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Master of Science

in Refining, Engineering and Gas


Module 34
Polymer Fundamentals (5)

Polymer structure, properties and


characterization

PDVSA / INTEVEP IFP School / IFP TRAINING


June 2009
Robert PELLETIER
1
I am inclined to think that the development of
polymerization is perhaps the biggest thing chemistry
has done, where it has had the biggest effect on
everyday life. Lord Todd, Chemistry Nobel Prize 1957

Yet, polymers and plastics have a poor image in the


general public, often looked at as cheap substitutes to more
noble materials such as glass or aluminum.
Lord Todds view is fully supported by the very fast
development of petrochemistry and of the industrial
polymers it produces.
This on-going development proves that the consumers
make increasing use of these materials, taking advantage
of their exceptional diversity and adaptability. 2
There is a sharp
contrast
between the
very poor image
of plastics in
the public and

WORLD YEARLY PRODUCTION OF STEEL,
PLASTICS, ALUMINUM AND RUBBER
M
T PLASTICS
At the worldwide
their quantitative S
level, needs of
developing
T STEEL
growth, which is E
countries maintain
plastics annual
commanded by the E
L
growth rate close
to 6 %. ALUMINUM
marketing decisions of
3
this same public. RUBBER
MONO

OLIGO + MER =

POLY

MONOMER, OLIGOMER, POLYMER

! Polymers # Plastics
4
POLYMERS

FUNCTIONAL
PLASTICS ELASTOMERS
POLYMERS

THERMO- THERMOPLASTIC
THERMOSETS
PLASTICS ELASTOMERS

1D : FIBERS
FIBERS

2D : FILMS

3D : OBJECTS 3D : OBJECTS 5
Thermoplastics, thermosets,
elastomers, thermoplastics elastomers
Thermoplastic materials.
Long chain molecules are held together by weak Van der Waals
forces. When heated, intermolecular forces are weakened, material
becomes soft and flexible; eventually, at high temperatures, it is a
viscous melt which can be put into any desired shape, that will be
retained by cooling. This process is reversible.

Thermoset materials.
Reactive molecules of a pre-polymer are heated in a mould with an
initiator, react with each other through intensive cross-linking,
leading to a huge molecular network of a single giant molecule.
Material is hard and strong, but cannot be softened again.
6
Thermoplastics, thermosets,
elastomers, thermoplastics elastomers
Elastomer materials.
Flexible twisted long chains are anchored together by only a
moderate level of cross-linking. When material is stretched,
molecules unwind but cannot slide, allowing return to the
original shape when strain is released.

Thermoplastic elastomers.
Behave as elastomer at room temperature. But the cross-
linking bonds between molecules weaken at elevated
temperature, leading to a viscous melt just as for
thermoplastics.
7
FUNCTIONAL POLYMERS

Thermoplastics, thermosets, elastomers, thermoplastic


elastomers are all used as materials, for the production of
goods which make use of their specific mechanical
properties.
Functional polymers, on the other hand, are not used for
their own structural properties but rather in association with
other materials to which they bring a very specific property...
...such as water impermeability, gas barrier, adhesion to
substrate, corrosion protection, piezzoelectric behavior,
absorption capability, etc.

8
Polymers : some historical milestones.

Bridgnorth's Northgate Museum


XIV century. Ersatz of cow horn
(casein) by a German monk.
For centuries, cow horn, when steam heated under
pressure, had been shaped into useful objects such as
gourds or transparent sheets for lanterns (lant-horn).
But few cows and big demand !

2nd half of XIX century. Natural


Polymers Galalith, Celluloid,
Goodyear.

Industrial polymers appeared at the


beginning of the XX century
9
Polymers : some historical milestones.

XIV century. Ersatz of cow horn (casein).


2nd half of XIX century. Natural Polymers Galalith,
Celluloid, Goodyear.
1909. Bakelite (Baekeland). The first truly synthetic polymer,
from coal tar. God said:" Let Baekeland be" and all was Plastics!
1930. Polystyrene (IG FARBEN).
1931. PVC (IG FARBEN)*.
1938. Polyamide ("NYLON" from DU PONT).
1939. High Pressure Polyethylene (ICI)*.
1957. Polypropylene (Montedison).
10
Remember : although significant, world petrochemistry
consumption amounts to only a small fraction of oil use.
Sources : IEA,
BP Statistical Data,

Coal

Hydroelectricity

Nuclear Energy
Natural Gas

Petrochemistry usage : ~350 MT/y


Oil
~280 MT/y polymers
11
Consumption of
various materials in
the United States.
(Log scale, volume unit)

Significant volumes of
plastics usage started
only after World War
II, but already over-
passed steel in the
80s.

Plastic Age !!!


12
PLASTICS

ALUMINUM

STEEL

At the worldwide level, needs of developing countries


13
maintain an annual growth rate close to 6 %.
World Demand PE, PP, PS, PVC, PES/PET
On-going
impressive
growth,
even 160
for PVC. 8
140 20
120
26
PET
100
17 PES
1
MT/year 80 9
28 PVC
18
60 PS
9
40 0
5 13 PP
9 49
5 PE
20 4,5 30
PET now 14
joining 0
the Big 4 1980 1990 2000
PES = polyester for fibers and films 14
PET= polyethylene terephtalate high molecular weight
POLYMER CONSUMPTION
per CAPITA
2001
Polymers consumption in kt / capita

200 8000

Population in Mio Hab.


175 7000
150 6000
125 5000
100 4000
75 3000
50 2000
25 1000
0 0
N.AMER. W.EUR L.AMER E.EUR. M.EAST ASIA+AFR. WORLD

PE PP PS PVC Other Population (Mio Hab.)

15
Quantitative growth, but also an astonishing
qualitative diversity
PRICE/PERFORMANCE
HIGH PERFORMANCE POLYMERS

ENGINEERING POLYMERS

COMMODITY POLYMERS

MARKET SIZE
16
PLASTIC PYRAMID

17
A BRIEF INTRODUCTION to
THE DIVERSITY OF
POLYMER CHEMISTRY and
STRUCTURE

18
Mer = unit Mono = single Oligo = some Poly = many

The degree of polymerization (DP) is the number of mers


(units) in a polymer molecule. DP of 1000 to 20000 are typical for
industrial polymers. Molecular weight of the polymer will greatly
influence the processing and mechanical properties. (1)Polyethylene
has an average DP of 10000. Molecular weight ? Average weight of a single molecule ? Average
length of streched molecule.

Classification of polymerization mechanisms.


When the polymer chain grows unit by unit, like pearls being
inserted one after the other into a necklace, the polymerization
mechanism is called chain growth polymerization .
When the polymer chain can add to a monomer, to an oligomer or to
an other polymer chain, and form a longer chain, polymerization
mechanism is called step growth polymerization.
19
Both chain and step growth chemical steps may involve the release of
a small molecule like H2O, MeOH, HCl, : in such case, the mass of
the polymer is lighter than the mass of the reactants: this mechanism is
called condensation. (The polymer is condensed with regard to the monomers).
When the whole reactive molecules are incorporated into the growing
chain, the mechanism is called addition.
Most industrial polymers belong to the two colored windows.

Chain growth Step growth


Polymerization Polymerization
Addition Pn + M Pn + Pm
P(n+1) P(n+m)
Condensation Pn + M Pn + Pm
P(n+1) + L P(n+m)20 + L
All polymers of petrochemistry have a carbon backbone.
The simplest hydrocarbon is
methane, with four strong covalent
bonds to four hydrogen atoms

Ethylene is the simplest hydrocarbon


with a double bond. Opening of this
double bond and forming a chain will
lead to the simplest and most important
polymer : polyethylene

21
The extraordinary diversity of polymers derives first from
the wide diversity of possible mono mers
all alkenes can be
Starting from the simple
polymerized one way or
ethylene
another,

with propylene being the fastest


growing and most important after ethylene.

With butenes, four isomers leading to totally different polymers :

1-butene 2- cis-butene 2- trans-butene 2-methyl-propene


or iso-butylene

Isomers number increases with the number of carbon atoms. 22


Substitution of one or more H atoms by various chemical
group leads to further diversity of mono mers

Some examples of the most important vinyl monomers,


which polymerize by opening of the double bond :

Styrene Vinyl Chloride Acrylic acid Methacrylic acid


and their esters (acrylates, methacrylates)

Vinyl acetate, monomer for Poly(vinyl acetate) PVAc, also


for Poly(vinyl alcohol) PVOH.

23
VF4 ? VF2 ? VDC ? Butadiene ?
Monomers with two (or more) reactive end groups lead to many
polymer families through step growth polymerization. Varying the
ends groups and the backbones yields a near infinity of polymers
Polyamides (containing amide functional groups in their main chain), , from di-acids
and di-amines, or from amino acids, or from lactams. Example :

adipic acid hexamethylene diamine nylon 6-6

Polyesters (containing ester functional groups in their main chain), from di-
alcohols (or epoxides) and di-acids (or di-chlorides). Example :

PET from terephtalic acid and


ethylene oxyde.

And also polyurethane, phenolics, epoxy, etc families.


24
The list of potentially useful monomers is very long.
Some of the
most usual end
groups of
monomers
which
industrially
used for step
growth
polymerization.

25
Some of the most important polymers
made by step polymerization

Diacid Diol Diamine Acid Isocyanate


anhydride

Diacid Polyesters Polyamide

Diol Polyesters Polyurethane

Diamine Polyamide Polyimide

Acid Polyimide
anhydride
Isocyanate Polyurethane

26
COMBINING DIFFERENT MONOMERS in the SAME
POLYMER MOLECULE ADDS ANOTHER DIMENSION TO
THE ART OF POLYMER TAILOR MAKING
Homopolymers are made up of only one monomer.
Copolymers make use of two or more monomers; the way these are
distributed in the copolymer chain will influence polymer properties.
Random, alternate, block, or grafted are the most usual distributions.

RANDOM COPOLYMER -A-B-B-A-A-A-B-B-B-A-B-A-A-B-A-B-A-

ALTERNATE COPOLYMER -A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-

BLOCK COPOLYMER -A-A-A-A-A-B-B-B-B-B-B-A-A-A-A-A-A-

GRAFTED COPOLYMER -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-


-B-B-B

-B-B

-B-B-B-B
27
FOR HOMOPOLYMER (and copolymers as well), VERY
DIFFERENT PROPERTIES CAN BE OBTAINED BY VARYING
THE SHAPE OF THE MOLECULES OF THE POLYMER
LINEAR -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T

-A-A-A-A-A-A-A-A-A-A-A-

A-
BRANCHED (short and long) -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T

--A-A-A

-A-A
CROSS LINKED -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T
--A-A-A-

--A-A-A-
-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T

Chemical nature of chain terminations can also be important. They are


often weak points which can initiate chain degradation. How could a28star
shaped polymer molecule be synthesized ?
FOR ASYMETRIC MOLECULES, THE WAY THE UNIT IS
INSERTED IN THE CHAIN WILL ALSO COMMAND THE
POLYMER PROPERTIES
Head-to-tail or Tail-to-tail:
monomeric units are
identically inserted or
alternately reversed.

Stereospecificity : if monomer always


adds in the same stereo arrangement

Same

Alternate

Random 29
Example of 1,3-butadiene polymerization

Cis Vinyl Trans

Three different
ways for the
The remaining
butadiene
double bond
molecule to be
can be within
inserted within
the chain, or on
the chain
the side of 30it.
Example of 1,3-butadiene polymerization

cis trans vinyl Different


Catalyst 1,4 1,4 1,2 Tg polymerization
Nd >96 2 <1 -109 catalysts yield
Co 96 2 2 -107 different % of various
Li 38 52 10 -93 configurations
Ti 92 4 4 -105 31
Source Lanxess
Average Molecular Weight of a Polymer is of prime importance for
its rheological and mechanical properties. But the distribution of
the molecular weight also plays an important role.
% broad distribution Same average molecular
narrow distribution weight, but very different
distribution quite different
polymer properties
Molecular weight

Number average molecular weight: Weight average molecular weight:


Mn = Ni Mi/ Ni Mw = Ni Mi2/ Ni Mi
Polydispersity = Mw/Mn
Mi : molecular weight of a chain Ni : number of chains of that molecular weight.

500 stones of 1 kg + 2 stones of 250 kg 400 stones of 1 kg + 100 stones of 6 kg


Mn ?
Mw ?
32
Polydispersity
More generally, one can define: Mq = Ni Miq+1/ Ni Miq

q = 0 M = Mn q = 1 M = Mw q = 2 M = Mz
Mn < Mw < Mz
The higher averages are increasingly more sensitive to the high
molecular weight fraction of the polymer.

Polydispersity index = Mw/Mn


The larger the polydispersity index, the broader the molecular weight.
A monodisperse polymer (all chain lengths equal such as a protein)
has an Mw/Mn = 1.
The best controlled synthetic polymers (eg narrow polymers
used for calibrations) have Mw/Mn of 1.02 to 1.10.
Step polymerization reactions typically yield values of Mw/Mn
of around 2.0, whereas chain reactions yield Mw/Mn values
between 1.5 and 20.
33
POLYMER MORPHOLGY
SEMI-CRYSTALLINE and AMORPHOUS THERMOPLASTICS

In the solid state, the polymer molecules can get organized into an
organized crystalline structure, only if molecules have a regular
chain structure, and if forces holding chains together are strong
enough to overcome disordering effect of thermal energy.
In practice, no polymer can exhibit a 100% crystalline structure,
hence the name of semi-crystalline. PE, PP, PA are examples of
semi-crystalline polymers.

Mixture of amorphous and


crystalline domains (a). When
material is stretched, orientation
of chains induces an increase of
crystallinity (b).
34
POLYMER MORPHOLGY
SEMI-CRYSTALLINE and AMORPHOUS THERMOPLASTICS

Beyond the order at the


atomic C-C bond level (~0.5
nm), crystallization organizes
chains into lamellae of ~20 to
100 nm, themselves into
spherulites of 50 to 500
microns.
Organization of the chains in
dimensions greater than wave
length of visible light makes
these semi-crystalline
polymers non transparent.
35
POLYMER MORPHOLGY
SEMI-CRISTALLINE and AMORPHOUS THERMOPLASTICS

If no crystalline structure exists, polymers are amorphous. PVC, PS,


PMMA are examples of amorphous polymers. The largest dimension of
organized matter is at the level of C-C bond (~0.5 nm), thus below
wave length of visible light : amorphous polymers are transparent.
Randomly entangled molecules of an
amorphous polymer are often viewed
as strands in a bowl of spaghettis.
(And crystalline domain as the uncooked spaghettis)

However, because of the constant


thermal motion of molecules, a
better image might be a bowl of
snakes !
36
POLYMER MORPHOLGY
SEMI-CRYSTALLINE and AMORPHOUS THERMOPLASTICS

Amorphous solid polymers (and amorphous phase of semi-crystalline polymers)


can exhibit two very different types of mechanical behavior.
Glass transition occurs when the temperature gets so low that
"snakes start hibernating", when the molecules stop moving
(translational and wriggling movement).
Below Tg, the material is hard, rigid, brittle, glassy.
Above Tg, it is a soft, flexible, rubbery material.
Glass Transition can occur well below the melting point of the
crystalline phase of the polymer and should not be confused with it.

Glassy at room temperature : PS Tg~100C, PVC Tg ~80 C


Rubbery " " : LDPE Tg~ -80C, natural rubber Tg ~-70C
37
Additives which can influence the polymer morphology.

Plasticizers may be used to decrease Tg and thus make the


material softer, more resistant to bending and impact.
Plasticized PVC, with up to 50% octyl-phtalate, is a totally
different product from Rigid PVC. Mineral Oil (up to 2 %) is
often used for Polystyrene.
Oligomers and low molecular weight fraction of the polymer can
behave as a plasticizing agent for the whole material.
Nucleating agents can be added to increase the speed of
crystallization of the cooling polymer and control the size of the
crystalline domain. Sodium Benzoate (500-1000 ppm) is often
used as a polypropylene nucleating agent, leading to increased
strechability and reduced shrinkage
38
Chain growth polymerization can proceed through different
chemical routes: Free radical, Anionic, Cationic, Co-ordination

Free radical polymerization uses an initiator (e.g. peroxyde), which will generate
free radicals. Overall kinetics governed by initiation, propagation,and
termination rates.
1)Initiation I2R R + M M1 ki
2)Propagation M1 + M M2 .. Mn + M Mn+1 kp
3) Termination Mi + Mi Mi+j (or disproportionation) kt
But polymer quality will essentially be fixed by the various chain transfer
reactions that will determine the molecular weight distribution.
Mi + M Mi+ M1 Mi + S Mi+ S Mi + Mj Mi+
Mj Transfer to : Monomer Solvent or telogen Polymer

Free radical polymerization is probably the most widely used type of


polymerization, for a wide variety of processes and monomers.
39
White glue -
All these cups are Emulsion
made from "mass process
process"
polystyrene.

High Impact,General Purpose, Expanded PS


Greenhouse film - High
All these Pressure bulk PE Process
processes use
Free Radical
Polymerization
PVC Floor Covering -
Emulsion process
PVC Piping -
Suspension process
PMMA Sheet -
Cast sheet
process 40
Chain growth polymerization can proceed through different
chemical routes: Free radical, Anionic, Cationic, Co-ordination
Addition polymerization can be initiated by anions anionic polymerization
Butyl lithium is the most current of such initiators, in particular for styrene and
butadiene polymerization.
Main caracteristics are that there is no transfer reaction and that the active species
have long life time (living polymerization), especially useful for block copolymers.

Controlled termination
enables to yield various
shapes of polymer
molecules and
controlled end groups.

41
Example of anionic polymerization : SBS block copolymers
THERMOPLASTICS or THERMOPLASTIC ELASTOMERS (TPE) tri-block S-B-S
taylor-made by ANIONIC LIVING POLYMERIZATION (linear or star-shaped)

RUBBER LIKE MATERIAL (TPE): High Butadiene content SBS

Asphalt Modification,
Footwear,
Adhesives,
Plastics
modifier

THERMOPLASTICS: High Styrene content

42
Chain growth polymerization can proceed through different
chemical routes: Free radical, Anionic, Cationic, Co-ordination

Polymerization of vinyl monomers, with electron


rich substituent next to double bond, can be
catalysed by strong Lewis acid cationic
polymerization
BF3 and AlCl3 are the most common catalysts.
Petroleum resins and polyisobutylene are produced
using this type of polymerization. 43
Example of cationic polymerization : Polyisobutylene

~ -100C for
reaction control

Polyisobutylene is sometimes called butyl


rubber, or PIB. It is similar to Polyethylene in
structure, except that every other carbon is
substituted with 2 methyl groups.

Polyisobutylene is a synthetic rubber. It has


been developed during WW II, when Japanese
occupied Malaysia and severed natural rubber
supply to the Allied nations.

PIB is the only rubber that is gas


impermeable. Because it will hold air, it is
used to make the inner liner of tires, or the 44
inner liners of basketballs.
Example of cationic polymerization : Petroleum Resins
Petroleum Resins are low molecular weight
polymers obtained by cationic polymerization of
olefins, diolefins and aromatic vinyl compounds
contained in C5 and C9 cuts (AlCl3 or BF3
catalysts) . They are used as additives in a wide
range of applications:
- Pressure sensitive adhesive
- Hot-melt adhesive
- Hot-melt road-marking paint
- Synthetic rubber
- Belt tyre
- Shoes adhesive
- Paint
- Printing ink
where they act as tackifing, reinforcing, softening,
compatibilizing, filling, etc., agents.

Petroleum resins are especially useful for


tack , the instantaneous sticking effect.
Rolling-ball tack tester is universally used to
45
measure this instant tack ! Simple, isnt it ?
Chain growth polymerization can proceed through different
chemical routes: Free radical, Anionic, Cationic, Co-ordination
The ability of certain heterogeneous catalysts Today, most of the
(TiCl3, chromium oxyde on silica) to polymerize
ethylene was discovered in the early 50s. The capacities for
polyethylene produced was very linear and polyethylene and all of
crystalline compared to the early high pressure those for polypropylene
polyethylene. are using this type of
Giulio Natta in Italy extended this potential to polymerization.
the highly stereospecific polymerization of - Development of the new
olefins, of propylene in particular. First PP plant family of catalyst
started in 1957.
(metallocenes) further
expands the potential of
the field of co-ordination
catalysis. In tonnage, this
is the most important
type of polymerization
catalysis. 46
HDPE Sewer waste water tank.

PP Bumpers

Ethylene-Propylene-
Diene monomer Rubber HDPE films

Bi-oriented film PP

HDPE Gas Piping

47
Step Polymerization

Monomers with two (or more) reactive end groups


lead to many polymer families through step growth
polymerization. Varying the ends groups and the
backbones yields a near infinity of polymers.

Polycondensation was used for the


early thermosets resins such a
Bakelite. Wallace Carothers made
history when he and his team
invented the famous Nylon after
developing the first synthetic silk
(polyester). 48
Polyesters (containing ester functional groups in their main chain), from di-
alcohols (or epoxides) and di-acids (or di-chlorides). Example :

PET from terephtalic acid and


ethylene oxide.

PET bottles Medical


everywhere tissues

Main
application
is textile

Thermoformed
packaging

Excellent
aptitude to
recycling
49
Polyamides (containing amide functional groups in their main chain), from di-acids
and di-amines, or from amino acids, or from lactams. Example :

adipic acid hexamethylene diamine nylon 6-6

Actuator
injected
piece
Textiles

Colson
tier

Castor oil
PA11 Dish
washer 50
basket
Polyurethanes (containing amide functional groups in their main chain), from di-
isocyanates and diols. Example :

51
Optimizing the polymer properties

We have briefly reviewed how the proper selection :


of (co)monomer(s),
of polymerization mode,
of catalysts or initiators,
of molecular weight and molecular weight distribution,
will control the molecular structure of the polymer and will
offer an infinity of potential materials.
Example of copolymerization.

52
Free Radical Copolymerization kinetics

RANDOM FREE RADICAL COPOLYMERIZATION

- M1-M2-M2-M1-M1-M1-M2-M2-M2-M1-M2-M1-M1-M2-M1-M2-M1-

Is it really random ?
~~~~~~~~M1. + M1 M1. k11
~~~~~~~~M1. + M2 M2. k11
~~~~~~~~M2. + M1 M1. k21
~~~~~~~~M2. + M2 M2. k22
Simplified but realistic model assumes reactivity only dependent on the last
monomer unit (independent of penultimate monomer).
If k11 >> k12 and k22 >> k21 block copolymer
If k11 << k12 and k22 << k21 alternating copolymer
If k11 ~ k12 and k22 ~ k21 true random copolymer 53
Free Radical Copolymerization kinetics

Pseudo steady state hypothesis states that [M1.] and [M2.] can
be considered as constant in any time interval small compared to the
overall reaction time, M1. and M2. are being consumed and
produced at the same rate . dM dM 0
1

2

dt dt

Combination of these three equations enables elimination


of [M1.] and [M2.]
54
Free Radical Copolymerization kinetics

It is a standard practice to
define:
and to use mole fractions :
F1 and F2 in the copolymer
being produced
instantaneously,
f1 and f2 in the reactive media.

Fancy algebra manipulations r1f1 f1f2


then yield a relationship F1
between F1 and f1 at any r1f1 2f1f2 r2f2
given time.
55
Free Radical Copolymerization kinetics
Of course, f1=F1=1 or =0 are
the simple cases of
homopolymers of M1 and M2.

Note that, when r1 and r2


are < 1, there is another
concentration where
f1=F1. This is called the
polymerization
azeotrope.

Whenever F1 significantly differs from


f1, concentration drift will occur in batch
reactors, requiring special control means
to insure polymer homogeneity. 56
Free Radical Copolymerization kinetics

Methyl acrylates /
Vinyl acetate
r1= 9 , r2= 0.1

Ethylene /
Vinyl acetate
r1=0.97 , r2= 1.02

Vinyl acetate /
Vinyl chloride
r1= 0.23 , r2= 1.68

Acrylonitrile /
1-3 Butadiene
r1=0.02 , r2= 0.28

Styrene /
Maleic Anhydride
r1= 0.01 , r2= 0.0

57
A few examples of benefit from copolymerization
Modifying the Glass Transition temperature. Polyacrylonitrile could be an
exceptional wonderful polymer (e.g. barrier properties), but its Tg is so high that
material would degrade rather than soften at high temperature: not a thermoplastic.
Copolymerizing with acrylates (70%AN, 30%AM) leads to a reasonably good
barrier material which can be thermoprocessed.
Polystyrene is an easy to process polymer, but its Tg does not allow high usage
temperatures. Copolymerizing with Acrylonitrile (70% St, 30%AN) will lead to a
polymer (SAN) with improved mechanical properties.

Changing the cristallinity. Random Copolymerization of Propylene with a few


% of ethylene (up to ~4%) will hinder the crystallization process and lead to a
more flexible and transparent polymer.
Changing the molecular weight. Adding some di-vinyl-benzene (~0.1%) to PS
Mass polymerization can lead to higher Mw without loss of productivity of the
reaction section.
Creating new structure. Tri-block polymers of the type S-B-S lead to
polybutadiene domains leading to very good impact resistance, yet small enough
58
to enable full transparency of material.
Phase Diagram for a Random
Copolymer System
Residence time distribution. Batch Continuous.
Batch reactors are closed systems, with no addition or removal of
reactants during the reaction.

In such simple case, all


volume elements have the
same residence time.

By contrast, continuous devices (open systems) have one or more inlets


for introduction of reactants and one or more outlets for products.
Batch reactors operate under unsteady conditions, while continuous
reactors are usually designed for steady state conditions.

In semi-batch (or semi-continuous)


systems, some additional reactants are
introduced continuously during60the
batch time.
Residence time distribution.
Ideal models of Plug flow and CSTR.
Q
Q V
V

Ideal plug flow reactors are continuous reactors (typically tubular type
of reactor) with flat velocity profile ; all volume elements have the
same residence time and the distribution is a Dirac function at
time = V/Q (V volume of reactor, Q volumetric flow rate through reactor).
Continuously Stirred Tank Reactors (CSTR) are continuous
reactors with an ideal agitation. Concentration of the various
chemicals are uniform throughout the reaction medium. All volume
elements in the reactor have the same probability to get out of it,
61
independently of their age in the reactor.
Residence time distribution. CSTR
Let f(t) be the residence time distribution. This means that the probability of a
volume element to get out of the reactor between time t and t+dt is equal to
f(t).dt
The cumulative residence time distribution, F(t), is the probability that an
element of volume has a residence time between 0 and t.
F(t) = f(t) dt from 0 to t
In a CSTR, the probability for an element inside the reactor to get out of it
during the next time interval dt is equal to dV/V= Q.dt/V= dt/ ( = V/Q)
The probability for an element to get out of the reactor between time t and t+dt
is equal to the probability that it did not go out before time t, multiplied by the
probability to get out of it during the next time interval dt.
f(t).dt = [1-F(t)]. dt/ leading to a differential equation for F(t)
dF/dt = (1/).[1-F(t)] Ln[1-F(t)] = - t/

F(t) = 1- exp(-t/ ) and f(t) = (1/ ) exp (-t/ )


for a CSTR 62
Residence time distribution: CSTR
Reactor cascade

Using cascade of CSTR reactors in


series moves the residence time
distribution closer to that of a plug flow
reactor.

Example of
MITSUI PP
Process

INEOS PE Gaz Phase process seen in Lavera uses one


single fluidized bed reactor, close to a CSTR. But catalyst is
first pre-polymerized before being injected into the reactor.
63
Residence time distribution.
Ideal models of Plug flow and CSTR.
Of course, real industrial reactors
are not strictly ideal plug flow or
CSTR. Velocity profiles in tubes,
for instance, are never flat. Ideal Turbulent Laminar

Distribution of real reactors can be simulated by combination (series


or parallel) of CSTR and plug flow reactors. 64
The art of making a useful plastic : a long chain

Other
Chemicals Monomer(s) Product engineer
preferred domain

Polymerization Polymer
Additives
Technology Structure

Processing Processing Material


Technology Properties Properties

Plastic
Properties Application End of life
65
Analytical methods of characterization are important tools for the
proper understanding of the whole chain towards the right plastic.
Length of the chain requires a sophisticated traceability system:
the completeness of the information about every step in the process
chain. (Example of Jeanneau polyester boats: wrong pexyde premature aging
of the boat structure after some years).

Monomers and Chemicals : their proper quality and consistency


is key to the stable operation of plants. Being within the specs
is a must, but far from being enough !
Polymerization Process. Just like any other process, needs to
follow the critical parameters of operation. Time is critical as most
polymerization plants change grades from twice a day to twice a
week.
Modern tools like NMR are now standard equipment in the plant,
enabling faster control. Trend towards on-line analysis (or 66
automatic at-line analysis) and use of intelligent sensors.
Analytical methods of characterization are important tools for the
proper understanding of the whole chain towards the right plastic.

Material Properties. The most important characteristics, to


assess suitability of a polymer for a given application, are:
Mechanical properties (strength, stiffness, toughness, fatigue
resistance, and their sensitivity to high and low temperatures)
Corrosion susceptibility and degradation
Wear resistance and frictional properties
Optical properties (haze, gloss, color)
Special properties like electrical and thermal conductivity,
damping capacity, permeability, adhesion, etc. and ....
Total Cost, of course, which is key in the polymer selection.
67
Mechanical Properties
Stress-strain curves show the response of a material to an
applied stress information on material's elastic modulus
and yield stress.
. Polymer stress-strain curves produced by stretching
sample at constant rate through the application of a tensile
force. Please, note that polymers have a marked inherent time-
dependence in their response to deformation, which sets their behavior
apart from other classes of material.

Stress (s ) = force applied per


unit area s = F/A
s

Strain (e) = deformation per unit


dimension. For tensile experiment: e = D l/l
Hookes law: E = s /e in elastic
region. 68
e
Mechanical Properties. Typical stress-strain behavior
Hard brittle material, such as
amorphous polymer far below its Tg.
Usually very high modulus, typical
elongation is about 2 per cent. (GPPS)
Hard and strong polymers have high
modulus of elasticity, high strength,
and elongation at break of
approximately 5 per cent. (HIPS)
Hard, tough polymers have high yield
points and high modulus, high
strengths and large elongations. Most
polymers of this group show cold-
drawing or "necking" during the
stretching process. (PA)
Soft and tough polymers show low
modulus and yield values, moderate
strength at break, and very high
elongation ranging from 20 to 69
1000
per cent. (Plasticized PVC, rubbers)
Mechanical Properties. Impact Strength

Toughness is the resistance to fracture.


Several methods are used to measure the
impact resistance of plastics - Izod,
Charpy, Gardner, tensile impact, etc. The
Izod impact test is the most common test
in North America.

Polymeric materials sensitive to the stress concentrations at


the notch will perform poorly in the notched Izod test. They
should be avoided in designs with create high stress
concentrations such as sharp corners or cutouts. Unnotched
specimens also frequently tested via the Izod method to give
complete understanding of impact resistance.

70
OTHER MECHANICAL TESTS
IMPACT RESISTANCE

Izod test In all cases, very high sensitivity


Standard: ISO 180 of the polymer impact strength to
the temperature. Care should be
exercised when interpreting data
obtained at one temperature.

Charpy test
Standard: ISO 179
Impact
Strength

Instrumented
impact test
Standard: ISO 66-03/2
Temp
71
Mechanical Properties. POLYMER DEGRADATION
Degradation of plastics occur through
breakdown of its chemical structure. Not
only acids or solvents, but also water
(hydrolysis), oxygen, heat, stress,
radiation, or combination of those can
contribute to the degradation. Semi-
crystalline polymers usually offer better
environment resistance.

In some plastics, contact with certain substance can induce brittle


cracking, where there is residual internal stress : environmental
stress cracking (ESC). Most organic liquid will induce ESC.
Polyethylene, ABS, PS are prone to ESC, believed to be due to small
molecules diffusing to surface defects, promoting fracture by
modifying surface energy. 72
Processing Properties.
Certainly, the most important processing property of a polymer is its
flow behavior, when it is shaped into a plastic.
Rheology: the science of the deformation and flow of matter. (Term
inspired by Heraclitus's famous expression panta rhei , "everything flows".)

But one should not forget that, before entering the plastic phase, the
polymer needs to be stored, conveyed, dosed, fed, molten. And after
it has been shaped into a plastic, it has to go through cooling,
crystallizing, demolding stages. All of these operations are part of
the processing phase.
Size, shape and homogeneity of
pellets, content of fines or of angels
hair, crystallizing speed, content of
demolding agent, etc., have to be Lenticular and cylindrical pellets do
measured and controlled in the not behave in the same way in the
feeding zone of an extruder
polymerization plant. 73
Processing Properties. Rheology

In practice, rheology is principally concerned with extending the


disciplines of elasticity and Newtonian fluid mechanics to
materials whose mechanical behavior cannot be described with the
classical theories.
A non-Newtonian fluid is a fluid in which the viscosity changes
with the applied strain rate. As a result, non-Newtonian fluids may
not have a well-defined viscosity.
Starch and water is an example of
shear-thickhening non newtonian
behavior.
Most industrial polymers are on the
contrary shear-thining, i.e. their
viscosity decrease with increased shear. 74
The following properties are more specific
of thermoplastics, i.e. polymers that soften into
viscous liquids when heated and freeze into solid state
when cooled sufficiently.

Processing Flow Properties and Rheology

Optical properties
Structure characterization, G.P.C.

75
PROCESSING PROPERTIES MELT FLOW INDEX
Very simple, unsophisticated piece of
equipment, used to characterize
Weight
Masse
fluidity of a molten polymer. It
measures the flow rate of a molten
polymer (in g per 10 mn) through a
Heating
Chauffage
die.
It decreases when increasing the
190
average molecular weight.
Cylinder
Cylindre Standards: ISO1133, ASTM1238, DIN53735
Molten
Polymre Polymer
fondu

DieFilire MFI high fluid polymer, short chains


DiePorte-filire
holder MFI low viscous polymer, long chains
MFI rigidity
Insulation
Isolant impact resistance
extrudability

Using two different weights (typically 2.16 and 21.6 kg) can give
an idea of the non-newtonian character of the polymer.
Melt Flow Ratio (MFR) = MI21.6/MI2.16 76
PROCESSING PROPERTIES MELT FLOW INDEX
Molecular weight / MFI relationship
Example of non plasticized PS
Linear relationship
between Log(MFI) and
Mw of polymer.

If mixing two grades 1 and 2 of


different MFIs, in proportions
x1 and x2 (x1+ x2=1) then :
Log(MFI of mixture) ~
x1Log(MFI1) + x2 Log(MFI2)

Note.
For certain polymers (PA, PET), the melt viscosity measurement is highly
sensitive to moisture regain Consequently, the preferred test method is the
solution viscosity measurement.
Standard for PA: ISO 307 - for PET: ISO 1628/5
77
OPTICAL PROPERTIES

Transparency measures light Amorphous polymers


transmission. often allow high levels of
Standard: ASTM D542 light transmission: PS
crystal, PVC.
The presence of
crystalline zones tends
to reduce the level of
light transmission. Semi-
Gloss measures light crystalline polymers in
reflection. 60 moderate thickness are
Standard: ASTM D523 generally translucent: PE,
PP.
PET is an example of
transparent crystallizing
polymer.

Additives can help


Haze measures light 25 translucent polymers to
diffusion. be more transparent.
Standard: ASTM D1003 Example: nucleation
agents for clarified PP.
78
STRUCTURE CARACTERIZATION
GEL PERMEATION CHROMATOGRAPHY (GPC)
(or Size Exclusion Chromatography)

For a given volume of solvent flow,


molecules of different size travel
different path lengths within the
column.The smaller ones travel greater
distances than the larger molecules
due to permeation into the molecular
maze.Hence, the large molecules are
eluted first from the column, followed 79
by smaller and smaller molecules.
STRUCTURE CARACTERIZATION
GPC gives direct access to the full distribution and has now replaced
all of the former methods for molecular weight characterization
(membrane osmometry, boiling point elevation, freezing point
depression, light scattering, capillary viscometry).
In the laboratory, modern analytical techniques enable better and better
knowledge of the molecule structure.
Electron microscopy enables to visualize the spherulite level.
NMR can detect the number of tail to tail accidents in polypropylene or describe
the distribution of a comonomer within the chain.
TREF (Temperature Rising Elution Fractionation) can separate polyolefins
molecules according to the content of comonomer, etc, etc ..

New powerful analytical tools certainly plaid a great role in the


scientific development of polymers.
However, there is still a great part of empiricism in this profession.
Developing a new grade for a new plastic is
80
both a science and an art !