POLYMERS

Pre - requisite : Polymer, Monomer, Polymerization, Degree of polymerisation,

Classification of polymers, Mechanism of polymerisation.
• Molecular weight of polymers: Average molecular weight (weight average and
number average) of a polymer, Polydispersity Index, Numerical problems.
• Polymer crystallinity - glass transition temperature and factors affecting Tg,
Viscoelasticity
• Additives in polymers
• Commercially important polymers - Polyethylene, Polyvinyl acetate,
Polydimethyl Siloxane , Epoxy resins , Polylactic acid (PLA)
• Conducting polymers - Mechanism of conduction in polymers, Examples
and applications.

A polymer is a material which is composed of very large molecules. They

are formed by joining together thousands of small molecular units by chemical
bonds. Due to their large size they are also called macromolecules. A polymer
can be defined as a substance of high molecular weight built up by linking
together a large number of small molecules. Therefore the polymers have a
repeated structural part. Eg: polyethene , (CH2 = CH2)n
n.CH2 = CH2 → (CH2 = CH2)n
Monomer is the simple substance of low molecular weight which can be
converted into a polymer. A monomer molecule should possess at least two easily
reacting positions.
Ex: ethylene glycol, HO−CH2−CH2−OH possesses two reacting groups and it can
form a polymer like polyester.
The small molecules with π bonds can also function as a monomer.
Ex: CH2 = CH2, CH2 = CH−Cl (vinyl chloride) etc.
When the π bond breaks, two reactive sites are formed on the neighboring carbon
atoms.
Functionality
It can be defined as the number of functional group or reactive sites in a
monomer molecule. Monomers have two or more functional groups.
Bi functional monomers: Ex: ethylene, glycine, styrene, vinyl chloride etc.

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 Here the two reacting groups attached side by side to each other forming
a straight chain molecule. Linear molecule consists of monomer units linked by
1o covalent bonds, but the different chains are held together by 2o van der Waal’s
forces. This gives the possibility of chain movement in one direction.
Tri functional monomers: Ex: glycerol, phenol
It has three functional groups or reactive positions and forms highly
branched or limited cross linked polymers.
Tetra functional (poly functional) monomers: Ex: acetylene, butadiene, urea,
dimethylol urea etc.
It has four reactive positions and forms a three dimensional network or
cross linked polymers.
Polymerization
It is the process of joining a large number of monomers to form large molecules
of polymers. During polymerization, the polymer molecules formed are of
different sizes depending on the number of monomers involved.
Ex: a polythene molecule may contain the repeating units −CH 2−CH2−, about
200-500. To know the size of the polymer, average numbers of repeating units
are considered.
Degree of polymerization (DP) is the average number of repeating units in the
polymer molecule. The DP increases with time, temperature, concentration of
monomer and initiator used in polymerization reaction. With increase in DP, the
molecular weight increases and the strength increases in a non linear way. For a
polymer to have desirable properties, the DP should be such that the polymer has
at least 20,000 as the mol: wt:
Molecular weight and DP are related by
M = nMo
Where n = DP, Mo = molar mass of monomer.

Polymer Crystallinity
The degree to which polymer molecules are arranged in orderly pattern with
respect to each other is a measure of its crystallinity. A small region of a
macromolecular material in which portions of large molecules are linked to each
other in some regular way is called a crystallite.

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No polymer is perfectly crystalline or perfectly amorphous. The longer molecules
are more partially crystalline than the shorter molecule.

Various polymers in use are made up of a mixture of crystalline regions embedded

in amorphous matrix. The crystalline region provides the rigidity and hardness
and the amorphous region account for flexibility.

Glass transition temperature and melting temperatures

The behavior of a polymer is temperature sensitive. When a polymer is cooled
slowly, it becomes hard solid and brittle and behaves like a glass. Glass transition
temperature is defined as the temperature below which the polymer becomes hard
and brittle and above which it becomes soft and flexible. It is denoted by Tg.
On heating, the polymer becomes too soft, that it behaves like a fluid called as
the visco fluid state. The temperature at which the soft, flexible polymer goes to
the viscofluid state is called the melting temperature Tm.

as compared to Tm, Tg is more important because the value decides the properties
and selection of polymer for desired purpose.
Factors influencing Tg

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a) Tg value depends on chain length. As the chain length increases, the mol: wt:
increases and hence Tg value increases. Eg: PE has a Tg value −90oC, while PP
has a value −18 oC
b) Cross linking increases the Tg value.
c) Presence of bulky groups increases the Tg value.
d) Polar side atoms or group of atoms increases the Tg value.
e) Double bonds and aromatic chain groups which tend to stiffen the back bone
increases the Tg value.
f) Addition of plasticizer decreases the Tg value.
g) Polymers having strong intermolecular forces of attraction decrease Tg value.
h) Coiled nature of the polymer molecules offers high flexibility and therefore Tg
is less.

Significance of Tg
Tg value (i)whether the polymer is flexible, hard
(ii)Correct processing temperature and techniques
(iii)Whether exhibits mechanical stress

Viscoelasticity
It describes materials that exhibit both elastic and viscous characteristics
while undergoing plastic deformation. Viscoelasticity is the result of diffusion of
atoms or molecules inside an amorphous material.
It is a molecular rearrangement. When a stress is applied to a viscoelastic material,
parts of the long polymer chain change its position. This movement is called
creep. Polymers remain a solid material even when these parts of their chains are
rearranging in order to accompany the stress and as this occurs it creates a back
stress in the material.

Molecular Weight of Polymers

All the molecules of the polymer in a polymeric material do not have identical
molecular weight. This is due to the random nature of polymerization process.
Thus the polymer molecules have different chain length and hence different

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molecular weight. Thus the molecular weight of a polymer is considered as an
average.
Number Average molecular weight
When the molecular weight is averaged according to the number of molecules.

Mn is determined by measuring the colligative properties like elevation in boiling

point, depression in freezing point etc.

Weight Average molecular weight

When the molecular weight is averaged according to the weight of molecules of
each type,

Mw is determined by light scattering measurements.

Mw is always greater than Mn

The ratio of Mw to Mn is called polydispersity Index. When Mw = Mn , it is called

monodispersed system.

Additives in Polymers
Usually high polymer material is mixed with a number of ingredients, each of
which perform useful function. The reasons for incorporating the additives are:
(i) They help in processing
(ii) They ensure general durability of polymers
(iii) They imparts useful mechanical properties.

The main types of additives are:

1. Binders

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 It is the main constituent. It holds the various constituents together. It
determines which method of processing is to be used. They may be liquid, viscous
or solid. Ex: Natural or synthetic resins.
2. Fillers or Extenders
These are cheap substances mixed with plastics to reduce the cost. Their
functions are:
a) To reduce the cost of plastics.
b) Increase the tensile strength and hardness.
c) Reduces the flexibility.
d) Decreases the shrinkage during moulding.
Ex: mica, talc, asbestos, saw dust, chalk etc.

3. Plasticizers
Plasticizers are added to increase the plasticity and flexibility. The plasticizer
molecule occupies between the polymeric chains and neutralizes the
intermolecular forces of attraction and thus allows freedom of movement.
The functions are:
a) Increases the flexibility of the plastics.
b) Lowers the softening temperature and hence processing can be done at
low temperature.
c) Imparts flame proofness.
Ex: esters of fatty acids, vegetable oils etc.
Plasticizers are not used with thermosetting resins.(cross linked polymers)
4. Lubricants
The functions are:
a) Imparts glossy finish to products.
b) Prevents sticking of plastic to the mould.
Ex: waxes, oleates, soaps etc.
5. Pigments
They provide colour to the final polymeric material. Examples are organic
and inorganic dye stuffs.
6. Catalysts

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 They are added only to crosslinked polymers. They accelerate the rate of
polymerisation.
Ex: H2O2, Zn, ammonia and its salts.
7. Stabilizers
In order to prevent the decomposition and discolouration of the polymer
at the processing temperature, stabilizers can be used.
Ex: PbCrO4, stearates of Pb, Ca, Ba, Pb silicate etc.

Commercially Important Polymers

Poly ethylene (PE)
It is prepared by the addition polymerisation of ethylene.

When polymerisation is carried out at high pressures of 1000-1500 atmospheres

at 250oC in the presence of free radical initiator, LDPE is obtained.
When polymerisation is carried out at 6-7 atmospheres at 60 - 70oC in the
presence of Ziegler Natta catalyst, HDPE is obtained.
Properties:
(i) Rigid , waxy, white, translucent, non polar material
(ii) Resistant to strong acids, alkalis, and salt solutions at room
temperature
(iii) Good insulator
Uses: Domestic appliances, flexible bottles, toys, packaging materials, tubes,
pipes, coated wires and cables.

Poly lactic acid (PLA)

Prepared from Lactic acid. Lactic acid is prepared by fermentation or by

chemical process.

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 Lactic acid forms a cyclic dimer (lactide) which opens to undergo
polymerisation (ring opening polymerisation)

Properties:

(i) Poly-lactic acid (PLA) is highly versatile, biodegradable, aliphatic

polyester which can be derived from 100 % renewable resources,
like corn and sugar beets.
(ii) Permeable to oxygen, water resistant
(iii) Has low decomposition temperature and gets decomposed in 60
days.
(iv) Do not release fumes or bad odour.

Uses: promising alternative for petroleum-based polymers, used for coating

drugs, used for manufacturing disposable products used in the food industry,
medical implants, disposable clothings

Poly Dimethyl Siloxane

It is prepared from di methyl silicon dichloride which on hydrolysis gives diol
which undergoes polymerization.

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Properties:
(i) Resistant to biodegradation
(ii) Optical transparency
(iii) water repellent
(iv) biocompatible
(v) shows viscoelastic properties
Uses: as seal, gaskets, making artificial heart valves, transfusion tubes,
component in silicon grease, damping fluids, cosmetics etc.

Conducting polymers
Polymers are insulators because of the absence of free electrons. In
becoming electrically conductive, a polymer has to imitate metal that is the
electron needs to be free to move. Such type of polymers are called conducting
polymers.
The conductivity of polymers can be compared to those of other materials,
varying from quartz (insulator) to copper (conductor). Polymers may also have
conductivities corresponding to those of semiconductors.
Two conditions for a polymer to become conducting are:
1. Polymer possess conjugated doublé bonds.
2. Polymer has to be disturbed either by removing or adding electron to the
material. This process is called doping.

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 Intrinsically Conducting Polymer (ICP)
Here the back bone or associated groups possess delocalized electron pair
or residual charge. Such polymers essentially contain conjugated π electron back
bone. In an electric field, these conjugated electrons get excited and can be
transported through the solid polymeric material.
The orbital of the conjugated π electrons get overlapped over the entire
back bone resulting in the formation of valence bands and conduction bands.
Ex: poly acetylene, poly quinoline, polyaniline, poly pyrrole, poly thiophene etc.

Doped Conducting Polymer (DCP)

It is obtained by exposing a polymer to a charged transfer agent either in
gas phase or in solution.
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 ICP possess low conductivity, but possess low I.P and high E.A. Hence
the conductivity of ICP can be increased by generating + ve or − ve charge by
oxidation or reduction. This technique is called doping. There are two types
a) p-doping
Here ICP is treated with Lewis acid. Then a positive charge is created on
the polymer backbone. Ex : I2, Br2, AsF5, PF6 etc. (p – dopants)
2 (C2H2)n + 3I2 → 2 [(C2H2)n+I3−]
The iodine molecule attracts an electron from the polymeric chain and becomes
I3-. The lonely electron of the double bond from which an electron was removed
can move easily. As a result, the double bond successively moves along the
molecule. The positive charge on the other hand is fixed by electrostatic attraction
to the iodide ion which does not move easily.
b) n-doping
Here ICP is treated with Lewis base. Oxidation takes place and charge is
created in the polymer backbone. Ex: Li, Na, Ca etc.
…. −CH = CH − CH = CH −… + Li → ….− CH = CH − CH =CH−….
B+
Extrinsically Conducting Polymer (ECP)
The conductivity is due to the externally added ingredient. There are two
types.
a) Conductive element filled polymer
It is a resin or a polymer filled with conducting element such as carbon
black, metallic fibres etc. The polymer acts as the binder to hold the conducting
element.
Properties: low cost, light weight, durable and strong, easily processible in
different sizes and shapes.
b) Blended conducting polymer
These produced by blending conventional polymer either by physical or
chemical change.
Coordination Conducting Polymer
It is a charge transfer complex containing polymer obtained by combining
a metal atom with a polydentate ligand. They are corrosion resistant.
Applications
1. In rechargeable light weight batteries.

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2. In optical display devices.
3. In wiring in aircrafts and aerospace components.
4. In electronic devices as diodes and transistors.
5. In solar cells etc.

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