Polymer Degradation: Polymer degradation means uncontrolled reduction in the molecular weight or

constitution of the polymer. In a technological sense any undesirable change in polymer properties due
to exposure to degradation agency is called polymer degradation.

A polymer can suffer degradation mainly at two stages of its life, First, during the fabrication process
and secondly during its daily usage.

The degradation caused by heating, mechanical stresses, solar radiations, atmospheric oxygen, moisture
etc.

Types of degradation: Polymer degradation is broadly of two types:

 Chain end degradation

 Random degradation

Chain and degradation: In this type, the degradation starts from the chain ends, resulting in successive
release of the monomeric units. This phenomenon is actually the reverse of the propagation step in
chain polymerization. For this reason, this type of degradation is also called Depolymerization.

In chain end degradation, the molecular weight of the polymer decreased slowly and a large quantity of
the monomer is liberated simultaneously:

Figure: Schematic representation of a polymer molecule undergoing chain end degradations.

We can represent this, another way:

Mn*------------------→Mn*-1+M

Mn*-1+M-------------→ Mn*-2+M and so on.

Where, M is the monomer and Mn*, Mn*-1 and so on represent the polymer chain and made up of so
many monomeric units and carrying an active end group.

Random degradation: This degradation occurs at any random point along the polymer chain instead of
at the chain ends, and it is the reverse of the polycondensation process.

Here the polymer degrades to lower molecular weight fragments but particularly no monomer is
liberated.
Factors for degradation: Degradation of polymer may be brought about either by physical agents or by
chemical agents or biological.

a) Physical degradation falls under

 Thermal
 Mechanical
 By ultrasonic waves.
 Photo degradation
 High energy radiation.
b) Chemical degradation falls under
 Oxidative/Reductive
 Hydrolytic
 Alcoholic
 Acidolytic
c) Biological by enzyme and bacteria

Degradation by ultrasonic waves: Ultrasonic waves are very high frequencies (above 20000 hertz), which
is beyond the audible range of the human ear.

When a dilute solution of a high molecular weight polymer is subjected to ultrasonic waves, the polymer
begins to degrade, thus reducing its molecular weight. Ultrasonic degradation is a special case of
mechanical degradation as the polymer here is subjected to very high vibrations, which are only
mechanical forces.

As ultrasonic waves pass through the solution, tear off the polymer molecules leading to chain
degradation. As a result average molecular weight of the sample goes down. The decrease in molecular
weight does not go below a certain value even after a long exposure to ultrasonic or mechanical
stresses.

Figure: Effect of ultrasonic degradation of two samples of the same polymer with different initial
molecular wt.
Mechanical degradation: When a polymer dissolved in a solvent and subjected to vigorous strring or
beating, the polymer undergoes considerable molecular degradation or fragmentation which is called
mechanical degradation.

For example, in rubber industry, rubber is masticated by passing it through two rotating rollers to reduce
its molecular weight and make it more processable. This mastication converts hard and tough rubber
into a seat, supple and even semisolid mass.

Rubber is polyisoprene with the following structure:

CH2-C=CH- CH2-C=CH- CH2-C=CH

Polyisoprene unit.

In polyisoperene, the bonds which are most vulnerable for scission are the CH 2-CH2 links between the
isoprene units. These bonds in the susceptible regions, cleave when the polymer is subjected to
mechanical stresses in the form of milling or mastication. The net effect is that the big molecules are
broken into small parts.

Besides milling and mastication, other mechanical degrade. For example agitation, grinding or extrusion
is other well known methods for effecting the mechanical degradation of polymer.

Effect of Mastification time on molecular wt. of a polymer undergoing mechanical stress for a sufficiently
long time. Mechanical degradation can reduce the average molecular wt., give a narrower molecular wt.
distribution and make the polymer easily processable.

Photodegradation: A molecular weight degradation process brought about by ultraviolet light is called
photodegradation. The yellowing of the transparent plastics or coloured rubber articles are due to their
interaction with ultraviolet light.
Photo Stabilizers: Photo-stabilizers protect polymers from the deteriorating effect of light to a
considerable extent. The function of Photo Stabilizer is to absorb the UV radiation and dissipate the
energy thus absorbed to the environment in some harmless form. The absorbed energy is transmitted
back as heat or radiations of a longer wavelength. In doing so, The stabilizer acts as a filter and does not
allow the radiation energy to attack the polymer molecules.

2, 4 hydroxy benzophenone (Uvinul 400), 2 hydroxy 4 methoxy bezophenone (Vinul M 40) etc. are used
as a Photostabilizer.

Oxidative Degradation: Oxidative degradation usually leads to hardening, discolouration as well as

surface changes. The early stage of oxidative degradation is the formation of free radical sites on the
chain backbone by the attack of oxygen, ozone etc.

P----------→P*

Where, P represents the polymer chain.

Once the free radical sites are formed, attack by oxygen becomes easier. Oxygen, because of its biradical
can now attack the neighboring segment, abstract hydrogen and form a hydroperoxide and a new free
radical site,

P*+O2-----------→POO*

The peroxy radical can now attack the neighboring segment, abstract hydrogen and form a
hydroperoxide and a new free radical site,

POO*+P----------→POOH+P

The hydroperoxide formed can lead to the formation of several new free-radical sites:

POOH---------------→PO*+*OH

P*+ POOH----------→PO*+POH

PO*+ POOH-----------→POH+POO*

Their recombination can occur and result in the termination of Chain reactions.

2POO*-----------→POOP+O2

2PO*-----------→POOP

P*+OH*-----------→POH

2P*-----------→P-P etc.

Antioxidants: Many polymers are protected against oxidative degradation by incorporating certain
chemical compounds called “antioxidants”. Even in small amounts of antioxidants are significantly
effective in preserving the original properties of the polymer. Antioxidants oppose oxidation and protect
many undesirable reaction promoted either by oxygen or peroxides.

Antioxidants can arrest a reactive polymer radical and prevent the polymer degradation through these
active radicals.

P*+XH-----------→PH+X*

PO*+XH-----------→POH+X*

POO*+XH-----------→POOH+X*

HO*+XH-----------→HOH+X*

Reactive Radicals + Antioxidants-----------→Stable Products+ Stabilized radicals.

The radicals (X) formed from the antioxidants are incapable of attacking a new polymer chain.

However, They can recombine:

X*+X*-----------→X-X