Dr Champa Verma

Associate Professor
JNGEC, Sundernagar, Mandi (HP)
• Polymers: A polymer is a long molecule formed by
joining together of many small molecular units by
chemical bonds.
n(CH2 = CH2) → (-CH2 - CH2-)n
Ethylene Polyethylene
• Monomers: Small molecules which combine together to
form polymer molecules are known as Monomers.
• Polymerization: The chemical process leading to the
formation of polymer is known as Polymerization.
• The number of monomeric units contained in the
polymer is known as the Degree of Polymerization. When
n is less than 10 then polymers are known as oligomers
in general and when n is large polymers are called high
polymers.
 Based on Origin or Sources

Natural Polymer :- Polymers which are isolated from

natural materials are called as Natural Polymers . E.g. :
Cotton , silk , wool , natural rubber.

Synthetic Polymer :- Polymers which are synthesized

artificially called as Synthetic Polymers . E.g. :
Polyethylene , nylon , terylene.

Semi-synthetic Polymers :- These polymers are mostly

derived from naturally occurring polymers by
chemical modification . E.g. : Rayon
 Based on Configuration/Stereochemistry
During formation of polymers there may be generation of stereocentres
(chiral centres) depending upon structure of monomer units. Depending
upon the configuration at stereocenters polymers can be classified as:

Isotactic polymer:The head-to-tail configuration, in which

all bulky side groups are on the same side of the chain, is called
isotactic polymer.

Atatic polymer:The arrangement of bulky side groups are

random.

Syndiotactic Polymer: The arrangement of the side

groups is in alternating fashion.
 Addition Polymers

Polymer synthesized by addition polymerization has the

same empirical formula as that of monomer. The monomer
molecules bond to each other without the loss of any atoms.
The addition polymers are formed by the repeated addition
of monomer molecules possessing double or triple bonds,
e.g., the formation of polythene from ethene and
polypropene from propene.

nCH2=CH-CH=CH2 + nC6H5CH=CH2
(1,3-butadiene) Styrene C6H5

(-CH2-CH=CH-CH2-CH-CH2-)n
SBR
 Condensation Polymers

Two different monomers combine with the loss of a small

molecule, usually water, HCl etc. Polyesters and polyamides
(nylon) are in this class of polymers.

nNH2-(CH2)6-NH2 + nHOOC-(CH2)4-COOH
Hexamethylenediammine (Adipic acid)

-2nH2O

(-NH-(CH2)6-NH-CO-(CH2)4-CO-)n
Nylon-6,6
Crystalline polymers have melting point while amorphous polymers
have glass transition temperature and semi-crystalline polymers can
have both melting point and glass transition temperature. Glass
transition temperature (Tg) is the temperature of transition from
glassy state to rubbery state or we can say below which polymer
behave as a glassy material and above which it behave as a rubbery
material. Glassy state is hard and brittle while rubbery state is soft
and flexible. According the end use application some of the polymers
are used above Tg and some are used below.

1. Flexibility: linear polymer chains made of C-C, C-O or C-N single

bond have greater degree of freedom of rotation on a single bond.
Presence of rigid groups, such as aromatic or cyclic groups or
bulky groups, in the carbon chain backbone hinders the freedom of
rotation. This restriction in chain mobility increases the Tg value.
For example:
 In a linear polymer like polyethylene, Tg = -110 ºC
 In polyethylene terephthalate with cyclic group in the C chain
backbone, Tg = 69 ºC.
 In polystyrene with aromatic group attached to one of the C atoms
in the carbon chain backbone, Tg = 100 ºC.
3. Effect of side groups: Poly(α-methyl styrene) has higher Tg (170
ºC) value while polystyrene has lower Tg(100 ºC) value, due to
presence of extra methyl side group in former which hinders the free
rotation about carbon-carbon bond of carbon chain backbone. This
restricts the chain mobility and thereby increases the Tg value.
4. Molecular Weight: The Tg of all polymers in general, increases
with increase in molecular weight upto 20,000, and beyond this the
effect is negligible.
5. Cross-linking: Cross-linking introduces restriction and stiffness in
the polymer therefore causes the increase in glass transition
temperature.
6. Plasticizer: Plasticizers are generally low molecular weight
substances and when added to polymer, cause separation of polymer
chains, reduction of co-hesive forces and overall increase molecular
mobility. Plasticizers reduces brittleness of polymers and reduces
glass transition temperature.
7) Cross-Linking: The presence of cross-links between chains restricts
rotational motion and hence, greater the degree of cross-linking , the
higher the Tg.
8) Stereo-regularity: The Tg increases with the stereo-regularity of
polymers. Thus Tg of isotactic polymer is greater than that of
syndiotactic polymer, which in turn has greater Tg than atactic
polymers.
9) Copolymerization: Random copolymers have lower Tg’s since it
tends to promote the disorder, reduce molecular packing and reduces
the inter chain forces of attraction.
 1. The Tg value is a measure of flexibility of polymer and the
type of response the polymer would exhibit to mechanical
stress.
2. Its value gives an idea of thermal expansion, heat capacity,
refractive index, electrical and mechanical properties of
polymer.
3. Its value can decide whether a polymer at the use
temperature will behave like rubber or plastic.
.
4. Knowledge of Tg and Tm is useful in choosing the right
temperature for fabrication of materials. (Fabrication
temperature is the region in which the polymer material can
be converted into a finished product through different
processing techniques, such as injection molding,
compression molding, calendering, extrusion, etc.)
PP (Polypropylene) :
Polypropylene is manufactured at low pressure using Zeigler-Natta
catalysts (aluminium alkyls and titanium halides) by coordination
polymerization. Usually 90% of the polymer is in isotactic form. The
isotactic PP is a stereo specific polymer in which the propylene units are
attached in a head-to-tail fashion and the methyl groups are aligned on the
same side of the polymer chain. Hence, isotactic PP cannot crystallize in the
same fashion as PE, since steric hindrance by the methyl groups prohibits
this conformation.

Properties:
1. It is inert to water and microorganisms and it is low cost polymer.
2. Polypropylene is known to have a high melting point, making it an
ideal material for the construction of microwave-friendly containers.
3. Polypropylene is chemically resistant towards water, alkalis, and
acids.
4. This polymer is also quite resistant to stress and cracking, even when
it is flexed. This is the reason why polypropylene is widely used in the
construction of hinges.
5. Polypropylene exhibits high resistance to wear and tear. Therefore,
this polymer is highly durable.
Uses:
1. Many plastic living hinges, such as those on flip-top bottles, are made
of polypropylene because it is fatigue resistant.
2. Polypropylene is used in the production of piping systems, both those
requiring high purity and those requiring strength and rigidity.
3. It's used in the production of polypropylene chairs.
5. Polypropylene can be used to make a variety of medical and
laboratory products because it can withstand the heat of an autoclave.
6. Extremely colorfast polypropylene is commonly used in the
production of domestic carpets, rugs, and mats.
7. Polypropylene is a popular material for ropes because it is light
enough to float in water.
8. Polypropylene is also used as an electrical cable insulation alternative
PVC (Polyvinyl Chloride)
Polyvinyl Chloride is produced by free radical initiated chain polymerization. It
is a thermoplastic polymer obtained by heating a water emulsion of vinyl
chloride in presence of a small amount of benzoyl peroxide or hydrogen
peroxide in an autoclave under pressure. PVC is most versatile of all plastics
because of its blending capability with plasticizers, stabilizers and other
additives.

Properties:
 It is a colorless, odorless, non-flammable material.
 It is a chemically inert and is highly resistant to acids and alkalis.
However, plasticized PVC is relatively less resistant to chemicals.
 It is resistant to atmospheric oxygen, i.e., resistant to oxidation.
 It possesses greater stiffness and rigidity compared to polyethene.
 Due to its versatile properties, such as lightweight, durability and easy
processability, PVC is now replacing traditional building materials like
wood, metal, concrete, etc.
 Applications:
 PVC is used for making building and construction materials,
pipes, flooring, vinyl siding.
 Plasticized PVC is used mainly in wire and cable insulations and
in packaging
materials.
 Flexible films and sheets are used as pool liners and roof
coatings, carpet backing, rain coats etc.
 PVC pipes are used for carrying corrosive chemicals in
petrochemical factories.
Polymethylmethacrylate/ Plexiglass (PMMA)
It is a thermoplastic and transparent plastic. Chemically, it is a synthetic
polymer of Methylmethacrylate. PMMA is obtained by the polymerization of
methylmethacrylate (MMA) using hydrogen peroxide as initiator by bulk or
suspension polymerization.
Properties:
• It is amorphous and transparent plastic. It is nearest alternative
of glass.
• It has good optical clarity, but poor scratch resistance.
• It has good outdoor weathering property and dimensional
stability.
• It is resistant to water, alkalies and inorganic salts but dissolves
in organic solvents.

Uses:
PMMA is used for making automobile-lamp housing, street-light
housing, aircraft windows, canopies and signal boards.

It is used in paints and adhesives.

Used for making artificial teeth and contact lenses, transparent bath
tubs and wash basins
 Polyurethanes
Polyurethanes (PU) are the polymeric materials in which
the monomer units are linked through –NHCOO- group.
They are prepared by polyaddition reaction between
diisocyanate and diols or triols or polyols.

PU resembles polyamides in their structure, with the presence

of one more oxygen making the chain more flexible.

During polyaddition H atom of OH migrates and adds to N

atom. This is also known as Rearrangement addition
polymerization.
Properties:

1. It is resistant to water, oil and corrosive chemicals.

2. It may be translucent or opaque.
3. It has high tensile strength.
4. It has excellent abrasion resistance.
5. The presence of additional oxygen in chain increases the flexibility
and thus reduces Tm.

Uses:
1. PU coatings are used as gymnasium and dance floors where high
abrasion resistance is required.
2. PU foams are used as cushions for furniture and automobiles because
of the improved strength, lower density and easier fabrication.
3. PU fabrics are used as light weight garments and swimsuits because of
their stretching property.
4. PU is used as soles for shoes.
5. PU elastomers are used as gaskets, seals, tyres and industrial wheels.
Epoxy resins
These resins derived their name from the fact that monomer and the
polymer(before cross-linking) contains epoxide groups.
They are prepared by condensation polymerization bis-phenol A and
excess of epichlorohydrin.
Final curing is done by adding di- and poly-anhydrides and acids or by
adding diamines. Which result in formation of three dimensional cross
linked polymer .
Properties:
They have excellent adhesive characteristics and are used as adhesives
for glass, metal etc. and are popularly known as araldite.
They are very good materials in electronic applications particularly in
moldings containing inserts and encapsulation.

Epoxy resins have excellent resistance to wear, they are also tough and
heat resistant. Hence, they are used for surface coatings particularly for
making skid resistant surfaces of highways and road junctions.
Applications:
They have excellent adhesive characteristics and are used as adhesives
for glass, metal etc. and are popularly known as Araldite.

They are used in industrial flooring, skid resistance, highway surfacing and
patching materials.

They are used as laminating materials in electrical equipments.

Molds made from epoxy resins are employed for the production of aircraft and
automobile components.

They are used as matrix in fiber reinforced plastics.

SILICONES (Organo-Silicon Polymers)

Silicones comprise of alternate silicon oxygen structure, in which alkyl
or aryl groups (mostly alkyl groups) are directly attached to silicon
atoms. They are also called as polydialkylsiloxanes. They can be
represented as:
 Silicones are prepared from chloroalkylsilanes. Hydrolysis of
chlorosilane gives dimethyl silicon hydroxide intermediate
(unstable), which undergoes polymerization to give dimethyl
silicon polymer (silicone rubber). Silicone rubber can be cross
linked between two adjacent chains by using organic peroxides.

Properties:
Wide service temperature range – excellent thermal and thermoxidative
resistance (-Si-O-Si- binding energy is higher than C-C bonds)
Excellent resistance to attack by oxygen, ozone and sunlight.
Good excellent insulation properties
Low chemical reactivity.
High bio-compatibility.
Excellent mechanical properties (high tear strength, high elongation) Excellent
non-stick and non-adhesive properties.
Low toxicity.
Flexible at low temperatures due to their low glass transition temperature (Tg).
Optical transparency.

Applications:
Silicone oils and silicone greases are used as high temperature lubricants and
in polishes as these have high water repellent tendency.
Silicon rubbers inert to chemicals and are biocompatible and hence, are used
for making artificial heart valves, for plastic surgery, etc.

Silicones are also used to manufacture laminates which can stand fairly high
temperatures without undergoing degradation.
Light weight foams are made from silicone resins by using foaming agents.
Vulcanized silicon rubbers are used for making tyres and these rubbers remain
flexible in the temperature range of -90 to + 150 oC.
 FIBERS
Fiber is generally defined as a flexible, macroscopically homogenous
body having a high length to width ratio and a small cross section.
Polyethylene Terephthalate (Polyester)

These are the polycondensation products of dicarboxylic acids and

diols. Dacron or terylene is the best known example of polyesters. It is
manufactured by heating a mixture of ethylene glycol and terephthalic
acid at 420 to 460 K. Dacron fiber (terylene) is crease resistant and is
used in blending with cotton and wool fibers and also as glass
reinforcing materials in safety helmets, etc.

By Esterification
By Trans-esterification
 Properties of
Terylene:
It has low moisture Terylene has high
absorbing power mechanical
and dries up very strength and
quickly. dimension stability.

It shows creep and It is a very strong

abrasion resistance fibre and will
and good suffer very little
insulating loss in strength
properties. when wet.

It is elastic in nature
It is stable in the
and posses the
temperature range
property of high
of -40 – 100 oC.
crease resistance.
 Applications of
Terylene:

The fibre may be It is used for making

blended with wool video and audio
and other natural tapes.
fibres.

The fibre may be

blended with cotton It is used in textile
and wool to form industry for making
another fabrics like hard wear clothes and
terycot and terywool, other dress material.
respectively.

It is used for making

clear bottles for food
and beverages.
Kevlar
Kevlar Aramid fiber was commercialized by DuPont in
1972. It is an aromatic polyamide with benzene rings linked to the
amide group, -CONH- group.
PREPARATION:
It is prepared by polycondensation between aromatic dicholoride
like terephthalic acid dichloride (terephthaloyl chloride) and
aromatic diamines like 1,4- phenylene diamine (1,4-diamine
benzene).
PROPERTIES:
 It is exceptionally strong, 5 times stronger than steel
and 10 times stronger than aluminium.
 It has high heat stability and flexibility.
 It has resistance against almost all the solvents except
some powerful acids.
 It does not loose its strength at -196 oC .

USES:
 It is used in aerospace and aircraft industries.
 It is used for making car parts such as tyres and
brakes, clutch, lining etc.
 It is used for preparation of ropes, cables, helmets etc.
Lexan
Lexan is a polycarbonate resin thermoplastic. Polycarbonate
(PC), was first developed in 1953 by Bayer in Germany, and
General Electric in the US independently. Its most popular trade
name is LEXAN .
Polycarbonate (PC) are high-performance tough thermoplastic
polymers that have organic functional groups linked together
by carbonate groups (-O-(C=O)-O-). It is widely used for bullet-
proof windows and safety or crash helmets. Lexan is the most
common example of Polycarbonates.

Preparation of Polycarbonate

Polycarbonate is produced by condensation polymerization

between bisphenol A and either Carbonyl chloride or diphenyl
carbonate
a) Preparation of Polycarbonate by condensation polymerization
between bisphenol-A and Carbonyl Chloride
The polymer is usually formed by the reaction of bisphenol-A and
carbonyl chloride in a basic solution where polymerization takes
place at the interface between the aqueous and organic layer with
the help of a catalyst amine.
(b) Preparation of Polycarbonate by condensation polymerization
between bisphenol-A and diphenyl Carbonate
Polycarbonate can also be made by condensation polymerization of
bisphenol-A and diphenyl carbonate to eliminate the use of carbonyl
chloride (Phosgene) which is an extremely poisonous gas.
Properties of Lexan:
 Lexan has high impact resistance and a high strength-to-
weight ratio. It is 200 times more impact resistant than glass
while being 5–6 times lighter. For these reasons, Lexan is easier
to transport, handle, and install than glass.
 Lexan has low flammability, high polish, and glass-like clarity.
However, for applications like eyeglasses, it requires a scratch-
resistant coating since its surface can be easily scratched.
 It’s flexible and can be molded without cracking. Lexan can be
repeatedly heated and cooled without any deterioration in its
properties.
 It holds up well to high temperatures and corrosive
WHERE IS LEXAN USED? Common Lexan applications touch every
part of our lives. Industries that often use Lexan include:
 Aerospace and automotive: These to make stroindustries use Lexan
ng but light windshields for planes, trains, and automobiles. This
material is also used to build bullet-resistant windows for automobiles
and isolation walls for bank counters.
 Defense: Military manufacturers value Lexan for its light
weight and high strength. This material is used to build
components for military vehicles and jet fighters. Several
accessories carried by soldiers are also made with Lexan to reduce
the total weight that they carry.
 Technology: The technology industry, especially electronic
component manufacturing, uses Lexan because it insulates well
against electricity and resists heat and corrosive chemicals. Lexan
is used in large quantities to make CDs, DVDs, and Blu-Ray discs
as well as computer and television screens. Lexan’s low weight
and high impact resistance also make it suitable for use as laptop
and cell phone cases along with video game controllers.
 Environmentally friendly products: Eco-conscious products
are composed of Lexan because this material is highly recyclable.
Reusable water bottles, food containers, canteens, and glasses are
made with Lexan. Lexan is far better than glass for these
applications since it resists fractures while retaining the
transparency of glass.
CONDUCTING POLYMERS
In 1977, Alan J. Heeger, Alan MacDiarmid and Hideki Shirakawa proved that
polyacetylene doped (oxidized) with iodine has high conductivity. This
research earned them the 2000 Nobel Prize in Chemistry. It has great
applications in day to day life.

Organic polymers having electric conductance of the order of metallic

conductors are now known as conducting polymers.

Classification of conducting polymers:

• Extrinsically conducting polymers: They are prepared by mixing
conducting fillers like metal fibers, metal oxides, carbon black with
insulating polymers. In this type of conducting polymers, insulating
polymers forms the continuous phase and the added fillers form the
conducting network.
• Intrinsically conducting polymers: In intrinsically conducting
polymers, conductivity is due to the organic polymers themselves. They
conduct electricity when doped with oxidizing or reducing agents or
protonic acids.
• Conducting polymers with conjugated π-Electrons
Organic polymers with highly delocalized π-electron system having
electrical conductance of the order of conductors are called
intrinsically conducting polymers. The basic requirement for
organic polymers to be conducting is the formation of continuous
conjugation through the polymer chain.
These conjugated organic polymers in their pure state are either
insulators or semiconductors. The π-electrons are normally
localized and do not take part in conductivity. But these electrons
delocalize on doping and conduct electricity. The dopant may be
oxidizing or reducing agent or protonic acid. Accordingly, they
are called p-doping, or n-doping and H-doping polymers.

Mechanism of conduction in Polyacetylene

Applications of Conducting Polymers:

 In rechargeable light weight batteries based on

perchlorate doped polyacetylene Li system. These are 10
times stronger than conventional lead storage batteries.
 In wiring in aircrafts and aerospace component.
 In transistors and diodes.
 In electromagnetic screening materials.
 In photovoltaic devices.
 In molecular wires and switches.
 Manufacturing of chemical sensors.
 Antistatic coatings.
 Corrosion inhibitors.