature
high-pressure water to a decomposition product mixture,
a water supplier, which feeds either supercritical water or Item 262
high-temperature high-pressure water to the reactor and a Polymer Process Engineering ‘97. Conference
post-processor, which causes the decomposition product proceedings.
mixture discharged from the reactor to be subjected to a London, July 1997, p.197-201
post treatment procedure, such as dehydration, addition, CHEMICAL ASSIST FOAMING AND THE ROLE
distillation, separation, or liquid separation, to recover OF SUPERCRITICAL FLUIDS IN EXTRUSION
a polyamine compound and/or a polyol compound. Reedy M E
The required energy cost is reduced as is the size of Reedy International Corp.
the machine. Foreign substances are removed from the (Institute of Materials)
shredder dust and the required quantities of substances Processing and properties of polymers are the two
for decomposition are reduced. most important criteria that are many times in conÁict
EUROPEAN COMMUNITY; EUROPEAN UNION; JAPAN; with each other. The processor looks for the largest
WESTERN EUROPE-GENERAL processing window while the designer looks for good
Accession no.777712 surfaces, optimum density reduction, excellent thermal
properties and great impact behaviour. Now, chemical
Item 260 foam assist (CFA) technology enables both commodity
British Plastics and Rubber and engineering polymers to process more easily and
May 2000, p.4-9 with improved properties for a wide variety of extrusion
FOAM EXTRUSION OF ENGINEERING AND processes. Carbon dioxide is used extensively as a physical
COMMODITY POLYMERS USING CARBON blowing agent in the production of thermoplastic foams.
DIOXIDE AS A BLOWING AGENT For example, in the extrusion of foam sheet, carbon
Gale M dioxide alone or in conjunction with other gases can
Rapra Technology Ltd. produce lightweight products with excellent physical
properties. Recent studies have shown that CO2 has
The use of carbon dioxide as blowing agent has been unique low pressure solubility. In most polymers, CO2
shown to be feasible on a laboratory scale using a when pressurised to 1,700 psi becomes a supercritical Áuid
conventional extruder retroÀtted with a Cavity Transfer and acts as a solvent resulting in a lowering of the glass
Mixer to mix gas and polymer with some cooling, followed transition temperature and improved polymer melt Áow
characteristics. During transition between a supercritical terephthalate and ethylene glycol) was investigated
Áuid and a gas, the CO2 will absorb heat energy, improve and the proper conditions for the depolymerisation
melt cooling and consequently facilitate increased of PETP with supercritical methanol established. The
extrusion rates. The improved melt Áow characteristics maximum yield of dimethyl terephthalate was 94% and
and heat energy absorption result in improved physical that of ethylene glycol was 80%. Supercritical methanol
properties of extruded board and sheet materials. 8 refs. minimised secondary decomposition or side reactions of
USA the monomers. 8 refs.
Accession no.775992 JAPAN
Accession no.772137
Item 263
Materials World Item 266
8, No.5, May 2000, p.10-2 Macromolecules
CO2 UNDER PRESSURE - A CLEAN SOLUTION 33, No.6, 21st March 2000, p.1917-20
FOR POLYMER PROCESSING DISPERSION POLYMERIZATION OF 1-VINYL-2-
Cooper A; Howdle S PYRROLIDONE IN SUPERCRITICAL CARBON
Liverpool,University; Nottingham,University DIOXIDE
Carson T; Lizotte J; Desimone J M
The use of supercritical carbon dioxide during the
North Carolina,State University
synthesis of polymers is examined, and its ability to
produce novel materials which are difÀcult to obtain by The low molec.wt. polymeric surfactant poly(1,1-
more conventional methods. Supercritical carbon dioxide, dihydroperÁuorooctyl acrylate)(polyFOA) was used in
as a solvent for polymer synthesis, also addresses concerns the dispersion polymerisation of 1-vinyl-2-pyrrolidone in
over volatile organic solvent emissions and the generation supercritical carbon dioxide. It was found that increasing
of aqueous waste streams. It can be used to produce concentrations of polyFOA yielded a decrease in
a variety of polymers with tailored properties such as polymer particle diameter, while increasing the monomer
polymeric implants with modiÀed bioproperties, and the concentration produced an increase in particle size. No
building macroporous monoliths. signiÀcant change was observed in the particle morphology
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN for polymerisations conducted at different pressures. 20
EUROPE refs.
Accession no.773641 USA
Accession no.771863
Item 264
Patent Number: US 6025459 A1 20000215 Item 267
SYNTHESIS OF POLYAMIDES IN LIQUID AND Macromolecules
SUPERCRITICAL CO2 33, No.5, 7th March 2000, p.1565-9
DeSimone J; Givens R; Ni Y DISPERSION POLYMERISATION OF
North Carolina,University ACRYLONITRILE IN SUPERCRITICAL
A nylon salt is condensed in carbon dioxide to form CARBON DIOXIDE
a polyamide and water. A polyamide is formed by Shiho H; DeSimone J M
polymerising a lactam monomer in carbon dioxide to JSR Corp.; North Carolina,University
form a polyamide. Details are given of the dispersion polymerisation
USA of acrylonitrile in carbon dioxide using a styrene-
Accession no.773536 dihydroperfluorooctyl acrylate block copolymer as a
stabiliser. The effects of the initial concentrations of
acrylonitrile and the stabiliser and the reaction pressure on
Item 265
the resulting size of the colloidal particles are discussed.
Polymer Journal (Japan)
31 refs.
32, No.2, 2000, p.178-81
JAPAN; USA
RECOVERY OF CONSTITUENT MONOMERS
FROM POLYETHYLENE TEREPHTHALATE Accession no.771261
WITH SUPERCRITICAL METHANOL
Sako T; Okajima I; Sugeta T; Otake K; Yoda S; Item 268
Takebayashi Y; Kamizawa C Journal of Vinyl and Additive Technology
Japan,National Institute of Materials & Chemical 6, No.1, March 2000, p.39-48
Research CHALLENGE TO FORTYFOLD EXPANSION
The inÁuence of temperature, pressure and reaction time OF BIODEGRADABLE POLYESTER FOAMS
on the recovery of the constituent monomers (dimethyl BY USING CARBON DIOXIDE AS A BLOWING
monomer dimethyl 2,6-naphthalene dicarboxylate (DMN) Áuid before subsequent reaction to the diester could take
and oligomer. The oligomer was deÀned as a product place. 11 refs.
which was hydrolysed with sodium hydroxide aqueous USA
solution to disodium 2,6-naphthalene dicarboxylate and Accession no.756188
ethylene glycol. The liquid phase contained ethylene glycol
monomer, DMN monomer and oligomer. 5 refs.
JAPAN
Item 280
Cellular Polymers
Accession no.758005 18, No.5, 1999, p.301-13
MEASUREMENT AND PREDICTION
Item 278 OF BLOWING AGENT SOLUBILITY IN
Industrial and Engineering Chemistry Research POLYSTYRENE AT SUPERCRITICAL
38, No.10, Oct.1999, p.3655-62 CONDITIONS
POLYMER COATINGS BY RAPID EXPANSION Seong Uk Hong; Albouy A; Duda J L
OF SUSPENSIONS IN SUPERCRITICAL Pennsylvania,State University
CARBON DIOXIDE
Partition coefÀcients of several blowing agents (HFCs
Jae-Jin Shim; Yates M Z; Johnston K P
AND HCFCs) in PS at the infinitely dilute solvent
Texas,University
concentration region were measured using capillary
Suspensions of poly(2-ethylhexyl acrylate) in supercritical column inverse gas chromatography. The measured
carbon dioxide formed by dispersion polymerisation with partition coefÀcients were then used to calculate binary
a polydimethylsiloxane-based surfactant were sprayed interaction parameters in the perturbed soft chain
to form uniform Àlms. The viscosity reduction of the theory(PSCT). Using these values, solubility data of
dispersed phase caused by dissolved carbon dioxide was blowing agents in the Ànite solvent concentration region
crucial for atomisation to produce Àne droplets and for were predicted as a function of pressure in accordance
coalescence and levelling on the surface to form a uniform with the PSCT. The prediction results from the PSCT were
Àlm. Resuspension of the polymer after depressurisation comparable with the experimental data in the literature.
and repressurisation led to fairly large droplets in the In addition, the PSCT was found to be very sensitive to
suspension which produced a Àlm nearly as uniform the partition coefÀcient and, hence, the binary interaction
as the original one. Inferior films were produced by parameter. 21 refs.
suspensions without surfactant. Unlike previous studies of USA
rapid expansion of homogeneous polymer solutions and Accession no.755884
related techniques, Àlms were produced from concentrated
polymer mixtures without any organic solvent. 24 refs.
USA
Item 281
Macromolecules
Accession no.756190 32, No.9, 4th May 1999, p.3167-9
SOLID STATE POLYMERISATION OF
Item 279 POLYCARBONATES USING SUPERCRITICAL
Industrial and Engineering Chemistry Research CARBON DIOXIDE
38, No.10, Oct.1999, p.3622-7 Gross S M; Flowers D; Roberts G; Kiserow D J;
SUPERCRITICAL FLUID SEPARATION FOR DeSimone J M
SELECTIVE QUATERNARY AMMONIUM North Carolina,University; US,Army Research OfÀce
SALT PROMOTED ESTERIFICATION OF
Polycarbonate prepolymer was synthesised by step-growth
TEREPHTHALIC ACID
polymerisation of bisphenol A and diphenyl carbonate
Brown J S; Lesutis H P; Lamb D R; Bush D;
using an aqueous solution of lithium hydroxide as the
Chandler K; West B L; Liotta C L; Eckert C A;
initiator. The prepolymer formed beads when dripped
Schiraldi D; Hurley J S
into room-temperature water.The beads were crystallised
Georgia,Institute of Technology; KoSa; Buckeye
by treatment with supercritical carbon dioxide. The
Technologies
crystallisation of the low molecular weight (2500)
A study was conducted of the selective removal of a polycarbonate was studied as a function of time and
desired reaction intermediate with a supercritical Áuid in temperature. DSC gave melting point, Tg, enthalpy of
a new synthesis route to PETP, avoiding ethylene glycol. fusion and crystallinity. The crystallised prepolymer was
The esteriÀcation of terephthalic acid with ethylene oxide then polymerised in the solid state at 3C below the onset
in a supercritical Áuid was successfully catalysed using of melting (160C) and samples removed after 2, 4, 6,
a series of quaternary ammonium salts to form mono(2- and 12 hours. Because the melting point increased with
hydroxyethyl terephthalate). This desired monoester was polymerisation the process was repeated at 180C, 205C,
removed from the non-volatile bed of terephthalic acid 230C and 240C. It was repeated also with a 5000 molecular
and catalyst by continuous extraction with supercritical weight prepolymer. The development of crystallinity,
molecular weight and melting point over 12h is shown. crystallinity after being subjected to scCO2. The various
12 refs. crystalline forms induced by CO2 in syndiotactic PS
USA are characterised via FTIR spectra. FTIR spectroscopy
Accession no.754788 is also used to measure the kinetics of CO2-induced
crystallisation in these polymers. 19 refs.
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
Item 282 EUROPE
Journal of Polymer Science: Polymer Physics Edition Accession no.749592
37, No.19, 1st Oct.1999, p.2771-81
RHEOLOGY OF MOLTEN POLYSTYRENE
WITH DISSOLVED SUPERCRITICAL AND Item 284
NEAR-CRITICAL GASES Antec ‘99. Volume II. Conference proceedings.
Kwag C; Manke C W; Gulari E New York City, 2nd-6th May 1999, p.2811-5. 012
Wayne State,University MORPHOLOGY DEVELOPMENT IN CARBON
DIOXIDE ASSISTED POLYMER BLENDING IN
The viscosities of PS melts containing three different BATCH AND CONTINUOUS PROCESSES
dissolved gases, carbon dioxide and the refrigerants Elkovitch M D; Lee L J; Tomasko D L
R134a (1,1,1,2-tetrafluoroethane) and R152a (1,1- Ohio,State University
difluoroethane) were investigated at pressures up to (SPE)
20 MPa. These pressures reached near-critical and
supercritical conditions for the three gas components and The compatibility of individual homopolymers is one of the
produced polymer-gas solutions containing up to 10 wt % most important parameters inÁuencing polymer blending.
gas. The measurements were performed in a sealed high- Often blending involves components with vastly different
pressure capillary rheometer at 150 and 175C and at shear viscosities and interfacial tensions. Supercritical carbon
rates ranging from 1 to 2000/s. Very large reductions in dioxide can be added to polymer melts as a processing
melt viscosity were observed at high gas loading, 10 wt aid such that effective polymer blending will occur. A
% R152a at 150C reducing the Newtonian viscosity by blend system of a high viscosity PMMA and low viscosity
nearly three orders of magnitude relative to pure PS. The PS is analysed. Carbon dioxide has a higher afÀnity for
viscosity data for all three PS-gas systems followed ideal PMMA than for PS. Therefore, a greater plasticising effect
viscoelastic scaling, whereby the set of viscosity curves will occur for the PMMA than for the PS. The improved
for a polymer-gas system could be scaled to a master curve results in polymer blending are shown. The morphology
of reduced viscosity versus reduced shear rate identical to development of the polymer blends is analysed in a
the viscosity curve for the pure polymer. The viscoelastic high-pressure batch mixer and the continuous extrusion
scaling factors representing the effect of dissolved gas process. 13 refs.
content on rheological behaviour were found to follow USA
roughly the same variation with composition for all three Accession no.749543
PS gas systems. 20 refs.
USA
Item 285
Accession no.754124 Antec ‘99. Volume II. Conference proceedings.
New York City, 2nd-6th May 1999, p.2806-10. 012
Item 283 EXTRUSION OF PE/PS BLENDS WITH
Antec ‘99. Volume II. Conference proceedings. SUPERCRITICAL CO2 IN A TWIN-SCREW
New York City, 2nd-6th May 1999, p.2433-5. 012 EXTRUDER AND A TWIN/SINGLE TANDEM
APPLICATIONS OF FTIR SPECTROSCOPY TO SYSTEM
CHARACTERISE POLYMERS PROCESSED Lee M; Tzoganakis C; Park C B
WITH SUPERCRITICAL CARBON DIOXIDE Waterloo,University; Toronto,University
Kazarian S G (SPE)
London,Imperial College of Science,Technology & The effects of dissolved supercritical carbon dioxide on
Medicine the viscosity and morphological properties are investigated
(SPE) for PE, PS and their blends in a twin-screw extruder and
Supercritical CO2 can induce crystallisation of amorphous a twin/single screw tandem system. The viscosities of the
polymers. Molecular level insight into the microstructures polymer/CO2 and the blend/CO2 solutions wae measured
of CO2-processed polymers is needed to form a basis using a wedge die mounted on the twin-screw extruder.
for utilisation and optimisation of supercritical fluid The effect of CO2 on the morphology of PE/PS blends is
processing of polymeric materials. FTIR spectroscopy is investigated using a twin/single screw tandem system. This
applied to elucidate the morphology and microstructure system allows for preferential dissolution of the CO2 into
of polymers processed with supercritical CO2. FTIR the matrix and/or dispersed polymer phase. By introducing
spectra of syndiotactic PS show an increased degree of devolatilisation to the tandem system, the morphological
in all runs regardless of reactor type. The results show be formed in SCF CO2. Fe(acac)3 is deposited closer to
SCWO to be a promising remediation alternative to the the surface of the LDPE plaques. In general, increasing
waste tyre problem. 32 refs. infusion temperature increases concentration of Fe(acac)3
USA deposited within LDPE. The thermal degradation of
Accession no.732310 LDPE-Fe(acac)3 composites in the 400-450 deg.C range
is slower in comparison to virgin LDPE. 13 refs.
USA
Item 295
Accession no.730044
Industrial and Engineering Chemistry Research
38, No.4, April 1999, p.1391-5
DECOMPOSITION OF PREPOLYMERS AND Item 297
MOULDING MATERIALS OF PHENOL RESIN IN ACS Polymeric Materials Science & Engineering.
SUBCRITICAL AND SUPERCRITICAL WATER Volume 74. Conference proceedings.
UNDER AN ARGON ATMOSPHERE New Orleans, La., Spring 1996, p.260-1. 012
Suzuki Y; Tagaya H; Asou T; Kadokawa J; Chiba K EFFECT OF ADDED HELIUM ON PARTICLE
Yamagata,University; Sumitomo Bakelite Co.Ltd. SIZE AND PARTICLE SIZE DISTRIBUTION OF
DISPERSION POLYMERISATIONS OF METHYL
Seven phenol resin prepolymers and moulding materials
METHACRYLATE IN SUPERCRITICAL
were decomposed into their monomers by reactions at
CARBON DIOXIDE
523-703K under an argon atmosphere in subcritical and
Hsaio Y-L; DeSimone J M
supercritical water. The decomposition reactions were
North Carolina,University
accelerated by the addition of sodium carbonate. 28 refs.
(ACS,Div.of Polymeric Materials Science & Engng.)
JAPAN
Accession no.732130 The synthesis of spherical polymers particles with a range
of diameters has been an active area of research due to the
wide variety of applications for such materials. Practical use
Item 296 of these particles includes standards for the determination
Polymer Preprints. Volume 40. Number 1. March 1999. of pore size and the efÀciency of Àlters, column packing
Conference proceedings. material for chromatographic separation, support materials
Boston, Ma., March 1999, p.228-9. 012 for biochemicals, toner, cosmetics, drug delivery vehicles,
METAL-POLYMER COMPOSITES IN etc. Control of particle size and uniformity has been a
SUPERCRITICAL FLUID CARBON DIOXIDE major area of interest. It is particularly challenging to
Rajagopalan P; McCarthy T J prepare monodisperse polymer particles in the micron
Amherst,Massachusetts University size range. Dispersion polymerisation is one of the best
(ACS,Div.of Polymer Chemistry) synthetic methods for the preparation of uniform particles
The synthesis of metal-polymer nanocomposites in in the micron range. As a means to control particle size and
supercritical Áuid (SCF) carbon dioxide has recently particle size distribution, a number of investigations has
been reported. Supercritical Áuids have very attractive focused on the inÁuence of the reaction initiator, monomer
properties enabling them to be viable reaction media, some and stabiliser concentrations; reaction temperature, and
of these properties include gas-like diffusivity combined cosolvents. These studies concluded that the nucleation
with a liquid-like density and a tunable solvent strength. period plays an important role in determining particle size
Previously, an organo-platinum complex was dissolved in characteristics. One of the factors that strongly inÁuence
SCF CO2 under a given set of conditions and then infused the nucleation period is the solvency of the reaction
within a polymer substrate (PTFE). Upon further reduction medium. There are numerous examples using cosolvents
of the organoplatinum complex, nanoscale platinum to manipulate the particle size and particle size distribution
particles were deposited through the entire polymer through changing the solvency of the reaction media. It is
substrate. The infusion of an additive (dissolved in SCF demonstrated that it is possible to control the particle size
CO2) into a SCF CO2 swollen polymer substrate has been characteristics of the dispersion polymerisation of methyl
studied. The additive was iron acetylacetonate, (Fe(acac)3), methacrylate in supercritical CO2 by varying the amount
and LDPE was chosen as the polymer substrate. Fe(acac)3 of a gaseous cosolvent - helium. 31 refs.
has been reported to impart Áame retardant properties to USA
polymeric substrates, thus satisfying another objective Accession no.724895
which is to observe thermal degradation properties of
metal/polymer composites. Fe(acac)3, in addition to
being a Áame retardant additive, is also a precursor to
iron oxide. Iron oxide, a dehydrogenation catalyst, can
promote char formation during thermal degradation of
polymers, thus enhancing their Àre retardant properties.
It is demonstrated that HDPE-Fe(acac)3 composites can
procedures involving mixing or kneading the modiÀer of model polymers in selected fluid systems, and is
with the polymer with the application or generation of conducting extraction studies on both simulated and real
heat which is often detrimental to the stability of the paper/plastic waste samples. The miscibility and extraction
modiÀer itself or can even degrade the polymer. As an of selected polymers using carbon dioxide and alkane
alternative method, dissolution of a polymer in a solvent mixtures are described. 6 refs.
followed by addition of the modiÀer can be successful, USA
but exhaustive removal of the solvent is often difÀcult, Accession no.724880
and the residual solvent present in the modiÀed polymer
can affect the intended use of the polymer and can present
environmental and safety problems for the end product. Item 303
Supercritical Áuids offer an inexpensive, non-toxic, non- ACS Polymeric Materials Science & Engineering.
Áammable alternative to typical organic solvents and Volume 74. Conference proceedings.
these Áuids have the ability to swell and plasticise some New Orleans, La., Spring 1996, p.230. 012
polymers, resulting in a signiÀcant reduction of the glass FORMATION OF MICROCELLULAR
transition temperature of the polymer. The adsorption of POLYMERIC MATERIALS VIA
chemically reactive modiÀers/catalysts into the polymer POLYMERISATION IN CARBON DIOXIDE
is described. Under modiÀcation conditions, the modiÀers Parks K; Sparacio D; Beckman E J
react with different polymer pendant groups adding new Pittsburgh,University
chemical functionality to the polymeric material. For (ACS,Div.of Polymeric Materials Science & Engng.)
example, in this process, long chain hydrophobic groups Microcellular materials have been produced via phase
could be added to hydrophilic polymers resulting in new separation in a liquid solution, via gas expansion in molten
materials with distinctly different chemical and physical polymers and via combinations of both approaches. Phase
properties. 6 refs. separation can be accomplished via a temperature quench,
USA pressure quench or the addition of a non-solvent to a single
Accession no.724888 phase polymer-solvent mixture. Phase separation can also
be induced by an increase in molecular weight or crosslink
density, such as in the polymerisation of ion exchange
Item 302
resin systems in solution. While the two gas expansion
ACS Polymeric Materials Science & Engineering.
techniques produce what is considered to be macrocellular
Volume 74. Conference proceedings.
foam, it has been shown that when a polymer sample is
New Orleans, La., Spring 1996, p.2331-2. 012
saturated with gas, then rapidly heated to a point above the
HIGH-PRESSURE MISCIBILITY AND
glass transition, a microcellular material is produced. The
EXTRACTION OF POLYMERIC COATINGS
formation of microcellular materials via generation of a
AND HOT-MELT ADHESIVES WITH CARBON
PU network in carbon dioxide, followed by solvent (CO2)
DIOXIDE AND PENTANE MIXTURES
removal has been investigated. It has been shown that the
Kiran E; Malki K; Pohler H
PU precursors, polyols and isocyanates, are miscible with
Maine,University
CO2 above certain threshold pressures. The polymerisation
(ACS,Div.of Polymeric Materials Science & Engng.)
of the precursors can be conducted under conditions where
More than 150 million tons of municipal solid waste is the system is initially a single homogeneous phase. Here,
generated each year in the USA; of this, paper and paper the reaction pressure, type of isocyanate reacted with a
board accounts for 40% and plastics account for 8% by particular polyol blend, ratio of diol to crosslinker in the
weight. A major source of waste is packaging materials polyol blend, reaction temperature and foaming agent
(about 32%) of which paper and paper board, and plastics are varied. Bulk densities, cell sizes and cell densities of
represent 18 and 3 %, respectively. The major plastic the resultant foams are measured. It is examined how the
components found in the municipal solid waste are mechanism for phase separation affects the pore size of
LDPE, HDPE, PS, PP and PETP. A variety of polymers the foams. There is a variety of possible mechanisms for
is also found in paper wastes as they are used as barrier introducing pores in a polymer/solvent mixture, several
film coatings, hot-melt adhesives, pressure-sensitive of which are accessible to this system.
adhesives, laser printer and photocopier toner inks and USA
binders in paper coatings. These polymeric constituents Accession no.724879
often represent difÀculties in recycling of reclamation
of secondary Àbres from waste paper. The University of
Maine has been involved in applications of supercritical
Áuids in the polymers, pulp and paper and forest products
industries. Some recent activity has been focused on
extraction of polymeric constituents from mixed plastics
and/or from paper/polymer composites. For this purpose
it has generated a fundamental data base on the miscibility
CO2 are compared to similar behaviour in other supercritical (ACS,Div.of Polymeric Materials Science & Engng.)
Áuids that exhibit certain physicochemical properties similar
Supercritical CO2 has been found to be a suitable substitute
to CO2. 16 refs.
for organic solvents in polymerisation reactions in which
USA
CO2 is also a reactant. Furthermore, the use of CO2 (at
Accession no.724852 pressures greater than 700 psi) results in higher selectivity
for polycarbonate versus polyether formation. In addition,
Item 307 the advantage of using supercritical carbon dioxide is that
ACS Polymeric Materials Science & Engineering. it is as effective a solvent as inert organic solvents, such
Volume 74. Conference proceedings. as methylene chloride, for the copolymerisation, yet it is
New Orleans, La., Spring 1996, p.433-4. 012 environmentally benign. 7 refs.
FREE RADICAL DISPERSION USA
POLYMERISATIONS IN LIQUID CARBON Accession no.724784
DIOXIDE USING A REDOX INITIATOR
Dessipri E; Hsiao Y-L; Mathes A C J; Shaffer K A;
Item 309
DeSimone J M
ACS Polymeric Materials Science & Engineering.
North Carolina,University
Volume 74. Conference proceedings.
(ACS,Div.of Polymeric Materials Science & Engng.)
New Orleans, La., Spring 1996, p.430. 012
Supercritical carbon dioxide has proved to be an excellent SUPERCRITICAL CO2 AS A MONOMER
medium for the performance of free radical polymerisation AND SOLVENT: POLYCARBONATES FROM
reactions because of obvious environmental and toxicity CYCLOHEXENE OXIDE AND CARBON
advantages afforded by CO2 combined with its inertness DIOXIDE
towards free radicals, low viscosity and the ability to obtain Costello C A; Berluche E; Han S J; Sysyn D A;
high initiator efÀciencies. The use of carbon dioxide for Super M S; Beckman E J
homogeneous polymerisations is rather limited because Exxon Research & Engineering Co.;
of the insolubility of most common polymers in CO2. On Pittsburgh,University
the other hand, dispersion polymerisation of a variety of (ACS,Div.of Polymeric Materials Science & Engng.)
oleÀnic monomers can be carried out in carbon dioxide to
Supercritical CO2 has received much attention in
yield polymers in the form of free Áowing powders made
extraction processes and in fractionation of polymers.
of uniform spherical particles. When considering dispersion
Recently, there has been much interest in replacing
polymerisations at lower temperatures, two issues are of prime
organic polymerisation solvents with supercritical CO2
concern: the kinetics of polymerisation should allow for the
in various types of polymerisation processes due to the
formation of high molecular weight materials at high yields
low toxicity CO2 possesses. Success has been realised
and within reasonable reaction times, and the stabilisers used
in solution polymerisation, dispersion polymerisation
must be effective in liquid CO2. The successful polymerisation
and inverse emulsion polymerisation. There is interest
of methyl methacrylate at 30 deg.C using a low temperature
in using supercritical CO2 as a monomer as well as a
initiator, 2,2’-azobis(4-methoxy-2,4-dimethyl valeronitrile),
polymerisation solvent, thus providing a route to polymers
and a PDMS macromonomer as stabiliser in liquid C02.
using an inexpensive C1 feed. The concept of using
One system that can be used with organic solvents is the
supercritical CO2 as a reactant and solvent has been
combination of BPC N,N-dialkylanilines. The rate of BPO
demonstrated in small molecule organic chemistry. The
decomposition is reported to increase by at least three orders
application of CO2 as a monomer in polymerisation has
of magnitude in the presence of dialkylanilines. The use of this
been reviewed. Most of the reactions reported are run
initiating system for the dispersion polymerisation of methyl
at subcritical conditions and employ organic solvents
methacrylate in carbon dioxide using various polymeric steric
in addition to CO2. Recent work on Ni(0)-catalysed
stabilisers is described. 13 refs.
alternating cycloaddition copolymerisation of acyclic
USA
diynes with CO2 also employs additional organic solvent.
Accession no.724785 The alternating copolymerisation of CO2 and epoxides
using zinc-based catalysts, which produces a polycarbonate
Item 308 with some ether linkages, is investigated. Cyclic carbonate
ACS Polymeric Materials Science & Engineering. is also produced in appreciable amounts. The development
Volume 74. Conference proceedings. of a CO2-soluble Zn catalyst for cyclohexene oxide/CO2
New Orleans, La., Spring 1996, p.431-2. 012 copolymerisation in the absence of any additional organic
ZINC CATALYSTS FOR THE solvents is reported, together with the pressure and
COPOLYMERISATION OF EPOXIDES AND temperature dependence on the conversion and selectivity
CARBON DIOXIDE TO POLYCARBONATES of the reaction. 12 refs.
Darensburg D J USA
Texas A & M University Accession no.724783
(b) supplying a supercritical Áuid capable of swelling 89, No.4, 1998, p.647-56
the polymer to the mixture under a temperature and a DYEING OF POLYOLEFIN FIBRES IN
pressure sufÀcient to maintain the Áuid in a supercritical SUPERCRITICAL CARBON DIOXIDE. I.
state, (c) allowing the supercritical Áuid to penetrate and THERMOMECHANICAL PROPERTIES OF
liquefy the polymer while maintaining temperature and POLYOLEFIN FIBRES AFTER TREATMENT
pressure sufÀcient to maintain the Áuid in a supercritical IN CARBON DIOXIDE UNDER DYEING
state, and (d) rapidly releasing the pressure to solidify the CONDITIONS
polymer around the core material to form a microcapsule. Bach E; Cleve E; Schollmeyer E
This method requires neither that the polymer nor core Deutsches Textilforschungszentrum Nord-West eV
materials to be soluble in the supercritical Áuid and can be
Viscoelastic properties of gel-spun PE and PP Àbres after
used to rapidly and efÀciently microencapsulate a variety
treatment in supercritical carbon dioxide at 280 bar were
of materials for a variety of applications.
examined to determine the optimum conditions for dyeing
USA
without causing Àbre damage. Melting, shrinkage and
Accession no.723418 thermomechanical properties of PE and PP Àbres after
treatment in carbon dioxide was presented. 18 refs.
Item 314 EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
WESTERN EUROPE
Journal of Polymer Science : Polymer Physics Edition
37, No.6, March 1999, p.553-60 Accession no.721405
HDPE FRACTIONATION WITH
SUPERCRITICAL PROPANE Item 317
Britto L J D; Soares J B P; Penlidis A; Krukonis V ACS Polymeric Materials Science & Engineering,
Waterloo,University; Phasex Corp. Spring Meeting 1998. Volume 78. Conference
Supercritical propane was used to fractionate HDPE by proceedings.
molecular weight and short chain branching. The use Dallas, Tx., Spring 1998, p.155. 012
of this solvent to obtain fractions of uniform molecular DECOMPOSITION OF MODEL COMPOUNDS
weight or chemical composition without generating AND PREPOLYMERS OF PHENOL RESIN
hazardous solvent waste is discussed. 20 refs. WASTE WITH SUPERCRITICAL WATER
CANADA; USA Tagaya H; Suzuki Y; Karasu M; Kadokawa J; Chiba K
Yamagata,University
Accession no.723319
(ACS,Div.of Polymeric Materials Science & Engng.)
Phenol resin is known to be a thermosetting thermally
Item 315
stable resin. It has been found that model compounds of
Journal of the Textile Institute - Part 1: Fibre Science
phenol resin wastes such as p- and o-bis(hydroxyphenyl)
and Textile Technology
methanes are decomposed into phenol and cresol easily by
89, No.4, 1998, p.657-68
reaction with supercritical water. However, condensation
DYEING OF POLYOLEFIN FIBRES IN
reaction giving trimer is also conÀrmed. By the addition of
SUPERCRITICAL CARBON DIOXIDE. II. THE
small amounts of NaCl, product yield increases, however
INFLUENCE OF DYE STRUCTURE ON THE
basic compounds are more effective additives than NaCl.
DYEING OF FABRICS AND ON FASTNESS
The chemical participation of water is suggested from the
PROPERTIES
structure of reaction intermediates which are obtained by
Bach E; Cleve E; Schollmeyer E
the reaction at mild conditions. Prepolymers of phenol
Deutsches Textilforschungszentrum Nord-West eV
resin are also decomposed into their monomers even by the
Dyeing of gel-spun PE Àbres of low and high draw ratio, reaction at below critical temperature of water. Addition
PP Àbres, and PETP Àbres was carried out in supercritical of basic compounds are also effective and yields of
carbon dioxide at 280 bar and in water under optimum monomers are greater than 90% in the case of prepolymers
dyeing conditions at 120 C. The inÁuence of the chemical of p-isopropylphenol resin. This abstract includes all the
structure of different disperse azo and anthraquinone dyes information contained in the original article.
on the dye uptake and also on the washing-, sublimation-, JAPAN
and light-fastness of the Àbres was presented. 23 refs. Accession no.719085
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
WESTERN EUROPE
Accession no.721406
Item 316
Journal of the Textile Institute - Part 1: Fibre Science
and Textile Technology
are forcing many chemical companies to re-evaluate the chromatography process and to take advantage of the
possibility of replacing existing chemical technology variation of the solvent properties of supercritical Áuids
by supercritical fluids. These fluids, and particularly is proposed. Extended abstract only.
supercritical CO2, scCO2, are becoming increasingly EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;
attractive as solvents for environmentally more acceptable WESTERN EUROPE
chemical processes. High-pressure reactions, however, Accession no.704079
are more capital intensive than conventional low pressure
processes. Therefore, supercritical Áuids will only gain
Item 327
widespread acceptance in those areas where the Áuids give
Supercritical Fluid Technology. Conference
real chemical advantages as well as environmental beneÀts.
proceedings.
A number of examples illustrate some of these advantages.
Birmingham, 15th-17th Sept.1997, paper 1. 91141T
The examples range from promising laboratory reactions
POLYMER FRACTIONATION
to processes which have already been commercialised or
Clifford A A
will be soon. Extended abstract only. 8 refs.
Express Separations Ltd.
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
EUROPE
(Royal Society of Chemistry,Process Technology
Group; SCI Separation Science & Technology Group;
Accession no.704080 SCI Process Engineering Group; Environmental
Technology Best Practice Programme)
Item 326
Fractionation of polymers using supercritical Áuids is well
Supercritical Fluid Technology. Conference
established. In fact fractionation in supercritical Áuids
proceedings.
has been a feature of polymer production from the 1940s
Birmingham, 15th-17th Sept.1997, paper 2. 91141T
and subsequent fractionation using a compressed gas was
PREPARATIVE CHROMATOGRAPHY: LIQUID
patented then. Time is a factor in these extractions which
OR SUPERCRITICAL ELUENTS
has previously been neglected. Modelling involves time
Nicoud R-M
and this leads to the idea of using a density gradient during
NOVASEP
extraction. An example of the use of a density gradient for
(Royal Society of Chemistry,Process Technology
the production of narrow fractions of polymers, i.e. those
Group; SCI Separation Science & Technology Group;
with low polydispersity, is given. However, by choosing an
SCI Process Engineering Group; Environmental
appropriate density programme, any distribution of molar
Technology Best Practice Programme)
mass in a polymer can, in principle, be produced. Narrow
Chromatography processes are being developed as fractions of polymers are used as analytical standards
production techniques with gas and mainly liquid for calibration in size-exclusion or gel permeation
eluents. These techniques are more and more used in chromatography. A wide range of polymer samples are
the pharmaceutical industry, because of their Áexibility produced, typically with polydispersities of 1.05, for this
and their ability to solve difÀcult problems at reasonable purpose. For example, polymers can be fractionated by
costs. First industrial chromatographic processes using extracting them with a liquid using a solvent gradient:
supercritical Áuids are announced. In order to transform initial extraction being a ‘poor’ solvent, which extracts
a concept (the use of supercritical Áuids) into a technique, the lowest molar masses, to which a ‘better’ solvent is
different technological aspects have to be carefully added in higher and higher proportions to extract fractions
addressed: the column, the devices performing the solute/ of progressively higher molar mass. For some polymers
eluent separation, the eluent loop, the co-solvent module. of lower molar mass, this and other methods are not
Whatever the physical state of the eluent, modelling is a successful because of their high solubility and the polymer
key tool allowing the rapid development and optimisation fractions are made by preparing directly polymers of low
of chromatographic processes. Good prediction models polydispersity. However, the fractions made in this way
allow optimisation of classical elution systems, but also the have higher polydispersity than is desirable and at the same
design of new processes for which intuition is of limited time these samples are more expensive. A possible solution
help simulated moving bed or extrography. The chemical is to extend the solubility range downwards by using
engineering tools allowing modelling of PSFC are similar supercritical Áuid extraction. Extended abstract only.
to those allowing to model LC: mass balances, knowledge EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
of adsorption isotherms, mass transfer coefÀcients. The EUROPE
main differences are due to the dependence of the Áuid Accession no.704078
viscosity and of the adsorption isotherms with respect
to the pressure and thus to the position in the column.
Item 328
These properties make supercritical Áuids ‘adjustable’
Macromolecules
solvents and most processes are based on these solvent
31, No.19, 22nd Sept.1998, p.6481-5
power variations. A new and innovative process based
PULSED-LASER POLYMERISATION OF
on the association of columns to allow a continuous
METHYL METHACRYLATE IN LIQUID AND
incinerated or discarded. (or the surface tension of the polymer). With this decrease
JAPAN in surface tension, the polymer cohesive energy density
Accession no.694962 became closer to that of carbon dioxide. Solubility was
thus governed primarily by polymer-polymer interactions,
while polymer-carbon dioxide interactions played a
Item 333 secondary role. The solubility was strongly dependent
Polymer Engineering and Science on molec.wt. for the less carbon dioxide-philic polymers.
38, No.7, July 1998, p.1112-20 The solubilities of high molec.wt. polyÁuoroalkoxyphosp
EXTRUSION OF PE/PS BLENDS WITH hazenes in carbon dioxide were comparable with those of
SUPERCRITICAL CARBON DIOXIDE poly(1,1-dihydroperÁuorooctylacrylate). 56 refs.
Minhee Lee; Tzoganakis C; Park C B USA
Waterloo,University; Toronto,University
Accession no.691497
The effects of dissolved supercritical carbon dioxide on the
viscosity and morphological properties were investigated
Item 336
for PE/PS blends in a twin-screw extruder. The viscosities
Revista de Plasticos Modernos
of the blend/carbon dioxide solutions were measured at
73, No.488, Feb.1997, p.141-8
various carbon dioxide concentrations using a wedge
Spanish
die mounted on the extruder. The effect of processing
LATEST TECHNOLOGICAL DEVELOPMENTS
parameters on the size of the dispersed PS phase and cell
IN THE PRODUCTION OF POLYETHYLENE
structure were investigated at various extrusion conditions
Vargas L
and carbon dioxide concentrations. 47 refs.
Repsol SA
CANADA
Accession no.694905 Developments in metallocene catalysts and suspension
and gas phase polymerisation processes for PE production
are reviewed, and the advantages of bimodal PE resins are
Item 334 examined. Statistics show world production capacities for
Japan Chemical Week PE in 1995 with forecasts for 2000, and West European PE
39, No.1990, 3rd Sept.1998, p.2 consumption by application in 1993. 29 refs.
EPDM CAN BE RECYCLED WITH EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;
SUPERCRITICAL WATER WESTERN EUROPE; WESTERN EUROPE-GENERAL; WORLD
It is brieÁy reported that Nishikawa Rubber has Ànished Accession no.691292
a basic study on chemical recycling technology for
vulcanised EPDM. The technology enables the cracking of Item 337
used EPDM into a compound with a molecular weight of Journal of Applied Polymer Science
1,000-5,000 in supercritical water with sodium hydroxide 69, No.5, 1st Aug.1998, p.911-9
under a high temperature and pressure. SUPERCRITICAL FLUID DYEING OF PMMA
NISHIKAWA RUBBER CO. FILMS WITH AZO-DYES
West B L; Kazarian S G; Vincent M F; Brantley N H;
JAPAN
Eckert C A
Accession no.691538 Georgia,Institute of Technology
In-situ UV-vis spectroscopy was used to study diffusion
Item 335 of two azo dyes in a carbon dioxide-swollen matrix of
Industrial and Engineering Chemistry Research PMMA. The diffusivity of both dyes can be tuned simply
37, No.8, Aug.1998, p.3067-79 by changing the system pressure. The partitioning of the
SOLUBILITY OF HOMOPOLYMERS AND dyes between the polymer phase and the Áuid phase was
COPOLYMERS IN CARBON DIOXIDE measured. 40 refs.
O’Neill M L; Cao Q; Fang M; Johnston K P; Wilkinson
USA
S P; Smith C D; Kerschner J L; Jureller S H
Texas,University; Air Products & Chemicals Inc.; Accession no.689709
Unilever Research
The cloud points of various amorphous polyether, Item 338
polyacrylate and polysiloxane homopolymers and some Macromolecules
commercially-available block copolymers were measured 31, No.14, 14th July 1998, p.4614-20
in carbon dioxide at temps. from 25 to 65C and pressures PREPARATION AND CHARACTERISATION OF
of about 1000 to 6000 psia. The solubility parameters MICROCELLULAR POLYSTYRENE FOAMS
of the amorphous polymers, almost without exception, PROCESSED IN SUPERCRITICAL CARBON
increased with a decrease in the cohesive energy density DIOXIDE
to that of PS. An improvement in polymer blending 50nm), making their largest contribution at 10-20 nm, were
results. 10 refs. calculated from nitrogen adsorption isotherms. Surface areas
USA of the correct order of magnitude were obtained by assuming
Accession no.687407 that gas adsorption took place on the surfaces of lamellar
crystals. Crystallisation of isotactic PP from n-butane and
n-heptane generated foams of lower mesoporosity and
Item 343 smaller surface area. These more ‘liquid-like’ solvents did
European Chemical News not allow for formation of an open network of mesopores or
69, No.1815, 1st-7th June 1998, p.25 they promoted its collapse upon their removal. 22 refs.
TAKEDA/KOBE RECYCLING UNIT RECOVERS USA
TDA
Accession no.672015
It is brieÁy reported that Takeda Chemical Industries
has started up a recycling unit using supercritical water
Item 346
technology to recover toluene diamine during manufacture
Fibres and Textiles in Eastern Europe
of toluene diisocyanate at its Kashima plant in Japan.
5, No.3, 1997, p.70-3
The technology has been jointly developed by Takeda
WATER-FREE DYEING OF HIGH-
and Kobe Steel. The recycling unit has a TDA recovery
PERFORMANCE FIBROUS MATERIAL WITH
rate of 80%.
SUPERCRITICAL CARBON DIOXIDE AS
TAKEDA CHEMICAL INDUSTRIES LTD.; KOBE DYEING BATH (SFD)
STEEL LTD. Knittel D; Schollmeyer E
JAPAN Deutsches Textilforschungszentrum Nord-West eV
Accession no.680580 The results of water-free dyeing of high-performance
Àbres (aramids, polyarylketones, polyarylsulphides) are
Item 344 described. The new dyeing process is based on the use of
Polymers Paint Colour Journal supercritical carbon dioxide as a dyeing medium and on the
188, No.4400, Jan.1998, p.14-7 use of disperse dyestuffs. Selective laboratory screening
SUPERCRITICAL FLUID TECHNOLOGIES experiments are presented. Dyestuff uptake depends on
- NEW OPPORTUNITIES FOR COATING AND structure of the polymers and has to be optimised. High
IMPREGNATING PLASTICS AND ELASTOMERS washing fastnesses are obtainable. 17 refs.
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
Hay J N; Johns K
WESTERN EUROPE
Surrey,University; Chemical & Polymer
Accession no.668597
It is explained that, usually, large quantities of undesirable
solvents are released during the application of coatings.
This article looks at a new development which involves Item 347
replacing the solvent (in part or completely) by carbon Plastics Engineering
dioxide under supercritical conditions. Full details of the 53, No.12, Dec.1997, p.37-40
work are provided. 30 refs. CARBON DIOXIDE AS A CONTINUOUS PHASE
FOR POLYMER SYNTHESIS
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
EUROPE Canelas D A; Burke A L C; DeSimone J M
North Carolina,University
Accession no.677252
The use is investigated of supercritical carbon dioxide
Item 345 in polymer synthesis with reference to the advantages
Journal of Polymer Science : Polymer Physics Edition it affords beyond the simple elimination of the use of
36, No.4, March 1998, p.617-27 organic solvents or water. Advantages in the properties
ISOTACTIC POLYPROPYLENE FOAMS and processing of materials are examined, which can be
CRYSTALLIZED FROM COMPRESSED realised through the use of this medium, which are reported
PROPANE SOLUTIONS to be principally as a result of the lack of chain transfer
Whaley P D; Kulkarni S; Ehrlich P; Stein R S; and high plasticisation propensity. 82 refs.
USA
Winter H H; Conner W C; Beaucage G
Massachusetts,University; Cincinnati,University Accession no.667077
Crystallisation of isotactic PP from homogeneous solution
in supercritical propane yielded open-cell foams of high Item 348
surface area. Their morphology usually consisted of Patent Number: EP 818292 A2 19980114
microspheres with a dense core and a porous periphery of PROCESS FOR PREPARING EXPANDED
radiating Àbrils. Pore radii covering the mesopore range (2- PRODUCT OF THERMOPLASTIC RESIN
Nishikawa S; Yorita K; Ichikawa K; Inoue H; Eriguchi Polypyrrole was synthesised via thermal decarboxylation
M; Sueda T; Amemiya H of a precursor monomer, pyrrole-2-carboxylic acid,
Mitsui Toatsu Chemicals Inc. using ferric salts in both supercritical carbon dioxide and
supercritical Áuoroform. Pressed pellet conductivities were
Supercritical carbon dioxide and/or nitrogen is added,
determined, and SEM revealed an unusual non-spherical
as a blowing agent, to a thermoplastic resin and melted
morphology. 10 refs.
therein. The resulting molten resin composition is cooled
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
under a pressure not less than a critical pressure of the EUROPE
blowing agent and discharged from a die to lower the
pressure to a level not more than the critical pressure and Accession no.657616
the expanded product is cooled to a level not more than
the Tg or crystallisation temperature of the resin to control Item 351
the cell diameter of the expanded product. The process Patent Number: EP 798314 A1 19971001
uses a shear rate adjusting section, which generates a DEVOLATILISATION
shear rate in a speciÀed range and has a sectional area Krupinski S; McQueen J T
(A), and a Áow velocity distribution adjusting section, Nova Chemicals (International) SA
which lowers the shear rate and has a sectional area (B),
A polymer melt may be devolatilised to less than 500,
B/A being in the range of 1.3 to 20. The foams obtained
preferably less than 150 ppm, of residual volatile material
have excellent surface appearance, high strength and cells
by injecting into the melt an amount of a supercritical Áuid
of a Àne average cell diameter and a uniform average cell
greater than the amount of residual volatile material in the
density.
melt, typically not more than about 10 wt.%, and passing
JAPAN
the melt through a Áash chamber devolatiliser at a speciÀed
Accession no.664244 pressure and a temp. of from 200 to 350C.
SWITZERLAND; WESTERN EUROPE
Item 349 Accession no.656382
Journal of the National Institute of Materials and
Chemical Research
Item 352
5, No.4, 1997, p.175-183
Macromolecules
Japanese
30, No.4, 24th Feb.1997, p.745-56
APPLICATION OF SUPERCRITICAL FLUIDS
DISPERSION POLYMERISATION OF METHYL
TO EARTH ENVIRONMENT PROTECTION
METHACRYLATE IN SUPERCRITICAL
TECHNOLOGY
CARBON DIOXIDE
Sako T; Sugeta T
Lepilleur C; Beckman E J
Three kinds of promising innovative environmental Pittsburgh,University
applications using supercritical Áuids to solve problems
A series of graft copolymers, poly(methyl methacrylate-
of energy, resources and global environment are shown:
co-hydroxyethyl methacrylate)-g-poly(perÁuoropropylene
the complete decomposition of hazardous compounds
oxide), was synthesised for application as stabilisers
with supercritical water, the recycling of waste plastics
in dispersion polymerisation of methyl methacrylate in
with supercritical methanol or supercritical water, and
supercritical carbon dioxide. The backbone, poly(methyl
chemical reaction in supercritical carbon dioxide which
methacrylate-co-hydroxyethyl methacrylate), is effectively
is free from toxic organic solvents. Supercritical methanol
insoluble in carbon dioxide and the grafted chains,
depolymerised waste condensation polymers such as
poly(perÁuoropropylene oxide), are completely miscible
PETP and PEN into constituent monomers easily. The
in carbon dioxide at moderate pressures. The effect of
supercritical water decomposed composite plastics such as
molecular architecture on polymerisation rate and PMMA
FRP into the glass Àbre and fuel oil with high efÀciency.
particle size was evaluated by varying the molecular
12 refs.
weight of the anchor group (backbone of the copolymer),
JAPAN
molecular weight of the carbon dioxide-soluble graft
Accession no.662847 chain, and graft chain density. The efÀciency of the graft
copolymers as dispersants was demonstrated as micron-
Item 350 size polymer beads of molecular weight greater than
Journal of Materials Chemistry 100000 were produced. The results showed that a careful
7, No.10, Oct.1997, p.1965-6 balance between anchor group size (backbone length) and
FIRST EXAMPLE OF A CONDUCTING amount of soluble component (either graft chain length
POLYMER SYNTHESISED IN SUPERCRITICAL or graft chain density) is necessary, but not sufÀcient to
FLUIDS achieve adequate stabilisation and that the distribution
Kerton F M; Lawless G A; Armes S P of the soluble component along the anchor group was
Sussex,University also important. Furthermore, the backbone molecular
weight was shown as the key component for stabilisation, Item 355
provided that enough carbon dioxide-philic component has Informations Chimie
been included to ensure solubility. 38 refs. No.375, Feb.1996, p.83-94
USA French
Accession no.651555 REVOLUTION OF METALLOCENES AND NEW
POLYMERISATION PROCESSES
Gauthier X V
Item 353
Advances in Polymer Science Developments in metallocene polymerisation catalysts
No.133, 1997, p.103-40 for polyoleÀn synthesis are examined, and commercial
POLYMERIZATIONS IN LIQUID AND developments by a number of companies are reviewed.
SUPERCRITICAL CARBON DIOXIDE Some new polymerisation processes, including supercritical
Canelas D A; DeSimone J M suspension, high temperature and supercondensing mode
North Carolina,University gas phase polymerisation, are also described. 6 refs.
WORLD
A review is presented of the literature on the use of carbon
dioxide as an inert solvent for the synthesis and processing Accession no.643008
of polymers. Homogeneous solution polymerisations are
discussed with emphasis on free radical chain growth and Item 356
cationic chain growth in the synthesis of Áuoropolymers. Macromolecules
Heterogeneous polymerisations are then considered, with 30, No.9, 5th May 1997, p.2792-4
reference to free radical precipitation polymerisations, FORMATION OF CELLULOSE ACETATE
dispersion and emulsion polymerisations, heterogeneous FIBERS BY THE RAPID EXPANSION OF
cationic polymerisations, metal-catalysed polymerisations, SUPERCRITICAL METHANOL SOLUTIONS
step growth polymerisations and hybrid systems. 148 Aniedobe N E; Thies M C
refs. Clemson,University
USA
The rapid expansion of secondary cellulose acetate
Accession no.651346
from supercritical methanol solutions was investigated.
Particular attention was paid to determining whether or not
Item 354 continuous Àbres could be made and the extent to which
Journal of Polymer Science : Polymer Chemistry degradation of cellulose acetate occurred because of the
Edition elevated processing temps. 7 refs.
35, No.10, 30th July 1997, p.2009-13 USA
DISPERSION POLYMERIZATION OF METHYL Accession no.638826
METHACRYLATE IN SUPERCRITICAL
CARBON DIOXIDE: INFLUENCE OF HELIUM
CONCENTRATION ON PARTICLE SIZE AND Item 357
PARTICLE SIZE DISTRIBUTION Antec 97. Volume II. Conference proceedings.
Yu-Ling Hsiao; Desimone J M Toronto, 27th April-2nd May 1997, p.1991-5. 012
North Carolina,University ON-LINE MEASUREMENT OF PS/CO2
SOLUTION VISCOSITIES
Dispersion polymerisations of MMA using poly(1,1-
Lee M; Park C B; Tzoganakis C
dihydroperfluorooctyl acrylate) as a steric stabiliser
Waterloo,University; Toronto,University
in supercritical carbon dioxide were carried out in
(SPE)
the presence of helium. Particle size and particle size
distribution were found to be dependent on the amount The reduction of viscosity via gas dissolution in a polymer
of inert helium present. Particle sizes ranging from 1.64 is well explained in terms of the dilution and the free
to 2.66 micrometres were obtained with various amounts volume increase. The viscosity of polymer/supercritical
of helium. Solvatochromic investigations using 9- Áuid (SCF) solutions has been studied by theoretical
(alpha-perÁuoroheptyl-beta,beta-dicyanovinyl)julolidine prediction or off-line measurement to date. A technology
indicated that the solvent strength of carbon dioxide for the on-line measurement of melt viscosity of PS/SCF
decreased with increasing helium concentration. This solutions is presented using a linear capillary tube die
effect was confirmed by calculations of Hildebrand mounted on a single-screw extruder. Carbon dioxide
solubility parameters. Dispersion polymerisation results is injected into the extrusion barrel and the content of
indicated that PMMA particle size could be attenuated CO2 is varied in the range of 0 to 4% by weight using a
by the amount of helium present in supercritical carbon positive displacement pump. Single-phase polymer/SCF
dioxide. 34 refs. solutions are made using a microcellular extrusion system
USA and formation of two-phase mixture is prevented by
Accession no.648202 maintaining a high pressure in the capillary tube die. By
measuring the pressure drops through the die, the viscosity or plugs in metered dose delivery devices, such as aerosols
of PS/CO2 solutions is determined. The solubility of CO2 for demanding medicinal and pharmaceutical uses.
is estimated by monitoring the pressure drops and the USA
absolute pressure in the die. The effect of pressure on the Accession no.633883
viscosity of a PS/CO2 solution is also discussed. 27 refs.
CANADA
Item 361
Accession no.638327 Journal of Polymer Science : Polymer Physics Edition
35, No.3, Feb.1997, p.523-34
Item 358 RHEOLOGY OF POLYDIMETHYLSILOXAN
Patent Number: US 5559198 A 19960924 E(PDMS) SWOLLEN WITH SUPERCRITICAL
PROCESS FOR PREPARING POLYVINYL CARBON DIOXIDE
TRIFLUOROACETATE AND POLYVINYL Gerhardt L J; Manke C W; Gulari E
TRIFLUOROACETATE/VINYL ESTER Wayne State,University
COPOLYMERS IN SUPERCRITICAL CO2
Viscosity curves were measured for PDMS melts swollen with
Eian G L; Elsbernd C L S
dissolved carbon dioxide at 50 and 80C for shear rates ranging
Minnesota Mining & Mfg.Co.
from 40 to 2300/s, and for carbon dioxide contents ranging
Polyvinyl triÁuoroacetate (PVTFA) is obtained in relatively from 0 to 21 wt %. The measurements were performed with
high yield under mild conditions by using carbon dioxide a capillary extrusion rheometer modiÀed for sealed, high-
under supercritical conditions, as a solvent. Synthesis of pressure operation to prevent degassing of the melt during
syndiotactic PVTFA on a commercial scale without the extrusion. The concentration-dependent viscosity curves for
use of environmentally-harmful solvents is made possible these systems were self-similar in shape, exhibiting low-shear
by the process, which provides a convenient route to rate Newtonian plateau regions followed by shear-thinning
syndiotactic PVAL. power-law regions. Considerable reduction of viscosity was
USA observed as the carbon dioxide content increased. Classical
Accession no.635518 viscoelastic scaling methods, employing a composition-
dependent shift factor to scale both viscosity and shear rate,
were used to reduce the viscosity data to a master curve at each
Item 359 temp. The dependence of the shift factors on polymer chain
Journal of Applied Polymer Science density and free volume were investigated by comparing
64, No.7, 16th May 1997, p.1309-17 the shift factors for PDMS-carbon dioxide systems with
HIGHLY REFLECTIVE POLYIMIDE FILMS those obtained by iso-free volume dilutions of high molec.
CREATED BY SUPERCRITICAL FLUID wt. PDMS. This comparison suggested that the free volume
INFUSION OF A SILVER ADDITIVE added to PDMS upon swelling with dissolved carbon dioxide
Boggess R K; Taylor L T; Stoakley D M; St.Clair A K was the predominant mechanism for viscosity reduction in
US,NASA,Langley Research Center; those systems. 19 refs.
Radford,University USA
Supercritical Áuid infusion of a silver-containing additive Accession no.625151
into a fully cured polyimide was achieved with moderately
high-density carbon dioxide at 110C. The nature of the
Item 362
silver and its distribution within the Àlm and on the Àlm
Polymer Recycling
surface were established via microscopy and surface
2, No.2, 1996, p.77-82
analysis techniques. 25 refs.
CHEMICALS OF COMMERCE FROM
USA
RECYCLED SCRAP TYRES
Accession no.635399 Dhawan J C; Huddleston H T
South Alabama,University
Item 360 Tyre disposal problems are highlighted. The application
Patent Number: US 5550211 A 19960827 of supercritical Áuid (SCF) technology to produce liquid
METHOD FOR REMOVING RESIDUAL hydrocarbons is discussed. The SCF-liquid can be blended
ADDITIVES FROM ELASTOMERIC ARTICLES with crude oil for upgrading in an existing reÀnery scenario or
DeCrosta M A; Jagnandan I it could be fractionated to produce a variety of low molecular
Schering Corp. weight aromatic hydrocarbons, The SCF-tyre oil process
The articles are cleaned by contacting them with at least one is safe to operate since the pressure energy at supercritical
supercritical Áuid under conditions and for a time sufÀcient conditions is contained in the liquid. The process would only
to remove the phthalates and/or polynuclear aromatic require ‘off the shelf’ processing equipment. 16 refs.
hydrocarbons contained therein. Articles having reduced USA
phthalate contents can be used as gaskets, valves, seats, Áaps Accession no.622309
Item 372 also very high. In addition to morphology, the polarity of the
Patent Number: WO 9518834 A1 19950713 polymer was also crucial in determining the solubility in carbon
SUPERCRITICAL FLUID EXTRACTION dioxide. Comparison was also made with the behaviour of
INVOLVING HYDROFLUOROALKANES crystalline polymers. 12 refs. (Pt.I, ibid, p.695-705)
Blackwell J A; Chen D T; Alband T D; Perman C A USA
Minnesota Mining & Mfg.Co. Accession no.576754
A composition containing Àrst and second components
is contacted with a supercritical Áuid comprising 1,1,1,2- Item 375
tetraÁuoroethane or 1,1,1,2,3,3,3-heptaÁuoropropane or a Journal of Applied Polymer Science
mixture thereof, in the supercritical state under conditions 59, No.4, 24th Jan.1996, p.695-705
and for a time sufÀcient to remove the Àrst component INTERACTION OF SUPERCRITICAL CARBON
from the composition. DIOXIDE WITH POLYMERS. I. CRYSTALLINE
USA POLYMERS
Accession no.582627 Shieh Y T; Su J H; Manivannan G; Lee P H C;
Sawan S P; Spall W D
Item 373 Lowell,University; Los Alamos National Laboratory
2nd Annual Recycling Conference: Putting Plastics The interaction of supercritical carbon dioxide with nine
Recycling Technology to Use. Retec proceedings. different crystalline polymers (four types of substituted and
Akron, Oh., 2nd-3rd Nov.1995, p.9-16 8(13) unsubstituted PE), PP, nylon 66, PETP, polyoxymethylene
INNOVATIVE APPROACH TO IMPROVE THE and PVDF) was studied systematically over a wide range
QUALITY OF RECYCLED PLASTIC of pressures and temps. Critical factors such as changes
Agrawal R; Lancaster T; Papinsick J in appearance and weight, temp., pressure and time of the
Liquid Carbonic Inc. supercritical Áuid treatment and dimension of samples were
(SPE,Recycling Div.; SPE,Akron Section) observed. The effect of supercritical carbon dioxide on the
A novel technique is presented for removal of impurities from thermal properties of treated polymers was investigated
plastic using supercritical carbon dioxide in a twin-screw through TGA analysis. Changes in the mechanical
extruder. A 34 mm counterrotating, intermeshing twin-screw properties, such as yield strength, ultimate elongation and
extruder was used. The source of plastic used was from kerbside elastic modulus, of the crystalline polymers studied were
collections consisting of detergent, fabric softener and milk also observed. The possible implications of the observed
bottles. The impurities contained in these bottles were aromatic changes for certain applications are discussed. 23 refs.
hydrocarbons and fragrance type compounds like d-limonene. USA
Control experiments were run by doping virgin plastic with Accession no.576753
naphthalene and then processing with supercritical carbon
dioxide. It is shown that this process can remove contaminants Item 376
within the plastic to 95% or greater efÀciencies. PolyoleÀns IX. Conference Proceedings.
USA Houston, Tx., 25th Feb-1st March,1995, p.31-47. 42C1
Accession no.579418 THIRD-GENERATION POLYOLEFIN
TECHNOLOGIES AND THEIR CAPABILITIES
Sinclair K B
Item 374
SRI International
Journal of Applied Polymer Science
(SPE,South Texas Section; SPE,Thermoplastic
59, No.4, 24th Jan.1996, p.707-17
Materials & Foams Div.)
INTERACTION OF SUPERCRITICAL CARBON
DIOXIDE WITH POLYMERS. II. AMORPHOUS Three developments in polyoleÀn technology are discussed,
POLYMERS together with their advantages over current commercial
Shieh Y T; Su J H; Manivannan G; Lee P H C; polyoleÀn processes. The developments are supercritical
Sawan S P; Spall W D slurry processes for PE and PP, high-temperature PP
Lowell,University; Los Alamos National Laboratory processes and supercondensing gas-phase processes. These
developments in process operating techniques, combined
Eleven different polymers of amorphous type were subjected
with recent developments in catalysis, promise to provide
to supercritical carbon dioxide treatment under a wide range of
great improvements in productivity and product range
pressures and temps. The effects of the treatment on appearance,
capability. 5 refs.
weight change, and thermal and mechanical properties were
NESTE OY; HOECHST; MITSUBISHI PETROCHEMICAL;
followed systematically. In addition, the effects of treatment NOVACOR; DOW; UNION CARBIDE; EXXON; BASF
conditions and dimension of the samples of weight changes USA
were also monitored. It was found that amorphous polymers
could absorb carbon dioxide to a greater extent than crystalline Accession no.576276
polymers and, in turn, the phenomenon of plasticisation was
equation of state. 15 refs. form hollow Àbres and highly oriented microÀbril. In the
USA dilute region, microÀbrils are produced with diameters as
Accession no.564824 low as 100 nm due to the dipole forces, in contrast with
microspheres produced from solutions of PS in toluene.
For PAN microÀbrils, orientation increases with shear,
Item 382 then goes through a maximum and eventually decreases at
Adhesives Age higher Áow rates due to an expanding jet. The concentration
38, No.10, Sept.1995, p.34-6 for the transition from microÀbrils to a single hollow Àbre
UNGLUING BY SUPERCRITICAL FLUIDS is in agreement with the calculated transition concentration
Manivannan G; Sawan S P (C) from the dilute to semidilute region. In the semidilute
Massachusetts,University region, the morphology changes from hollow Àbres to
The ability to unglue assembled parts will take on more highly oriented Àbrils with an increase in Áow rate. The
importance as recycling issues continue to gain more increase in turbulence enhances convective mass transport,
importance. The use of supercritical carbon dioxide leading to more uniform nucleation throughout the cross-
could Ànd a niche among various existing dismantling section of the jet, favouring the highly oriented Àbrils. The
technologies. Aspects covered include adhesives and enhanced transport of carbon dioxide into the jet lowers the
supercritical Áuid treatment. 6 refs. solvent quality, raising the above transition concentration
USA (C), which further favours Àbril formation. For both PAN-
DMF and PS-toluene solutions, the transition from highly
Accession no.562909
oriented microÀbrils to hollow Àbres occurs at about 3C
(in a good solvent), suggesting some similarities in the
Item 383 mass-transfer pathways in each system. 27 refs.
Cellular Polymers II. Conference proceedings. USA
Edinburgh, 23-25th March 1993, paper 5. 6124
Accession no.562479
GENERATION OF MICROCELLULAR
POLYMERS USING SUPERCRITICAL CO2
Goel S K; Beckman E J Item 385
Pittsburgh,University Polymer
(Rapra Technology Ltd.) 36, No.16, 1995, p.3099-102
PLASTICISATION OF A POLYURETHANE BY
Supercritical CO2 is known to be a very good swelling CARBON DIOXIDE AT HIGH PNEUMATIC
agent and plasticiser for PMMA, a consequence of STRESSES
an interesting combination of liquid-like and gas-like Briscoe B J; Kelly C T
properties exhibited by supercritical fluids. Making London,Imperial College of Science,Technology &
use of this behaviour, a constant temperature process Medicine
of generating microcellular polymers which employs
a sudden pressure drop to induce phase separation in a The interaction of high pressure, subcritical and
solution of supercritical CO2 and PMMA is studied. The supercritical carbon dioxide with a polyesterurethane
method is different from commonly-used temperature elastomer (Diprane 54) was studied. A novel optical high
quench methods in that it makes use of the glass transition pressure cell was employed to examine the gas-polymer
depression due to the presence of diluent in the polymer interactions at a molecular level, using FTIR. Spectra
rather than heating the polymer to above its normal glass indicated that the hydrogen bonding between the polymer
transition temperature. 24 refs. chains was disrupted by the imbibed gas. The data were
USA then used in conjuction with temperature-dependent
spectral data and the modulus-temperature characteristics
Accession no.562718
of the polymer, to estimate the change in modulus of the
polymer as a function of gas pressure. The predicted
Item 384 modulus of the PU was seen to fall as the gas pressure
Polymer was increased, indicating that the PU was plasticised by
36, No.16, 1995, p.3173-82 the carbon dioxide. The plasticisation effect became the
SEMICRYSTALLINE MICROFIBRILS AND less dominant process at pressures above 12 MPa. The
HOLLOW FIBRES BY PRECIPITATION WITH A procedure provides a relatively convenient method for
COMPRESSED FLUID ANTISOLVENT quantifying plasticisation in PU systems in the presence
Luna-Barcenas G; Kanakia S K; Sanchez I C; Johnston of high pneumatic stresses. Such data are valuable in
KP predicting the consequences of gas-induced rupture during
Austin,University of Texas ambient gas decompression. 13 refs.
Precipitation with a compressed-Áuid antisolvent was EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN
EUROPE
studied theoretically and experimentally. Solutions of PAN
in DMF sprayed into supercritical Áuid carbon dioxide Accession no.562469
Item 401 coverage and cost data for conventional and supercritical
Patent Number: EP 590842 A2 19940406 Áuid plastics coating formulations are presented. 9 refs.
PROCESS FOR PREPARING LOW MOLEC.WT. USA
POLYMERS Accession no.503913
Dada E A; Lau W; Merritt R F; Paik Y H; Swift G
Rohm & Haas Co.
Item 404
Polymerisation is conducted in supercritical carbon dioxide Plastics World
at temps. of at least 200C and pressures above 3,500 psi. 52, No.1, Jan.1994, p.10
The process may be continuous, semi-continuous or NOVEL GAS PROCESS MAKES UNIQUE FOAMS
batch. The polymers, which have molec.wts. below 5000 Miller B
and polydispersity below 2.5, are useful as detergent
additives, scale inhibitors, dispersants and crystal growth A new approach to producing thermoplastic foams has been
modiÀers. developed at Massachusetts Institute of Technology. These
USA
microcellular foams (MCF) contain billions of micron-size
voids per cubic centimetre, a structure that is claimed to
Accession no.512984 retain unusually high levels in mechanical properties, even
at substantial density reductions. The MCF process involves
Item 402 using supercritical liquid carbon dioxide, injected into the
Recycle ‘93. Conference Proceedings. extruder barrel, as the blowing agent. Applications are foreseen
Davos, 22nd-26th March 1993, paper 14/4. 8(13) in light-weighting all types of thermoplastic extrusions
INCORPORATION OF RECYCLABILITY including proÀles, Àlms and Àbres. Commercialisation of
THROUGH MOLECULAR DESIGN MCF is being handled by Axiomatics Corp.
Beckman E J
Pittsburgh,University MASSACHUSETTS INSTITUTE OF TECHNOLOGY;
(Maack Business Services) AXIOMATICS CORP.
USA
The use of molecular design in different ways to incorporate
Accession no.501618
recyclability into thermoplastic and thermoset materials is
reviewed. Design of a material whose molecular properties
allow easier separation from a mixed thermoplastic waste Item 405
stream or creation of a material which degrades chemically Macromolecules
in a predetermined way are both aspects of recyclability by 26, No.19, 13th Sept.1993, p.5052-60
molecular design. Examples are discussed. All decisions PHASE BEHAVIOUR OF
about molecular design must take into account the full POLYMER-SUPERCRITICAL
life cycle of the material so that improved recyclability CHLORODIFLUOROMETHANE SOLUTIONS
by molecular design does not result in a negative impact Haschets C W; Shine A D
of the polymer on the environment. 35 refs. Delaware,University
USA
The phase behaviour of solutions of PMMA and
Accession no.505789 polycaprolactone in supercritical chlorodiÁuoromethane
was studied using a high pressure variable-volume view
Item 403 cell. The effect of polymer polydispersity and the critical
In Tune with the Newest Decorating Technologies. state of the solvent on the phase behaviour was examined,
Retec proceedings. and the ability of lattice Áuid and hydrogen bond models to
Nashville, Tn., 12th-13th Oct.1993, p.104-17. 8(11)34 describe the experimental data was investigated. 43 refs.
SUPERCRITICAL FLUID SPRAY APPLICATION USA
OF LOW-POLLUTION COATINGS FOR Accession no.494354
PLASTIC SUBSTRATES
Miller W P Item 406
Union Carbide Corp. Resources, Conservation and Recycling
(SPE,Decorating Div.; SPE,Tennessee Valley Section) 9, No.1/2, Aug.1993, p.75-88
The supercritical Áuid spray coating process, use of which DENSITY-BASED SEPARATION OF
can result in signiÀcant reductions of volatile organic THERMOPLASTICS FOUND IN THE POST-
content(VOC) emissions, is described. Particular attention CONSUMER WASTE STREAM
is paid to supercritical carbon dioxide as a coating solvent, Super M S; Enick R M; Beckman E J
reduction of the ‘greenhouse effect’, spray generation and Pittsburgh,University
conditions, spray characteristics, transfer efÀciency, and The use of near-critical CO2 and near-critical mixtures of
suitable polymeric coating systems. Comparative VOC, CO2 and SF6, Áuids with highly adjustable densities, to
Schut J H
Detailed information is presented on paint spraying
equipment being developed by several companies for use
with Unicarb technology from Union Carbide Chemicals
& Plastics Co.Inc. The Unicarb technology is reported to
have been developed for thinning paint with supercritical
carbon dioxide. Union Carbide is also said to have licensed
Àve paint companies to produce coatings compatible with
the Unicarb process. Advantages and limitations of the
Unicarb process are discussed in some detail.
UNION CARBIDE CHEMICALS & PLASTICS CO.INC.
USA
Accession no.419191
Subject Index
A ARTIFICIAL BONE, 210 286 275 280 338 348 357 383 395
ATOMIC FORCE MICROSCOPY, 402 404
ABS, 74 88 286 364 374 77 112 180 183 BORNYL METHACRYLATE
ABSORPTION, 1 22 39 56 61 193 ATTENUATED TOTAL COPOLYMER, 168
200 212 233 374 REFLECTION BOTTLE, 196 373 402
ACRYLIC, 344 SPECTROSCOPY, 132 341 BUILDING APPLICATION, 260
ACRYLIC ACID COPOLYMER, AUTOCLAVE, 7 17 116 135 193 BULK POLYMERISATION, 136
121 415 197 222 246 312 270
ACRYLIC POLYMER, 28 147 211 AUTOMOTIVE APPLICATION, BUMPER, 166
246 278 301 354 371 407 42 64 82 118 133 166 192 203 BUSINESS MACHINE, 167
ACRYLONITRILE-METHYL 344 382 402 416 BUTADIENE-ACRYLONITRILE
ACRYLATE COPOLYMER, AZOBISISOBUTYRONITRILE, COPOLYMER, 44 414
6 94 28 54 60 77 88 96 100 107 111 BUTADIENE-STYRENE
ACTIVATION ENERGY, 17 51 126 213 224 COPOLYMER, 205
110 197 238 328 378 BUTANE, 345 380
ADDITION REACTION, 259 BUTANEDIOL, 35 248
ADDITIVE, 8 10 24 115 116 165 B BUTYL METHACRYLATE
166 192 200 211 212 214 220 BATCH POLYMERISATION, 49 COPOLYMER, 254
237 262 270 280 296 318 329 155 168 401 BUTYLENE COPOLYMER, 336
334 346 355 359 363 364 383 BATCH REACTOR, 17 161 164 355
ADHESIVE, 43 68 211 302 174 205
ADIPIC ACID, 37 BENZENE, 110 125 205 238
ADSORPTION, 92 184 193 BENZOIC ACID, 193 205
C
AEROSOL, 193 360 370 BENZOIN ETHYL ETHER, 92 CABLE COVERING, 151
AIBN, 28 54 60 77 88 96 100 107 BIMODAL, 89 122 135 336 CABLE INSULATION, 143 153
111 126 213 224 BIOCIDE, 115 269 336
AIR, 71 104 219 BIOCOMPATIBLE, 40 125 CABLE TIE, 203
AIRCRAFT, 133 BIODETERIORATION, 12 39 76 CALORIMETRY, 5 53 84 86 111
ALBUMIN, 193 125 193 210 268 269 365
ALCOHOLYSIS, 138 171 BIOMATERIAL, 15 39 40 63 106 CAPACITY, 143 151 336 343 355
ALKYD RESIN, 407 198 376
AMINOCAPROIC ACID, 174 BIOMEDICAL APPLICATION, CAPROLACTAM, 174 175
AMMONIA, 52 209 402 410 15 193 CAPROLACTONE, 18
AMMONOLYSIS, 52 410 BIOPOLYMER, 149 209 CAPROLACTONE COPOLYMER,
AMORPHOUS, 127 183 300 335 BIREFRINGENCE, 182 200 212 57 415
336 365 374 386 388 247 CAPSULE, 70 193
AMPHIPHILIC, 150 223 BISETHYLHEXYL PHTHALATE, CAR, 166 192
ANALYSIS, 1 2 4 19 23 37 45 55 195 CARBOCATIONIC
65 75 81 83 93 96 108 124 132 BISPHENOL A, 75 162 231 POLYMERISATION, 400
135 136 160 161 176 280 294 BISPHENOL A CARBON FIBRE-REINFORCED
393 405 POLYCARBONATE, 47 281 PLASTIC, 260
ANIONIC POLYMERISATION, 388 CARBON MONOXIDE, 172 205
150 256 BLEND, 10 11 15 48 50 55 61 69 CARBON TETRACHLORIDE, 409
ANTISOLVENT, 292 384 95 101 103 107 112 127 130 CATALASE, 210
APPLICATION, 15 25 36 39 40 42 155 182 199 204 206 217 224 CATALYSIS, 336 355 376
62 64 70 79 82 99 106 115 118 242 251 270 274 276 284 285 CATALYST, 5 18 20 44 125 128
133 144 166 169 180 187 192 286 331 333 342 355 362 380 177 279 298 336 349 353 355
193 195 203 210 211 219 225 BLIND, 253 369 391
237 243 260 278 324 336 344 BLOCK COPOLYMER, 88 182 CATALYTIC DEGRADATION, 109
349 360 362 370 375 393 407 257 258 267 288 335 380 CATHETER, 195
AQUEOUS, 109 220 269 BLOW EXTRUSION, 228 CATIONIC POLYMERISATION,
ARGON, 237 295 BLOW MOULDING, 196 203 336 256 299 353 387 400
AROMATIC, 1 7 9 14 83 95 107 BLOWING AGENT, 19 24 39 69 CAVITY PRESSURE, 192
224 276 280 282 360 362 373 83 118 127 166 186 192 196 CAVITY TRANSFER MIXER, 204
ARRHENIUS’S LAW, 17 110 378 204 228 232 237 260 262 268 260
172 174 175 204 259 293 332 117 139 152 159 164 165 182 316
349 368 183 186 192 193 200 212 214 ELASTOMER, 2 28 44 45 64 68 82
DECOMPOSITION PRODUCT, 37 219 220 247 268 316 337 388 90 92 115 119 130 137 165 166
160 161 162 163 164 259 265 404 414 187 192 199 203 204 205 216
277 DIFFUSIVITY, 14 88 92 95 337 225 237 294 299 313 321 323
DECOMPRESSION, 117 385 392 DIFLUOROETHANE, 141 282 324 325 326 327 330 331 332
407 414 DILATION, 66 90 414 334 344 351 353 355 360 361
DEGRADABLE, 12 125 210 268 DILUENT, 88 263 336 376 383 366 367 371 372 377 378 380
DEGRADATION, 10 13 34 35 88 391 407 411 412 385 387 388 392 397 401
98 109 110 138 171 197 205 DIMENSIONAL STABILITY, 24 ELECTRICAL APPLICATION, 64
261 293 317 318 363 402 144 167 192 286 375 166 187
DEGRADATION PRODUCT, 17 DIMETHYL ACRYLAMIDE ELECTRICAL CONDUCTIVITY,
138 197 271 293 320 COPOLYMER, 96 58 63 93 108 187 350
DEGREE OF POLYMERISATION, DIMETHYL ETHER, 156 ELECTRICAL PROPERTIES, 63
11 378 387 389 390 392 393 DIMETHYL FORMAMIDE, 54 108 187 193 350 388
398 400 401 DIMETHYL SILOXANE ELECTROCHEMICAL
DEGREE OF SWELLING, 66 152 COPOLYMER, 257 POLYMERISATION, 93
219 DIMETHYL TEREPHTHALATE, ELECTRON MICROGRAPH, 111
DEMIXING, 378 405 17 34 35 171 197 248 265 368 127 213
DEMOULDING, 166 DIMETHYLACRYLAMIDE ELECTRON MICROSCOPY, 4 19
DENSIFICATION, 319 COPOLYMER, 96 23 29 55 83 93 130 150 170 173
DENSITY, 24 49 66 88 95 97 110 DIPHENYL DISULFIDE, 119 165 183 184 232 233 294 296
116 164 170 192 193 197 218 DIPHENYL ETHER, 38 ELECTRONIC APPLICATION,
237 240 255 260 336 338 361 DISPERSE DYE, 176 166 180 192 382
378 381 383 388 394 395 402 DISPERSE PHASE, 242 333 ELONGATION, 143 151 250 375
404 406 411 412 DISPERSE RED 1, 214 EMISSION, 344 407
DEPOLYMERISATION, 17 34 35 DISPERSION, 12 43 49 68 131 EMISSION CONTROL, 347
73 88 171 197 205 248 265 277 187 193 199 217 321 324 EMULSION, 115 134 269 304
349 402 DISPERSION EMULSION POLYMERISATION,
DEPRESSURISED, 140 193 221 COPOLYMERISATION, 96 49 88 134 150 155 270 329 353
278 338 DISPERSION ENCAPSULATION, 29 193 313
DESIGN, 41 64 90 97 178 192 215 POLYMERISATION, 7 28 59 370
322 357 376 67 86 88 96 111 147 157 181 END GROUP, 28 84 138 213
DESORPTION, 1 14 61 117 184 223 233 246 255 266 267 270 ENERGY CONSERVATION, 181
388 414 278 288 289 291 297 307 323 259
DETERGENT, 373 401 352 353 354 ENERGY SAVING, 167
DEVOLATILISATION, 242 351 DISSOLUTION, 44 164 242 268 ENGINEERING APPLICATION,
DEVULCANISATION, 2 45 119 292 348 380 42 88 166 192 204 221 260
165 DISSOLVING, 141 333 ENVIRONMENT, 88 102 181 188
DIAMINOTOLUENE, 343 DIVINYL BENZENE, 131 204 254 269 308 311 318 325
DICHLOROMETHANE, 5 106 DOMESTIC APPLIANCE, 166 344 349 368 369 397 402 403
DIE, 72 201 202 260 268 333 339 DOOR HANDLE, 286 407
DIE DESIGN, 196 DOPING, 108 350 373 ENVIRONMENTALLY
DIELECTRIC CONSTANT, 83 151 DRAWING, 71 104 208 252 287 FRIENDLY, 18 115 203 211 329
193 388 315 343 358 371
DIETHYL DRUG DELIVERY, 106 193 258 ENZYME, 18 99 209
PEROXYDICARBONATE, 89 386 EPDM, 331 334 355
122 135 222 DWELL TIME, 122 EPOXY NOVOLAC RESIN, 413
DIETHYLHEXYL PHTHALATE, DYE, 176 179 200 212 214 220 EPOXY RESIN, 73 102 162 382
195 227 247 315 337 346 399 402 407 412
DIFFERENTIAL THERMAL DYEING, 23 176 200 209 212 270 EPSILON CAPROLACTAM, 174
ANALYSIS, 5 19 23 47 51 53 315 316 329 337 175
55 61 66 71 80 81 84 90 107 EPSILON-CAPROLACTONE, 18
112 119 121 125 158 183 212 EQUIPMENT, 25 222 397 416
239 273 314 316 379 398 E ETHANOL, 70 80 187 190 220
DIFFRACTION, 19 23 53 54 61 69 ELASTIC MODULUS, 107 130 ETHYL METHACRYLATE
76 80 230 336 375 COPOLYMER, 239
DIFFUSION, 14 51 75 88 90 92 99 ELASTIC PROPERTIES, 141 142 ETHYLBENZENE, 205
GLYCOL COPOLYMER, 59 IMPACT PROPERTIES, 12 31 32 185 237 336 355 376 393
GLYCOLIDE COPOLYMER, 39 131 199 224 336 LIQUID CARBON DIOXIDE, 43
106 169 210 258 IMPLANT, 40 49 68 176 223 264
GRAVIMETRIC ANALYSIS, 7 14 IMPREGNATION, 48 55 61 108 LIQUID CHROMATOGRAPHY,
53 112 132 193 206 214 219 220 59 161 171 174 295 326
224 245 269 270 344 399 LIQUID CRYSTAL, 209
IMPURITY, 360 373 LITHOGRAPHY, 62 198 254 270
H INDOMETHACIN, 106 370 LIVING POLYMERISATION, 9 36
HARDNESS, 25 151 203 INFRARED SPECTRA, 3 10 23 61 150 312
HCFC, 204 237 280 80 92 107 126 132 138 171 191 LOW DENSITY
HEAT DEGRADATION, 45 109 213 283 294 341 POLYETHYLENE, 88 103 113
163 164 238 293 295 296 356 INITIATOR, 10 16 21 27 28 40 49 123 204 224 237 296 336 355
HEATING, 1 96 160 365 54 55 60 61 86 87 88 89 92 96 381 406
HELIUM, 297 354 100 107 111 120 122 126 131 LOWER CRITICAL SOLUTION
HEPTAFLUOROPROPANE, 372 135 145 157 207 213 222 224 TEMPERATURE, 155 405
HEPTANE, 345 230 239 256 299 307 310 330
HETEROGENEOUS INJECTION MOULD, 166 192
POLYMERISATION, 49 193 INJECTION MOULDED, 31 32 M
HEXAFLUOROPROPYLENE 129 MACHINERY, 12 29 42 79 105
COPOLYMER, 46 91 240 377 INJECTION MOULDING, 4 12 127 144 166 178 188 192 201
HFA-134A, 141 282 25 29 31 32 41 42 48 64 97 101 217 228 260 274 285 332 333
HFC, 244 280 321 118 129 144 166 167 178 188 339 357 373 406 416
HIGH DENSITY 192 203 229 245 286 336 MALEIC ANHYDRIDE
POLYETHYLENE, 33 88 204 INJECTION MOULDING COPOLYMER, 10 98 116
237 260 261 314 336 355 373 MACHINE, 29 42 105 166 192 MASS POLYMERISATION, 136
376 381 393 406 INJECTION PRESSURE, 42 166 270
HIGH PERFORMANCE LIQUID 167 192 MASS SPECTRA, 1 37 174
CHROMATOGRAPHY, 59 161 INJECTION RATE, 70 260 MATERIAL REPLACEMENT, 82
171 174 295 INJECTION SPEED, 4 31 41 97 88 181 204 269 310 329 344
HIGH PRESSURE, 132 155 158 129 167 402
172 182 208 248 252 259 332 INSULATION, 83 143 153 260 MATRIX, 50 83 131 193 214 337
334 366 405 414 INTEGRAL SKIN FOAM, 29 394 MEASUREMENT, 44 90 92 98 105
HIGH TEMPERATURE, 151 172 395 117 119 152 280 333 337 357
203 248 259 332 334 376 INTERACTION, 8 11 14 193 219 383
HOMOGENEOUS, 122 222 270 240 315 335 374 375 388 MECHANISM, 163 197 248 276
321 345 353 380 395 INTERCALATION, 33 53 78 293 361
HOT MELT ADHESIVE, 302 ISOTACTIC, 10 36 331 336 345 MEDICAL APPLICATION, 15 25
HOT WATER, 332 355 39 40 99 166 169 192 193 195
HOUSING, 203 286 ISOTHERM, 88 405 414 360 386
HYDROCHLORO- ISOTHERMAL, 316 392 393 MEDIUM-DENSITY
FLUOROCARBON, 204 237 POLYETHYLENE, 336
280 MELAMINE RESIN, 407
HYDROFLUOROCARBON, 244
K MELT, 10 33 79 140 141 237 268
280 321 KINETICS, 9 16 17 21 49 51 61 282 351
HYDROLYSIS, 124 162 174 259 75 92 110 136 146 147 152 182 MELT FLOW, 10 30 192
320 363 207 222 246 248 290 355 MELT FLOW INDEX, 167 222
HYDROLYTIC DEGRADATION, MELT FLOW RATE, 98 143
37 161 162 259 293 MELT RHEOLOGY, 6 30 94 142
HYDROPHILIC, 49 92 150 211 L 217
223 301 LACTIDE COPOLYMER, 39 106 MELT STRENGTH, 204 228 260
HYDROPHOBIC, 150 193 223 269 169 210 258 MELT TEMPERATURE, 4 6 94 97
315 LANGIVIN EQUATION, 17 61 66 129 167 183 192 201 231 260
HYDROXYAPATITE, 40 210 72 85 92 98 101 110 134 152 MELT VISCOSITY, 6 26 30 94 127
HYDROXYBENZENE, 75 205 271 193 142 192 217 274 282 339 361
LATICES, 139 155 211 233 415
LICENCE, 42 203 237 MELT VISCOSITY INDEX, 167
I LINEAR LOW DENSITY 222
IMMISCIBLE, 15 127 242 380 POLYETHYLENE, 88 170 183 MELTING, 47 66 80 90 91 132 316
284 288 297 304 307 328 337 POLYVINYL ALCOHOL, 358 62 79 97 99 104 112 115 116
341 342 352 354 374 379 383 POLYVINYL CHLORIDE, 88 100 127 143 165 178 182 195 198
394 395 398 405 117 195 237 367 374 381 402 200 201 208 209 218 223 270
POLYNORBORNENE, 128 404 406 271 320 329 333 353 356 373
POLYOLEFIN, 7 9 10 13 14 95 POLYVINYL CYANIDE, 54 87 267 376 395 403 407
107 116 149 204 208 212 224 POLYVINYL ETHER, 387 PROOFED FABRIC, 243
276 280 282 290 315 316 320 POLYVINYL ISOBUTYL ETHER, PROPANE, 88 149 170 314 331
336 344 345 355 375 376 381 387 336 345 393 405 411
391 400 POLYVINYL PYRROLIDONE, 49 PROPYLENE COPOLYMER, 10
POLYOLEFIN ELASTOMER, 355 181 257 266 98 116 355
POLYORGANOSILOXANE, 7 28 POLYVINYL PROPYLENE-ETHYLENE
58 88 115 117 216 225 226 234 TRIFLUOROACETATE, 358 COPOLYMER, 26
246 278 POLYVINYLBENZENE, 26 30 PROTEIN, 99 193 370
POLYOXETANE, 299 387 41 85 103 131 141 142 155 182 PULSED LASER
POLYOXYETHYLENE, 53 199 202 204 217 242 274 POLYMERISATION, 136 328
POLYOXYMETHYLENE, 375 POLYVINYLIDENE FLUORIDE, PURIFICATION, 79 218 270 373
POLYPHENYLACETYLENE, 177 66 81 88 89 90 91 122 127 135 392 409
POLYPHENYLENE OXIDE, 117 155 194 222 240 375 PYROLYSIS, 102 162 320
167 228 298 374 POLYVINYLPYRROLIDONE, 49
POLYPHENYLENE SULFIDE, 181 257 266
237 260 PORE SIZE, 77 134 170 263 345 R
POLYPHENYLOXAZOLINE, 256 PORE STRUCTURE, 149 319 RADICAL POLYMERISATION, 5
POLYPHENYLSULFONE, 228 POROSITY, 4 39 40 76 77 89 115 7 9 49 55 59 61 67 89 122 130
POLYPHOSPHAZENE, 335 134 149 166 170 263 269 276 131 145 146 190 191 222 223
POLYPROPYLENE, 10 12 13 64 345 413 257 263 276 299 328 353
88 98 101 105 107 116 131 166 POROUS, 58 63 99 115 184 193 RATE CONSTANT, 51 136 175
167 176 203 204 212 228 237 198 249 263 270 197
260 315 316 331 336 345 355 POWDER COATING, 115 269 300 RATE OF POLYMERISATION, 9
375 376 381 391 402 406 322 407 21 75 122 177 222
POLYPYRROLE, 58 93 108 187 PRECIPITATION, 88 193 292 324 REACTION CONDITIONS, 17 18
350 384 61 89 92 98 111 128 138 197
POLYSILOXANE, 7 28 49 88 96 PRECIPITATION 213 248 376
115 216 226 335 POLYMERISATION, 54 87 89 REACTION INJECTION
POLYSTYRENE, 7 9 14 19 26 29 120 122 126 135 145 222 270 MOULDING, 204 410
30 41 58 61 69 72 85 88 90 95 323 353 390 REACTION MECHANISM, 17 18
103 107 108 114 127 130 131 PRESSURE, 5 13 14 16 17 44 47 35 84 92 197 248 293
141 142 146 155 166 167 181 66 70 84 88 89 90 91 92 95 111 REACTION PRESSURE, 111 173
182 190 199 202 204 217 224 119 120 121 128 138 140 142 248 376
232 233 237 238 242 251 260 149 152 156 158 159 173 182 REACTION RATE, 21 197 248
274 276 280 282 283 284 285 192 193 200 220 221 224 227 REACTION TEMPERATURE, 17
289 312 319 333 336 338 340 237 240 247 248 249 268 275 174 248 376
342 355 357 374 384 402 404 280 282 286 292 315 316 335 REACTION TIME, 111 138 174
POLYSULFONE, 374 337 344 348 350 351 362 370 248
POLYTETRAFLUORO- 374 375 378 380 392 393 394 REACTIVE EXTRUSION, 11 98
ETHYLENE, 26 88 151 310 367 395 396 404 405 407 409 REACTOR, 3 89 122 197 376 391
389 PRESSURE CONTROL, 159 166 RECIPROCATING SCREW, 178
POLYTRIFLUOROCHLOROETH 167 192 275 286 RECLAIM, 109 294 302 318 363
YLENE, 58 PRESSURE DEPENDENCE, 22 31 364 381
POLYTRIMETHYLENE 129 137 201 202 252 316 337 RECLAIMING, 45 119 165 189
TEREPHTHALATE, 17 33 385 277 349 396 402 406
POLYTRIMETHYLOLPROPANE PRESSURE DROP, 41 201 202 RECLAMATION, 189 277 402
TRIMETHACRYLATE, 184 PRESSURE-SENSITIVE RECYCLING, 12 18 38 52 56 73
POLYURETHANE, 24 187 259 ADHESIVE, 43 68 74 79 88 102 109 160 161 171
303 344 374 382 397 402 407 PRESSURISATION, 275 278 172 189 195 197 226 248 250
410 PROCESS CAPABILITY, 31 32 376 259 271 277 292 294 302 318
POLYURETHANE ELASTOMER, PROCESSABILITY, 6 26 62 79 94 320 332 334 343 349 362 363
385 203 347 364 368 371 373 381 402 410
POLYVINYL ACETATE, 8 291 PROCESSING, 2 4 19 31 39 47 48 REINFORCED PLASTIC, 30 31
40 64 65 69 76 78 102 172 187 SILICONE COPOLYMER, 291 147 157 213 239 255 257 267
260 333 349 369 386 402 SILICONE ELASTOMER, 130 216 288 289 291 297 304 307 354
RHEOLOGICAL PROPERTIES, 2 408 STATIC MIXER, 204 260
6 10 26 30 48 54 72 78 79 80 87 SILICONE POLYMER, 7 28 88 96 STEP-GROWTH
88 94 98 101 105 113 114 116 115 216 226 335 POLYMERISATION, 353
123 127 141 142 166 167 186 SIMULATION, 8 17 197 276 388 STEREOREGULARITY, 126 355
191 192 193 201 202 206 215 SINGLE SCREW EXTRUDER, 26 STIRRED TANK REACTOR, 89
217 221 242 250 251 262 278 204 242 339 357 STIRRING, 122 135 222
282 284 285 305 333 340 342 SIZE EXCLUSION STRUCTURAL FOAM, 203
357 361 CHROMATOGRAPHY, 52 84 STYRENE, 61 172 205
RIBONUCLEASE, 99 210 136 146 190 232 256 314 327 STYRENE ACRYLONITRILE
RING-OPENING SKIN FORMATION, 394 395 COPOLYMER, 88 249
POLYMERISATION, 16 18 27 SKIN-CORE, 29 STYRENE-BUTADIENE-
128 174 207 299 355 387 415 SKIN-INSERT MOULDING, 167 STYRENE BLOCK
RUBBER, 2 28 44 45 68 82 90 92 SLIT DIE, 72 201 202 339 COPOLYMER, 90
115 119 130 137 165 166 187 SLIT-DIE RHEOMETER, 215 STYRENE COPOLYMER, 168
192 199 203 205 216 225 237 SLOT DIE, 72 201 202 339 257 267 355 380 398 415
294 313 321 323 324 325 326 SLURRY POLYMERISATION, STYRENE-MALEIC
327 330 331 332 334 344 351 376 391 ANHYDRIDE TERPOLYMER,
353 355 360 361 366 367 371 SMALL ANGLE NEUTRON 228 260
372 377 378 380 385 387 388 SCATTERING, 156 182 SUBCRITICAL, 110 293
392 397 401 408 409 410 414 SOLID STATE SUBCRITICAL FLUID, 38 162
POLYMERISATION, 75 231 174 175 385
273 281 SUBLIMATION, 88 315
S SOLUBILITY, 3 8 44 48 51 52 57 SUGAR COPOLYMER, 223
SATURATED POLYESTER, 179 62 70 88 90 92 95 100 113 114 SUPERCONDENSING MODE,
200 208 209 210 220 221 268 127 128 137 148 150 167 169 336 355 391
279 320 375 173 176 179 180 187 191 193 SUPERCRITICAL SOLUTION, 26
SCANNING ELECTRON 194 216 218 221 223 231 234 31 32 62 73 78 105 137 154 189
MICROSCOPY, 4 15 19 23 27 240 244 251 258 260 280 291 192 193 196 225 331 356 398
29 39 40 46 48 49 55 57 59 69 297 304 306 309 335 336 342 SUPERCRITICAL SOLVENT, 8
77 83 87 93 97 106 111 116 121 343 357 374 375 404 405 414 72 88 125 137 177 193 201 202
127 130 134 150 155 157 170 SOLUBILITY PARAMETER, 88 207 235 265 281 291 331 349
173 181 183 184 186 194 195 335 354 388 358 371 377
213 232 233 239 246 255 267 SOLUTION, 99 108 113 132 137 SURFACE ACTIVE AGENT, 15 49
274 294 296 331 333 338 350 182 192 193 219 292 331 333 57 88 96 106 150 173 193 211
359 377 383 384 390 413 345 378 380 395 405 236 288 304 321 352
SCRAP TYRES, 2 294 362 SOLUTION POLYMERISATION, SURFACE FINISH, 12 42 166 167
SCREW DESIGN, 196 21 88 125 136 148 190 218 308 192 262 286
SCREW EXTRUDER, 26 123 204 309 336 353 355 SURFACE PROPERTIES, 23 46 77
217 242 SOLVATION, 8 88 176 218 92 93 177 195 359 413
SCREW PLASTICISATION, 166 SOLVENT EMISSION, 403 407 SURFACE TENSION, 180 335 395
SEEDED POLYMERISATION, SOLVENT EVAPORATION, 380 SURFACE TREATMENT, 25 63 92
270 SOLVENT EXTRACTION, 56 193 236 316 359 403
SEMI-CONTINUOUS 370 409 SURFACTANT, 15 49 57 88 96
POLYMERISATION, 401 SOLVENT-FREE, 214 236 407 106 150 173 193 211 236 266
SEMICRYSTALLINE, 90 91 127 SORPTION, 14 55 61 117 132 158 278 288 304
149 183 244 336 384 182 218 220 242 388 414 SURFACTANT FREE, 135 148 222
SEPARATION, 36 56 259 279 292 SPECTRA, 5 34 35 111 SURGICAL APPLICATION, 210
367 372 381 402 406 SPECTROSCOPY, 1 2 3 5 10 23 34 263
SEQUENTIAL INJECTION 35 37 55 59 92 93 98 125 132 SUSPENSION, 106 193 211 278
MOULDING, 166 160 174 182 213 214 235 248 SUSPENSION
SHEAR FLOW, 105 202 337 339 341 POLYMERISATION, 57 88 100
SHEAR PROPERTIES, 105 215 SPHERE, 27 193 225 345 184 336 355
361 SPINNING, 87 200 230 247 SWELLING, 2 10 45 66 90 91 92
SHEAR RATE, 6 72 105 127 141 SPRAY COATING, 403 407 107 119 130 132 140 147 149
142 282 305 348 361 SPRAYING, 384 407 416 152 170 186 193 200 214 219
SHOT SIZE, 4 97 129 STABILISER, 7 28 60 67 86 111 249 296 313 337 361 395 408
Company Index
A CHIBA,INSTITUTE OF F
TECHNOLOGY, 37 248
ACHILLES CORP., 24 CHINESE ACADEMY OF FARADAY PLASTICS, 188
AIR PRODUCTS & CHEMICALS, SCIENCES, 17 61 130 131 171 FENG CHIA,UNIVERSITY, 212
304 335 CHINESE CULTURE FERRO CORP., 169 322
AIR PRODUCTS POLYMERS UNIVERSITY, 108 FRAUNHOFER-INSTITUT
GMBH & CO.KG, 291 CINCINNATI,UNIVERSITY, 345 FUER CHEMISCHE
AKRON,UNIVERSITY, 7 400 411 CLAUSTHAL,TECHNICAL TECHNOLOGIE, 56 246 363
ALICANTE,UNIVERSITY, 195 UNIVERSITY, 8 364
ALUSUISSE COMPOSITES, 237 CLEMSON,UNIVERSITY, 356 FUKUI,UNIVERSITY, 36 176
253 CNRS, 190 256 FUKUOKA,UNIVERSITY, 70 173
AMERICAN CHEMICAL CONNECTICUT,UNIVERSITY,
SOCIETY, 369 1 187
AMHERST,MASSACHUSETTS COPENHAGEN,UNIVERSITY, G
UNIVERSITY, 71 232 296 152 219 GEORGIA,INSTITUTE OF
ATOFINA CHEMICALS INC., 186 CORNELL UNIVERSITY, 180 TECHNOLOGY, 58 92 214 279
AUBURN,UNIVERSITY, 106 205 337 341
292 294 GERMAN TEXTILE RESEARCH
AUSTIN,UNIVERSITY OF D INSTITUTE NORTH-WEST
TEXAS, 384 DELAWARE,UNIVERSITY, 313 EV, 209
AXIOMATICS CORP., 404 380 398 405 GOTTINGEN,GEORG-AUGUST-
DEMAG ERGOTECH GMBH, 42 UNIVERSITAT, 8 9 136 168
DEUTSCHES GOTTINGEN,UNIVERSITY, 146
B DEXTILFORSCHUNGS- GUNMA,UNIVERSITY, 271
BARCELONA,INSTITUT DE ZENTRUM NORD-WEST EV,
CIENCIA DE MATERIALS, 193 315 316 346 399
BASF, 376 DOW, 376 388 H
BEIJING,INSTITUTE OF DSM HIGH PERFORMANCE HANYANG,UNIVERSITY, 197
CHEMISTRY, 95 107 224 FIBERS, 230 HARBIN,INSTITUTE OF
BEIJING,STATE KEY DSM RESEARCH, 84 TECHNOLOGY, 37 248
LABORATORY OF DU PONT DE NEMOURS E.I.,& HITACHI CABLE LTD., 160
ENGINEERING PLASTIC, 47 CO.INC., 377 HOECHST, 376
BEIJING,UNIVERSITY OF DUMAPLAST, 237 HOECHST CELANESE CORP.,
TECHNOLOGY & BUSINESS, DUPONT CO., 151 153 367 396
14 DUPONT FLUOROPOLYMERS, HUSKY INJECTION MOULDING
BRADFORD,UNIVERSITY, 324 143 SYSTEMS LTD., 192
BROOKLYN,POLYTECHNIC
UNIVERSITY, 18
BRUNEL UNIVERSITY, 123 201 E I
BUCKEYE TECHNOLOGIES, 279 ECLIPSE BLIND SYSTEMS INC., I-SHOU,UNIVERSITY, 221
237 253 ICI CHEMICALS & POLYMERS
C EINDHOVEN,UNIVERSITY OF LTD., 409
TECHNOLOGY, 5 74 84 139 INDIAN INSTITUTE OF
CAMBRIDGE,UNIVERSITY, 323 230 328 SCIENCE, 110 238
CANADA,NATIONAL ENGEL NORTH AMERICA, 167 INSTITUTO DE CIENCIA
RESEARCH COUNCIL, 21 229 Y TECNOLOGIA DE
CATALUNYA,UNIVERSITAT EPSRC, 371 POLIMEROS, 193
POLITECNICA, 88 ETABLISSEMENTS VALOIS, 392
CAVENDISH LABORATORY, 134 EXPRESS SEPARATIONS LTD.,
CHANGCHUN,INSTITUTE OF 327 J
APPLIED CHEMISTRY, 34 35 EXXON, 376 JAPAN,CHEMICAL
80 138 EXXON RESEARCH & INNOVATION INSTITUTE,
CHEMICAL & POLYMER, 115 ENGINEERING CO., 309 331 158 159
236 269 344
JAPAN,NATIONAL INSTITUTE
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