Dispersity

From Wikipedia, the free encyclopedia

Jump to navigationJump to search

A uniform (monodisperse) collection

A non-uniform (polydisperse) collection

Not to be confused with Dispersal (disambiguation) or Dispersion (disambiguation).

In physical and organic chemistry, the dispersity is a measure of the heterogeneity of sizes of
molecules or particles in a mixture. A collection of objects is called uniform if the objects have the
same size, shape, or mass. A sample of objects that have an inconsistent size, shape and mass
distribution is called non-uniform. The objects can be in any form of chemical dispersion, such as
particles in a colloid, droplets in a cloud,[1] crystals in a rock,[2] or polymer macromolecules in a
solution or a solid polymer mass.[3] Polymers can be described by molecular mass distribution; a
population of particles can be described by size, surface area, and/or mass distribution; and thin
films can be described by film thickness distribution.[citation needed]
IUPAC has deprecated the use of the term polydispersity index, having replaced it with the
term dispersity, represented by the symbol Đ(pronounced D-stroke[4]) which can refer to either
molecular mass or degree of polymerization. It can be calculated using the equation ĐM = Mw/Mn,
where Mw is the weight-average molar mass and Mn is the number-average molar mass. It can also
be calculated according to degree of polymerization, where ĐX = Xw/Xn, where Xw is the weight-
average degree of polymerization and Xn is the number-average degree of polymerization. In certain
limiting cases where ĐM = ĐX, it is simply referred to as Đ. IUPAC has also deprecated the
terms monodisperse, which is considered to be self-contradictory, and polydisperse, which is
considered redundant, preferring the terms uniform and non-uniforminstead.

Contents
[hide]

 1Overview
 2Effect of polymerization mechanism
 3Effect of reactor type
 4Determination methods
 5References
 6External links

Overview[edit]
IUPAC definition
ĐM = Mw/Mn
where Mw is the mass-average molar mass (or molecular weight) and
Mn is the number-average molar mass (or molecular weight).
Pure Appl. Chem., 2009, 81(2), 351-353

A monodisperse, or uniform, polymer is composed of molecules of the same mass.[5] Nearly all
natural polymers are monodisperse.[6] Synthetic near-monodisperse polymer chains can be made by
processes such as anionicpolymerization, a method using an anionic catalyst to produce chains that
are similar in length. This technique is also known as living polymerization. It is used commercially
for the production of block copolymers. Monodisperse collections can be easily created through the
use of template-based synthesis, a common method of synthesis in nanotechnology.[citation needed]
A polymer material is denoted by the term disperse, or non-uniform, if its chain lengths vary over a
wide range of molecular masses. This is characteristic of man-made polymers.[1]. Natural organic
matter produced by the decomposition of plants and wood debris in soils (humic substances) also
has a pronounced polydispersed character. It is the case of humic acids and fulvic acids,
natural polyelectrolyte substances having respectively higher and lower molecular weights. Another
interpretation of dispersity is explained in the article Dynamic light scattering (cumulant method
subheading). In this sense, the dispersity values are in the range from 0 to 1.
The dispersity index, or formerly polydispersity index (PDI), or heterogeneity index, or simply
dispersity (Đ), is a measure of the distribution of molecular mass in a given polymersample. Đ (PDI)
of a polymer is calculated:

where is the weight average molecular weight and is the number average molecular

weight. is more sensitive to molecules of low molecular mass, while is more sensitive to
molecules of high molecular mass. The dispersity indicates the distribution of individual molecular
masses in a batch of polymers. Đ has a value equal to or greater than 1, but as the polymer chains
approach uniform chain length, Đ approaches unity (1).[7] For some natural polymers Đ is almost
taken as unity.

Effect of polymerization mechanism[edit]

Typical dispersities vary based on the mechanism of polymerization and can be affected by a variety
of reaction conditions. In synthetic polymers, it can vary greatly due to reactantratio, how close
the polymerization went to completion, etc. For typical addition polymerization, Đ can range around 5
to 20. For typical step polymerization, most probable values of Đ are around 2 —Carothers'
equation limits Đ to values of 2 and below.
Living polymerization, a special case of addition polymerization, leads to values very close to 1.
Such is the case also in biological polymers, where the dispersity can be very close or equal to 1,
indicating only one length of polymer is present.
Effect of reactor type[edit]
The reactor polymerization reactions take place in can also affect the dispersity of the resulting
polymer. For bulk free radical polymerization with low (<10%) conversion, anionic polymerization,
and step growth polymerization to high conversion (>99%), typical dispersities are in the table
below.[8]

Batch Plug Flow Reactor Homogeneous Segregated

Polymerization Method
Reactor (PFR) CSTR CSTR

Free Radical Polymerization

1.5-2.0 1.5-2.0 1.5-2.0 1.5-2.0
(FRP)

Anionic Polymerization 1.0 + ε 1.0 + ε 2.0 1.0-2.0

Unbounded (~20-
Step-Growth 2.0 2.0 Unbounded (~50)
25)

With respect to batch and plug flow reactors (PFRs), the dispersities for the different polymerization
methods are the same. This is largely because while batch reactors depend entirely on time of
reaction, plug flow reactors depend on distance traveled in the reactor and its length. Since time and
distance are related by velocity, plug flow reactors can be designed to mirror batch reactors by
controlling the velocity and length of the reactor. Continuously stirred-tank reactors (CSTRs)
however have a residence time distribution and cannot mirror batch or plug flow reactors, which can
cause a difference in the dispersity of final polymer.
The effects of reactor type on dispersity depend largely on the relative timescales associated with
the reactor, and with the polymerization type. In conventional bulk free radical polymerization, the
dispersity is often controlled by the proportion of chains that terminate via combination or
disproportionation.[9] The rate of reaction for free radical polymerization is exceedingly quick, due to
the reactivity of the radical intermediates. When these radicals react in any reactor, their lifetimes,
and as a result, the time needed for reaction are much shorter than any reactor residence time. For
FRPs that have a constant monomer and initiator concentration, such that the DPn is constant, the
dispersity of the resulting monomer is between 1.5 and 2.0. As a result, reactor type does not affect
dispersity for free radical polymerization reactions in any noticeable amount as long as conversion is
low.
For anionic polymerization, a form of living polymerization, the reactive anion intermediates have the
ability to remain reactive for a very long time. In batch reactors or PFRs, well-controlled anionic
polymerization can result in almost uniform polymer. When introduced into a CSTR however, the
residence time distribution for reactants in the CSTR affects the dispersity of the anionic polymer
due to the anion lifetime. For a homogeneous CSTR, the residence time distribution is the most
probable distribution.[10] Since the anionic polymerization dispersity for a batch reactor or PFR is
basically uniform, the molecular weight distribution takes on the distribution of the CSTR residence
times, resulting in a dispersity of 2. Heterogeneous CSTRs are similar to homogeneous CSTRs, but
the mixing within the reactor is not as good as in a homogeneous CSTR. As a result, there are small
sections within the reactor that act as smaller batch reactors within the CSTR and end up with
different concentrations of reactants. As a result, the dispersity of the reactor lies between that of a
batch and that of a homogeneous CSTR.[8]
Step growth polymerization is most affected by reactor type. To achieve any high molecular weight
polymer, the fractional conversion must exceed 0.99, and the dispersity of this reaction mechanism
in a batch or PFR is 2.0. Running a step-growth polymerization in a CSTR will allow some polymer
chains out of the reactor before achieving high molecular weight, while others stay in the reactor for
a long time and continue to react. The result is a much more broad molecular weight distribution,
which leads to much larger dispersities. For a homogeneous CSTR, the dispersity is proportional to
the square root of the Damköhler number, but for a heterogeneous CSTR, dispersity is proportional
to the natural log of the Damköhler number.[8] Thus, for the similar reasons as anionic polymerization,
the dispersity for heterogeneous CSTRs lies between that of a batch and a homogeneous CSTR.

Determination methods[edit]
 Gel permeation chromatography (also known as size exclusion chromatography)
 Light scattering measurements such as dynamic light scattering
 Direct measurement via mass spectrometry using MALDI or ESI-MS

References[edit]
1. Jump up^ Martins, J. A.; Silva Dias, M. A. F. (2009). "The impact of smoke from forest fires on the
spectral dispersion of cloud droplet size distributions in the Amazonian region". Environmental
Research Letters. 4: 015002. doi:10.1088/1748-9326/4/1/015002.
2. Jump up^ Higgins, Michael D. (2000). "Measurement of crystal size distributions" (PDF). American
Mineralogist. 85: 1105–1116.[permanent dead link]
3. Jump up^ Okita, K.; Teramoto, A.; Kawahara, K.; Fujita, H. (1968). "Light scattering and
refractometry of a monodisperse polymer in binary mixed solvents". The Journal of Physical
Chemistry. 72: 278. doi:10.1021/j100847a053.
4. Jump up^ Stepto, R. F. T.; Gilbert, R. G.; Hess, M.; Jenkins, A. D.; Jones, R. G.; Kratochvíl P. (2009).
"Dispersity in Polymer Science" Pure Appl. Chem. 81 (2): 351–353. DOI:10.1351/PAC-REC-08-05-02.
5. Jump up^ "monodisperse polymer (See: uniform polymer)". IUPAC Gold Book. International Union of
Pure and Applied Chemistry. Retrieved 25 January 2012.
6. Jump up^ Brown, William H.; Foote, Christopher S.; Iverson, Brent L.; Anslyn, Eric V. (2012). Organic
chemistry (6 ed.). Cengage Learning. p. 1161. ISBN 978-0-8400-5498-2.
7. Jump up^ Peter Atkins and Julio De Paula, Atkins' Physical Chemistry, 9th edition (Oxford University
Press, 2010, ISBN 978-0-19-954337-3)
8. ^ Jump up to:a b c Dotson, Neil A.; Galván, Rafael; Laurence, Robert L.; Tirrell, Matthew
(1996). Polymerization Process Modeling. VCH Publishers, Inc. pp. 260–279. ISBN 1-56081-693-7.
9. Jump up^ Chanda, Manas (2013). Introduction to Polymer Science and Chemistry: A Problem-
Solving Approach, Second Edition. CRC Press. ISBN 978-1-4665-5384-2.
10. Jump up^ Levenspiel, Octave (1999). Chemical Reaction Engineering, Third Edition. John Wiley &
Sons. ISBN 0-471-25424-X.

External links
ARTICLE

Molecular Weight and The Effects on

Polymer Properties
Molecular weight can have a huge impact on a material’s final properties.
Understanding this materials characteristic can help you better position the proper
material for your application. Looking for assistance? Contact Amco Polymers today.

What is Molecular weight?

When we talk about molecular weight in terms of polymers, we are really talking about

the length of the individual chains. Molecular weight is the average weight of the

molecules that make up a polymer and gives an indication of the length of the polymer

chains

The polymerization process is subject to variation so there is no single chain length,

there is actually a wide range of lengths, so when we discuss molecular weight, we

really mean the average molecular weight of the material. This average is found by

measuring samples of the material as it is produced.

How does Molecular weight affect a material’s

properties?
Molecular weight and MWD (or molecular weight distribution) determine the polymers

properties
 This table shows the effects of molecular weight on selected properties. In general, as

molecular weight increase the strength, toughness and chemical stress crack resistance

increase. Lower molecular weight will typically flow easier.

Table1

 A High molecular weight increases how far the material can stretch before rupturing.
The higher degree of entanglement allows the material to be pulled further before the
chains break
 A High molecular weight increases the impact resistance of the material. The higher
degree of entanglement means that in order to rupture, more polymer bonds need to be
broken, this means that the polymer can absorb more energy before failing.
 A High molecular weight increases the chemical resistance - to a point. It takes more
damage to the main chains of the molecules before it will affect the strength of the
material.
 A High molecular weight increases the viscosity of the material – makes it harder to
process the material using conventional methods. The longer the chains, the harder it
is to get them to flow because they are more tangled.

This table shows the influence of melt flow on the impact properties of polycarbonate.

With increasing melt flow index, there is a significant drop off in notched Izod impact

properties. Low Molecular Weight polymers have lower properties due to lack of chain

entanglement and higher molecular mobility.

Table2
 Shorter chains have more end groups which increase free volume and molecular

mobility which makes it easier for the polymer chains to respond to stresses. This is

why the strength and modulus are reduced for lower MW (higher melt flow) polymer.

Molecular weight can decrease during the course of molding. Examples could be -

 Plasticizer in rigid PVC.

 Regrind in nylon.
 Hydrolytic degradation in PC or PBT Polyester

Amco Has the Experience to Select the Right Material