Isomerism in polymers

Isomers: Each of two or more compounds with the same formula but a different arrangement of atoms in the molecule
and different properties.
Polymers: structural-, stereo-, and conformational isomerism.

Structural isomerism (also referred to as constitutional isomerism): The nature of the covalent linkage of the atoms
with each other differs, similar to the low-molecular isomers acetone and propionaldehyde.

Structural isomerism using the example of (a)

polyvinyl alcohol and (b) polyethylene glycol

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 Isomerism in polymers

❑ In the polymerization of conjugated dienes such as

isoprene (2-methylbut-1,3-diene), each monomer unit
can be added to the macromolecule in different ways.

❑ The isomers shown rarely occur as pure forms in practice.

Stereoisomerism: cis-trans isomers and enantiomers.

Structural isomers of polyisoprene ❑ The cis-trans isomerism is particularly important for
polymers with a double bond in the main chain.

❑ cis-1,4-Polybutadiene (butadiene rubber) is an

amorphous, sticky material, whereas the trans isomer is
a (partially) crystalline material with a high melting point

cis-trans isomerism using the example of (a) cis-1,4-

polybutadiene and (b) trans-1,4-polybutadiene
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 Isomerism in polymers
Stereoisomerism using the example of polypropylene: isotactic,
syndiotactic, and atactic polypropylene
Enantiomerism:
Polypropylene (PP): The main chain (polymer
backbone) could be placed in a plane, and the
methyl groups of the C3 carbon point upwards
or downwards relative to this plane.
❑ Isotactic polypropylene (it-PP): all of its
tertiary carbon atoms are configured
identically.
❑ Syndiotactic polypropylene (st-PP): an
alternating configuration of its methyl groups
along the chain
❑ Atactic polypropylene (at-PP): the spatial
orientation of the methyl groups is irregular.
it-PP is a highly crystalline material with a melting
point of ca. 160 °C, at-PP cannot crystallize because
of its irregular structure and it is an amorphous,
sticky material.
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 Isomerism in polymers
Pseudo-asymmetry using the example of (a)
polypropylene compared to optical activity in (b)
polypropylene oxide
Enantiomerism
Stereoregular polyolefins are usually not optically active. This
is because the two polymeric chains attached to the chiral
center are very large and thus indistinguishable from a
physicochemical point of view. A mirror plane can thus be
placed approximately through the chiral center. This is also
referred to as pseudo-asymmetry.
In contrast to this, no mirror plane can be placed through the
molecule of polypropylene oxide because of the additional
oxygen atom. Therefore, this macromolecule can exhibit
optical activity if one succeeds in producing a stereoregular
product and separating the stereoisomers.
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 Isomerism in polymers
Conformational Isomerism
Even with macromolecules, individual molecular groups can rotate
around a single bond.

Consider polyethylene as the simplest organic polymer. The trans

conformation is approximately 4 kJ/mol more favorable than the
gauche conformation. Therefore, the all trans conformation is the
enthalpically most favorable conformation.

But the all trans conformation is extremely unlikely, as it is

entropically unfavorable. The enthalpy difference of 4 kJ/mol, which
corresponds to about 1.5 times kBT (kB: Boltzmann constant, T:
absolute temperature) at room temperature, is not particularly large.
The trans configuration is only approximately 1.6 times more likely
than the gauche configuration.

All-trans conformation (a) and “ball of wool” The molecule adopts a spatial arrangement quite different from the
conformation (b) of polyethylene extended form, which resembles rather a ball of wool

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 Copolymers

Copolymers are polymers composed of at least two chemically different monomers. In principle, with copolymerization
of different monomers in various quantities, an infinite variety of different macromolecules can be synthesized. This
chemical diversity is increased by the various possibilities available for incorporating the comonomers into the chain as
well as their sequences.

Statistical Copolymers
If two chemically different monomers M1 and M2 are polymerized in a random, statistically determined sequence to
each macromolecule, this is referred to as a statistical copolymer.
The incorporation of the monomers into the polymer main chain is determined by the relative reactivity of the
monomers and obeys statistical. The copolymer is referred to as poly(M1-stat-M2).

Statistical copolymer consisting of two monomers M1 and M2

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 Copolymers
Alternating Copolymers
❑ Two monomers M1 and M2 are built into the polymer main chain in regular alternation, poly(M1-alt-M2). The
polymerization of monomers can react with one another but not with themselves, e.g., polycondensation of a diol
and a diacid.
❑ Alternating copolymers result from vinyl polymerizations only when the reactivity of the individual monomers
with the other monomer is much greater than with itself.

Alternating copolymer consisting of two monomers M1 and M2

Block Copolymers
❑ The comonomers are arranged along the polymer backbone in blocks of consecutive identical monomers.
❑ Depending on the number of blocks in the polymer backbone, one refers to di-, tri-, or multiblock copolymers.
❑ The nomenclature for these macromolecules is PolyM1-block-PolyM2, polystyrene-block-polybutadiene.
❑ The designation Poly(M1-block-M2) has become common; e.g., poly(styrene-block-butadiene).

Block copolymer consisting of two monomers M1 and M2 Page 7

 Copolymers
Graft Copolymers
A side chain of M2 is linked to the main chain of M1 are called graft copolymers of the monomers M1 and M2. These
macromolecules are referred to as PolyM1-graft-PolyM2. Here, PolyM1 is the main chain, the so-called graft stock,
and PolyM2 is the grafted side chain.

Graft copolymer consisting of two monomers M1 and M2

Copolymers for which only the monomers are to be designated but in whose name no particular copolymer
architecture is to be specified are generally referred to as Poly(M1-co-M2).
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 Molar mass of a polymer
A key parameter for macromolecular substances is their molar mass or degree of polymerization.
Definition of molar mass parameters
Most polymerization methods result in a mixture of molecules with different chain lengths, each chain, in some
cases, being made up of a very large variety of monomer units.
The molar mass of a polymer can also be defined by an average value, but for a broad distribution the average can
be calculated in several different ways.
Example
Assume that a polymer sample contains three separate molecules, two of which have a molar mass of
10,000 g/mol and the third has a molar mass of 20,000 g/mol. If the average molar mass of this sample is
required, the “intuitive” answer is 13,333 g/mol.

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 Definition of molar mass parameters

where mi is the total mass of all molecules with a molar mass Mi.
The number average Mn
This is given by the product of the number of molecules with a
molar mass Mi, ni, and their individual molar mass Mi. The mole
fraction (xi=ni/Σni)

The weight average molar mass Mw

where wi is the mass fraction

of the molecules with a molar
mass Mi, that is, their mass
divided by the total mass of
the sample

Sketch showing a polymer sample

emphasizing the weight fractions

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 Definition of molar mass parameters

The centrifugal average Mz, determined from ultracentrifuge measurements

By definition, the mean molar mass increases in the following order:

Mn  Mw  Mz

These averages only take on the same value if all of the molecules of a sample are of exactly the same length and
composition. Such samples are referred to as monodisperse. One rare example being DNA. In non-monodisperse or
so-called polydisperse samples, the quotient of weight and number averages is a measurement of the breadth of the
molar mass distribution. This quotient is referred to as the polydispersity index PDI:

A monodisperse sample has PDI = 1. The larger the PDI, the broader the molar mass distribution
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 Polymers in solid state

The morphologies of polymeric solids

The mechanical properties of a solid are measured in terms of its so-called “moduli.” These include Young's modulus
for uniaxial extension, and the shear modulus for shear deformation of a test piece

Schematic representation of the shape change under uniaxial stress by Δx or shear stress by a shear angle α
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 Polymers in solid state

According to Hooke’s law, the uniaxial stress of a test piece is given by

The applied stress σ (force per unit area) is proportional to the elongation of the test piece ε. The proportionality
constant E is referred to as the Young’s or E-modulus.

If a test piece is deformed under shear, the stress σs—defined as the force applied to a given area—is proportional
to the tangent of the shear angle α. The proportionality constant is referred to as a modulus, the shear modulus G:

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 Phase transitions in polymeric solids
Sketch showing the change of volume with
melting. Tm melting temperature
For crystalline substances, at the melting point, an abrupt
rearrangement occurs in the material. Below the melting point,
there is crystalline order and this disappears during the melting
process. This is the reason why the properties such as volume
undergo a stepwise change at the melting point
First-order phase transitions: thermal transitions can be assigned
an enthalpy, in this case, the enthalpy of melting.
Because of the structural change on melting, the entropy of the
melted phase is greater than that of the crystalline phase so that
a ΔS can be defined for this transition as well as a corresponding
free enthalpy ΔG.
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