General Polymeric Characteristics

Characteristics of polymers depend on a number of factors that are related to their molecular structure.
The molecular structure itself depends on the nature of the monomers and the polymerisation technique.
The main factors that influence the properties of polymers are as follows:
 The chain length (molecular weight) of polymer and the distribution of molecular weights.
 Physical nature of the polymer chain (e.g. linear, branched, cross-linked etc.)
 The type of atoms in the main-chain (e.g. carbo-chain polymers, hetero-chain polymers, etc.)
 The number of monomers involved in making the polymer chain and their location in the polymer
chain (e.g.: - homopolymers, copolymers etc.)
 The spatial arrangement of atoms in the polymer chain. (e.g. cis-trans isomerism, tacticity, etc.)

Structure of polymer chains

Although polymers are said to be formed by combination of monomers, the exact way in which the
monomers are joined in the polymer chain and how the atoms are located in the chain can make a
significant difference in the properties of the polymer. Polymers with identical chemical structure and
different physical chain arrangements are called isomers. Isomerism is the structural variation that makes
one isomer different from another. The structural variations in polymers are categorised as constitutional,
configurational and conformational isomerism.

Constitutional Isomerism
The constitution of a molecule specifies what atoms are joined together and the types of bonds involved
in the process. For example, isobutane and n-butane both have the same chemical formula of C 4H10 but
C and H atoms are joined differently.

CH
3
|
CH  C  H CH  CH  CH  CH
3 | 3 2 2 3
CH
3
Isobutane n  butane
In polymers, the main constitutional differences are positional isomerism and branching.

a). Positional Isomerism

This type of isomerism takes place in polymers manufactured using unsymmetrical monomers such as
H vinyls and dienes. Study the following example of vinyl fluoride.
| One side of the monomer (e.g. CH2 side) can be arbitrarily called as the 'head' and the side
CH 2  C with CHF as the 'tail'. (This notification can even be reversed, as it is not a standard). When
| the polymer is made, the monomers can join either by 'head to head', 'tail to tail' or 'head to
F tail' orders. The polymer that would result may have the appearance as the figure below.

As vinyl polymers usually polymerise by either free radical or ionic polymerisation, the factors that affect
the constitutional changes are the steric hindrance and the charge de-localisation of the vinyl group.

6
Steric hindrance occurs when the atoms in a polymer chain prefer to take on the trans conformation
rather than the cis conformation to avoid interference between atoms. Charge de-localisation occurs
when an electrophelic or electrophobic group is involved in the vinyl monomer.
In the above example of polyvinyl fluoride, both head to head and head to tail constitutions exist because
the small fluorine atom does not cause any steric significant hindrance. In general, it is known that the
more stable constitution is head to tail.

b). Branching
Branching in a polymer chain is categorised as a type of constitutional isomerism. Branched polymers
behave differently from chemically similar linear ones, because the packing of the polymer chains is
affected by the presence of branches. Therefore, a branched polymer will have a lower density and less
rigidity. They will be more flexible and more transparent than the same polymer with linear chains.
Sometimes a small degree of branching is intentionally introduced to linear polymers to improve their
flow properties so that they can be processed easily.
Branching can be done either by introducing a different monomer (copolymerisation) or by altering the
polymerisation process to promote branching during polymerisation of a single monomer. One example
of branching by copolymerisation is the copolymerisation of ethylene with 1-butane in the presence of
diethyl aluminium chloride / titanium chloride catalyst. The resulting polymer is a polyethylene with ethyl
branches. This is one example of a grafted copolymer.

H H
| |
CH 2  CH 2  CH 2  C  CH 2  CH 2  CH 2  C  CH 2  CH 2 
| |
CH 2 CH 2
| |
CH 3 CH 3
If the copolymerisation were carried out with a bifunctional monomer and a polyfunctional monomer, a
cross-linked polymer can be produced.

Configurational Isomerism
Configuration of a polymer is the relative spatial arrangement of its atoms, neglecting the changes in the
molecular shape that can arise due to rotation of atoms about single bonds. To change the configuration,
atomic bonds must be broken and rearranged. Two types of configurational isomerism exist in polymers.
They are equivalent to geometrical and optical isomerism in micromolecular compounds.

a). Geometrical Isomerism

When conjugated dienes polymerise by 1,4- enchainment, the polymer backbone contains a carbon-
carbon double bond. Since the two carbon atoms cannot rotate about this double bond, two non-
superimposable configurations are possible if the substituents on each carbon atom are different from
each other. For example, in 1,4-polyisoprene, two different configurations occur as follows:

Trans Polyisoprene Cis Polyisoprene

Considering the carbon atom that contain the double bond, if the main chain continues across the double
bond on the same side then the configuration is said to be cis. If the main chain continues across the
double bond in a diagonal direction then the configuration is called trans.
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Trans isomers pack more closely together and crystallise more easily than cis isomers. Consequently,
cis polyisoprene is an elastomer while trans isomer is a thermoplastic with a low softening temperature
0
(26 C).

b). Stereo isomerism

Stereo isomerism occurs in vinyl polymers when one of the carbon atoms of the monomer double bond
carries two different substituents. There are three basic variations in stereo isomerism.
If the polymer chain's backbone is assumed to lie on a horizontal plane and all the similar substituents lie
on one side of that plane (above or below) then the configuration is called isotactic. If the two
substituents lie alternately on either side of the plane containing the main chain, then the configuration is
called syndiotactic. If the substituents lie on both sides of the plane in no particular order, the
configuration is called atactic.

Isotactic Configuration Syndiotactic Configuration

The main effect of configurational differences as above is reflected in the degree of crystallinity of the
polymer. In general, only isotactic polymers tend to crystallise.

Polymer conformation
The conformation of a macromolecule of a given constitution and configuration specifies the spatial
arrangements of various atoms in the molecule that may occur because of rotations about single bonds.
Molecules with different conformations are called conformational isomers, rotamers or conformers.
As conformational changes take place by rotation of atomic bonds, and not by bond rearrangement as in
the case of configurational changes, they can occur whenever the polymer chain has any freedom of
movement. The rate and ease of conformational changes will affect the solution and melt viscosity,
mechanical properties and the rate of crystallisation.

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Conformational changes in a polymer are similar to that of long chained monomers. The following
example illustrates the conformational changes in n-butane.
CH3-CH2-CH2-CH3  C1-C2-C3-C4

C1 C4

C2 C3

The conformational changes can be viewed by referring to the rotation of C 3-C4 bond around C2-C3 bond,
0
with respect to the trans conformation. That is, when the bond rotation angle is 0 , it assumes the trans
0
conformation and when it is 180 the cis conformation is assumed. These rotational conformations can
be clearly represented by an endwise projection of the molecular chain. These projections are called
Newman projections. The Newman projections of n-butane for the different conformations are shown
below.
CH3
CH3 CH3 CH3

CH3 H
H H CH3 H CH3

H H
H H H H
H H H
CH3 H H
H
+ -
trans cis gauche gauche
In the trans conformation, it can be seen that all atoms on the molecule have assumed a spatial
arrangement such that they occupy the maximum area around the main chain. This is the most stable
conformation. That is the molecule has the lowest free energy in that conformation. Almost similar
conformations can be achieved by rearranging the relative position of the CH3 groups. They are known
+ -
as gauche and gauche conformations. The latter two conformations are not as stable as the trans
conformation but are more stable than the cis conformation. It must be noted that in long polymer chains,
not all combinations of the gauche and trans conformations are possible because they may interfere with
each other. If interference occurs, it would increase the free energy of the system, and make that
particular conformation less stable.