Different aspects of polymer science

Polymer synthesis Polymer characterization Polymer physical chemistry Paul J. Flory, Nobel prize for chemistry, 1974 Polymer physics Pierre de Gennes, Nobel prize for physics, 1991 Polymer engineering Each of these aspects has considerable industrial and research significance. The successful polymer scientist has some understanding of all of these areas.
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Definitions

Indicates a chain of n units

Polymer: long molecule made up by the repetition of small units Synonym: macromolecule High molecular weight (M) Ex. polystyrene (PS) Monomer: molecule that combines with others (identical or different) to form a polymer Ex. ethylene (PE polyethylene) Oligomer: low molecular weight polymer, constituted of at least two monomers
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Classification of polymers
Thermoplastics: can be processed by melting (several cycles of heating and cooling are possible for thermally stabilized polymer) PS, PE PP PVC

PET

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Classification of polymers
Thermosets: cannot be melted or dissolved to be processed: chemical decomposition occurs before softening Formation of a 3D network Example: epoxy (resin and hardener)

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Vulcanization of rubber
Sulphur reacts with chain at the double bond

This kind of materials are referred to as elastomers

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Polymerization
Chemical reaction Functionality: number of sites on a molecule available for bonding with other molecules Bifunctional bond to 2 other molecules (ex. ethylene) Multifunctional more than 2 If an a-functional monomer reacts with a b-functional: the resulting molecule has a functionality equal to a+b-2 To obtain a macromolecule, it is necessary that a>1 and b>1 To obtain a network, it is necessary that either a > 2 or b > 2.
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Molecular forces
Intramolecular forces: generally covalent bonds (strong) Intermolecular forces: Van der Waals forces (PE), hydrogen bridges (PS) (stronger). Can become very strong as M Entanglements (physical) In the crystalline state the van der Waals bonds are very important. In the rubbery amorphous state the entanglements are very important.

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Molecular structure
How complicated can a homopolymer be? Identical basic molecules can give different structures (ex. branching) If asymmetric monomer several microstructures are possible Atoms or their arrangement on the 2 sides of the backbone
bond are different.

Three important types of isomerism in polymers: Sequence isomerism Stereoisomerism Structural isomerism

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Sequence isomerism
When a monomer adds to a growing chain, it usually does so in a preferred direction head-to-tail addition (H-T) PS, PMMA, PVC However, several specific polymers contain structural units that are incorporated backwards in the chain Ex. head-to-head (H-H) propylene tail-to-tail (T-T) monomer:
tail head

head to head
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Polymers that exhibit sequence isomerism

Poly(vinyl fluoride) (PVF) Poly(vinylidine fluoride) (PVDF) Vinyl polymers are those whose monomers have carboncarbon double bonds Polyisoprene Polychloroprene

Weaker T-T sites are initiation sites for thermal degradation

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Stereoisomerism

tacticity

Happens in polymers for which one of the C atoms in a double bond has two different constituents Steric isomerism site at every 2nd C atom in chain Site called Cx (chiral carbon atom: non-mirror image) Vinyl polymers contains many of these sites Ex. CH2 = CHY

If the successive configurations of Cx atoms are regular, the polymer is known to be stereoregular or tactic Stereoisomerism is related to the spatial locations of two successive Y units.ie. whether or not they are pointing in the same direction
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Stereoisomerism
If all Y units are in the same plane isotactic
tendency to form an helix

If a Y unit appears alternately on top and bottom syndiotactic

If random

atactic

Atactic polymers do not crystallize eg. PS and PMMA

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Structural isomerism
Occurs when there are carbon-carbon double bonds (C=C) in the backbone of the chain i.e. from the polymerization of dienes Rotation around double bonds is not possible Two configurations: H - C - COOH || H - C - COOH H - C - COOH || COOH C H

cis

trans

The 2 monomers shown (maleic acid : cis, and fumaric acid : trans) are structural isomers
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Structural isomerism
1 2 3 4 Ex.: CH2 = CX CH = CH2 where: X=H X = CH3 X = Cl
We use numbers to refer to the individual carbon atoms

butadiene isoprene chloroprene

The opening of 1 or 2 double bonds depends on the polymerization method Natural rubber is a "pure" cis isomer of 1,4-polyisoprene bond from the C-4 atom to the C-1 atom and so on Trans or cis configurations can also be of tactic nature
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Structural isomerism
Isoprene : monomer with 2 double bonds C=C Can join the chain such that the double bond is in the back bone (1,4 addition) giving cis and trans isomers. Can also join the chain such that the double bond is in a pendant group (1,2 or 3,4 addition) Polyisoprene chain segments can have 4 different structural isomers:

cis -1,4
1,2
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trans -1,4
3,4
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Structural isomerism

trans 1,4-polyisoprene

cis 1,4-polyisoprene

natural rubber

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Copolymer vs. homopolymer

2 or more monomers 1 monomer Statistical: the probability of finding a monomer in the chain depends on the relative proportion of the comonomer in the reaction mixture according to a known statistical law Random: a particular type of statistical copolymer in which the probability of finding a certain monomeric unit is independent of the types of units surrounding it Periodic: a particular sequence is repeated over and over along the chain Alternating: two monomers which alternate along the chain, ex. styrene and maleic acid, simplest periodic structure A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B
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Copolymers
Graft: a polymer is grafted to another preformed macromolecule Ex. Impact resistant PS: PS branches on polybutadiene (rubber) Also, ABS branches of SAN on polybutadiene

Block : long sequences of different repeating units A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-A-A-A

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Molecular weight of polymers

Related to the length of the chains Units: generally g/mol

Mechanical properties with M, but processing becomes more difficult Commercial polymers: large distribution of molecular weights
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Number distribution, n(M)

Shows the number fraction of the chains that have each molecular weight n(M)dM = number fraction of chains that have molecular weight between M and M+dM Statistical moments are used to characterize distributions Most used: arithmetic average or number (related to the 1st moment) Number-average molecular weight:

M N = M n (M )dM
0
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Weight distribution, w(M)

Shows the weight (or mass) fraction instead of number fraction w(M)dM = weight fraction of chains that have molecular weight between M and M+dM Related to the number distribution as follows: M w (M ) = n (M ) The integral is the 2nd MN moment of the distribution. Weight-average molecular weight:

1 M W = M w (M )dM = M 2 n (M )dM MN 0 0
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Z distribution, z(M)
Related to the other distributions as follows:

M M2 w (M ) = n (M ) z(M ) = MWMN MW
Z-average molecular weight:

1 M z = M z(M )dM = M 3 n (M )dM M NMW 0 0

The integral is the 3rd moment of the distribution.

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Why define different types of distributions and averages?

Because they are useful for different purposes in polymer science! Number distribution and MN are used in the analysis of polymerization reactions. The weight distribution is measured analytically in a very important technique called gel permeation chromatography. Many physical properties depend more strongly on MW than MN. Therefore it is often useful to compare two different polymers using MW. Light scattering from dilute solution is related to the zaverage molecular weight (technique for measuring the size of molecules).
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Distribution breadths
Central tendency is not sufficient to characterize molecular weight of commercial polymers Mass distribution: M Z > M W > M N (same if samples are monodisperse, but impossible) Example of two very different distributions:

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Polydispersity index (PDI)

Mw / Mn
Gives information about distribution breadth Highly branched polymers PDI > 20 Generally (commercial polymers) : 2 < PDI < 20 Metallocene polyethylene : 1 < PDI < 2 PDI = 1.04

PS synthetised by anionic polymerization (almost monodisperse)

PDI does not give any information about the skewness or any higher order of moments of the distribution
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Symmetry and asymmetry

1st moment: average 2nd moment: distribution breadth 3rd moment: skewness or asymmetry

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Nomenclature
IUPAC : International Union of Pure and Applied Chemistry Rarely used, another system of denomination is more commonly used polymonomer , even if the monomer does not exist poly(monomer name) more than one word Copolymers : if the monomer name consists of

co (random) (sometimes stat ) alt (alternating) graft block

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Repeat units
Sequence that repeats through the chain Only one precursor: (homopolymer) PS polystyrene PE polyethylene PVC poly (vinyl chloride) PAN polyacrylonitrile Composed of several small molecules (certain copolymers): PET polyethylene teraphtalate PA polyamide (nylon-6,6)

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Repeat Units
Use the repeat unit to show the structure of the polymer Ex. PS

Terminal groups: exact nature is not well known. They have only little effects on the polymer properties Ex. commercial PS : 1000 repeating units 2 terminal groups
The terminal groups are different from the repeat units in that they have one more hydrogen atom

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Polymerization degree (X)

Polymerization degree (X): number of repeat units M = X * M0 where M0 is the molecular weight of the repeat unit Mechanical properties increases with X In practice: limitation because processing becomes difficult with high M (relation viscosity M)

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Transition temperatures
Tm Tg

crystalline
1st order transformation
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amorphous
2nd order transformation
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Semicrystalline polymers
These materials exhibit both a glass transition and a melting temperature

viscoelastic liquid
Heat

glassy solid
Tg

Tm

rubbery solid

Temperature
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