Module 5

HIGH POLYMERS
Polymer is a macromolecule formed by the repeated linkage of simple molecules
called monomers.

The repeating units are covalently linked to each other in the polymer. The
properties of polymers are different from monomers. The average molecular mass
of a commercial polymer is in the range of 103 - 107
Examples : Polyethelene, Polystyrene, Teflon, Plexiglass etc.

Monomer is a simple molecule with two or more bonding sites through which it
forms covalent linkages with other monomer molecules to form the
macromolecules. Monomers are thus building blocks of polymers.

Polymerization
It is the chemical reaction by which the monomer is converted into polymers.
Polymerization reactions need suitable initiators.

nCH2 = CH2 → (-CH2-CH2-)n

Ethylene (monomer) Polyethelene (polymer)
Functionality
It is the number of bonding sites present in a molecule of the monomer.

Degree of polymerization
It is the number of repeating units present in a polymer molecule.

Methods of polymerization

Bulk polymerization

In this method polymerization occurs in homogeneous system. This method is

used for the polymerization of liquid monomers. The liquid monomer acts as a
solvent for the added initiator and chain transfer agent, if any. The entire reaction
mixture is kept under agitation for effective heat and mass transfer. The reaction
mixture is heated initially to polymerization temperature to initiate the reaction.
The polymer product formed being free from impurities, it can be used without
purification.
Advantages
The method is simple and requires simple equipment
The purity of the product is high

Disadvantages
Viscosity build up
Heat control is difficult

Applications
This method is used for the production of plexiglass, polystyrene etc.

Solution polymerization

In this method polymerization occurs in homogeneous system. The presence of

solvent facilitates heat and mass transfer and reduces viscosity build up. The
monomer, initiator and chain transfer agent if any used are dissolved in an inert
solvent. The reaction mixture is kept under agitation and heated to
polymerization temperature to initiate the reaction. After completion of the
reaction, the product is isolated from the solvent by evaporation or used as such
in solution form.
Advantages
Viscosity build up is negligible
Heat control is easy

Disadvantages
Isolation of product needs evaporation of solvent
Very high mol.wt polymers cannot be produced

Applications
This method is used for the production of polyethelene, PVC etc.
 Suspension( Pearl) polymerization
It occurs in heterogeneous system & this method is used only for water
insoluble monomers. Since the product separates as spherical pearls or beads,
therefore this method is called pearl polymerization.

The use of aqueous media facilitates easy agitation & heat control. The water
insoluble monomer is suspended in water as several tiny droplets by continuous
agitation. These droplets are prevented from coalescing by the use of small
amount of water soluble polymer such as polyvinyl alcohol or colloids.

The initiators are soluble in monomers and the reaction mass is heated to initiate
the polymerization. The product formed is water insoluble and separates out in
the form of ‘Pearls’ or ‘Spherical Beads’ and they are isolated by filtration
followed by washing with fresh water.

Advantages
Effective thermal control.
The process is more economical, since water is used in the place of solvents.
Disadvantages
It is applicable only for polymerization of water insoluble monomers.
It is difficult to control particle size.

Applications
It is used in the production of PVC, Polyvinyl acetate, etc.

Emulsion polymerization

In This method monomer is water insoluble & the initiator is water soluble,
such as potassium persulphate & H2O2 etc. The water insoluble monomer is
dispersed in water like a uniform emulsion and this emulsion is stabilized by
adding surface active agents like soaps & detergents (RCOONa & RSO3Na).

After the addition of initiator, the system is kept agitated in the absence of
oxygen at 700 C. The surfactant used is normally a soap or detergent and it has
hydrophilic head & hydrophobic tail. At very low concentration, it gets
completely dissolved in water and at little higher concentration it gets
dispersed.
 When the concentration of surfactants exceeds critical micelle concentration
then they will form micelle (aggregation of 50-100 molecules) oriented with tails
inwards and head outwards.

The interior of micelles provides hydrocarbon environment and when the

monomer is added, bulk of its remains in the aqueous phase but some of it
dissolves in each of the micelle. The free radicals generated in the aqueous phase
diffuses into micelle and causes its swelling.

H2O2 → 2OH.

The monomers consumed inside the micelle are replaced by continuous

diffusion of fresh monomers from aqueous phase. The polymer chain grows
continuously till the radical termination. The polymer formed is in the form of well
stabilized latex further it is isolated either by coagulation using electrolytes or by
freezing method.
Advantages
Easy heat control.
Very high molecular weight polymers are obtained.

Disadvantages
The polymer needs additional cleanup & purification.
The method requires rapid agitation.

Application

In the synthesis of PVC, Polyvinyl acetate, etc.,

Preparation, Properties & Applications of Polyurethane, Epoxy
resin and Kevlar.

Polyurethane (PU)

Polyurethane is a polymer composed of organic units joined

by carbamate (urethane, -NH-CO-O-) linkage. Polyurethane is prepared by the
poly addition reaction between diisocyanate and a diol, triol or polyol with
tertiary amine as a catalyst. During addition reaction the H atom of OH group
migrates and adds to nitrogen atom hence it is called rearrangement addition
polymerisation.
Properties
Highly flexible due to additional oxygen present in it
It is highly resistant to water, oil and corrosive chemicals
It has high tensile strength
It has excellent abrasion resistance

Applications
Used as gymnasium and dance flooring material
Used as surface coatings, films, foams and adhesives
PU foams are used as cushions for furniture's and automobile etc,.
PU fabrics are used in the manufacturing of swim suits and lightweight garments.

Epoxy Resin

Epoxy resin is prepared by the condensation polymerization of bis-phenol-

A and Epichlorohydrin in the presence of alkali. The obtained epoxy pre
polymer resin is linear, low molecular weight and a soluble liquid
 This epoxy resin is further cured or hardened at room temperature on mixing
with hardeners like diamine, dicarboxylic acid or acid anhydrides to get cross
linked epoxy resins.

Epoxy prepolymer + hardeners cross linked epoxy resins

Properties

Epoxy resins show outstanding toughness, chemical

inertness, flexibility and adhesion.
Epoxy resins are highly resistant to water, solvents, acids
and alkali materials

Applications

Used in surface coating materials

Used in laminating materials
These are also used in industrial flooring, adhesives,
 Kevlar

Kevlar is synthesized in solution from the monomers 1,4-

phenylene-diamine (para-phenylenediamine) and terephthaloyl
chloride in a condensation reaction yielding hydrochloric acid as a
byproduct.
1,4-phenylene-diamine Terephthaloyl chloride Kevlar
Properties

High tensile strength

High modulus of elasticity
Low weight, high chemical inertness, high cut resistance, flame resistance,
very low coefficient of thermal expansion and textile processibility

Applications

Used in cables, brake linings and body armor

Used in plastic reinforcement for boat hulls, airplanes and bicycles
Used as inner lining for some bicycle tyres to prevent punctures
These fibers are used in woven rope and in cables.
Properties

High tensile strength

High modulus of elasticity
Low weight, high chemical inertness, high cut resistance, flame resistance,
very low coefficient of thermal expansion and textile processibility

Applications

Used in cables, brake linings and body armor

Used in plastic reinforcement for boat hulls, airplanes and bicycles
Used as inner lining for some bicycle tyres to prevent punctures
These fibers are used in woven rope and in cables.
 GLASS TRANSITION TEMPERATURE
When an amorphous polymer is heated, the temperature at which the
polymer structure turns “viscous liquid or rubbery" is called the Glass Transition
Temperature, (Tg). It is also defined as a temperature at which
amorphous polymer takes on characteristic glassy-state properties like
brittleness, stiffness and rigidity (upon cooling).This temperature (measured in
°C or °F) depends on the chemical structure of the polymer and can therefore
be used to identify polymers.

Factors affecting Tg
Crystallinity
The Tg value of a polymer depends on the degree of Crystallinity. Higher
the Crystallinity, higher the Tg value of a polymer. Segmental & chain mobility’s
are easier in non crystalline or amorphous polymers than in crystalline
polymers. In crystalline polymer, the linear or stereo regular chains are linked
up parallel to each other & are held by strong cohesive forces. This leads to a
high Tg value of the polymer.

Molecular weight
The Tg value of all polymers in general increases with molecular weight up
to 20,000 and beyond which the effect is negligible.
 Side group
Poly (α- methyl styrene) has higher Tg value (1700C) while polystyrene has lower
Tg value (1000C). This is due to the presence of methyl side group in Poly (α-
methyl styrene) which hinders the free rotation about C-C bond, these restricted
chain mobility increases the Tg value.

Plasticizers
Plasticizers are low molecular weight non volatile substances, which when added
to a polymer improves its flexibility & processibility. The presence of plasticizers
decreases the Tg value because plasticizers molecules penetrate in to polymer
matrix, occupying the space between polymer molecules & thereby reducing the
cohesive forces between them.

Significance of Tg
Tg value is a measure of flexibility of polymers. Thus the use of any polymer at
any temperature is decided by its Tg value. Tg value along with Tm helps in
choosing the right temperature of processing the polymer by different
techniques.
 DETERMINATION OF MOLECULAR WEIGHT OF POLYMERS

Number average molecular mass

It is defined as the total mass of all molecules in a polymer sample divided by the
number of molecules present. The number average molecular mass is experimentally
determined by measurement of colligative properties that is elevation in boiling
point, depression in freezing point, lowering of vapor pressure & osmotic pressure.
Thus, the number average molecular mass is defined by,

Where, N is the number of molecules of mass M.

If, in a sample Ni molecules are having a molecular mass Mi, N2 molecules with
molecular mass M2 etc…then, the expression for number average molecular mass
is
.
Weight average molecular mass
Weight average molecular mass is the mass obtained when sum of the products
of total mass of group of molecules (Having different molecular masses) and their
respective molecular masses is divided by total mass of all the molecules. It is
experimentally determined by light scattering and ultra centrifugation techniques;
which measure molecular size.

The weight average molecular mass is always greater than the number average
molecular mass. Therefore, the ratio of these two is greater than or equal to one.
This ratio is called distribution or “Poly dispersity index”.
 CONDUCTING POLYMERS

An organic polymer with highly delocalized pi electron system, having the

electrical conductance in the order of a conductor is called conducting
polymers.

Ex: Polyacetylene, Polyaniline, Polypyrrole, Polythiophene etc.,

The conducting polymers are synthesized by doping, in which the charged

species are introduced in organic polymers having pi back bone. The important
doping reactions are:

Oxidative doping [p- doping]

Reductive doping [n-doping]

Oxidative doping [p- doping]

In this process, pi back bone of a polymer is partially oxidized using a suitable

oxidizing agent like iodine vapors, iodine in CCl4, perchloric acid etc., this creates
positively charged site on the polymer back bone, which are current carriers for
conduction.
Mechanism of conduction

The removal of an electron from the polymer pi back bone using a suitable
oxidizing agent like iodine in CCl4 leads to the formation of delocalized radical ion
called polaron. A second oxidation of a chain containing polaron followed by
radical recombination yields two charge carriers on each chain.

The positive charge sites on the polymer chains are compensated by anion I-3 (tri
iodide) formed by the oxidizing agent during doping. The delocalized positive
charges on the polymer chain are mobile. Thus these delocalized positive charges
are current carriers for conduction. On doping polyacetylene using iodine in CCl4,
for partial oxidation, the conductivity increases from 10-5 S/cm to 105 S/cm.
 Reductive Doping [n- doping]
In n- doping, pi back bone of a polymer is partially reduced by a suitable
reducing agent. This creates negatively charged sites on polymer back bone. These
negatively charged sites are responsible for the conduction. The most commonly
used reducing agent is a solution of sodium naphthalide in THF (tetra hydro furan).

Mechanism of conduction

The addition of an electron to the polymer back bone by using a reducing agent
generates a radical ion or polaron. A second reduction of chain containing polaron,
followed by the recombination of radicals yields two negatively charged carriers on
each chain. These charged sites on the polymer chains are compensated by cation
(Na+) formed by the reducing agent.
Applications of conducting polymers

As electrode material for commercial rechargeable batteries.

As conductive tracks on printed circuit board.
As bio-sensors, humidity sensor, gas sensor, radiation sensors.
In electro chromic display windows.
As information storage device.
As film membranes for gas separations.
As light emitting diodes.
In the fuel cells as the electro catalytic materials.
 SLE

Classification of Polymers

Based on occurrence
• Natural polymers. Ex: Wood, cellulose, Jute etc.
• Synthetic polymers. Ex: PVC, PMMA, PTFE etc.

Based on thermal behavior

▪Thermoplastic polymers. Ex: PTFE, PMMA etc.
▪Thermosetting polymers. Ex: Bakelite, Epoxy resin etc.

Based on type of polymerisation

▪Addition polymers. Ex: PMMA, PVC etc.
▪Condensation polymers. Ex: Polyester, Epoxy resin, Nylon-6,6 etc.

Based on chemical structure

▪Linear polymer. Ex: High Density Polyethylene (HDPE)
▪Branched polymer. Ex: LDPE, Polystyrene and PMMA.
▪Cross linked polymer. Ex: Bakelite.