Polymer Chemistry

A notes of Dr.
Bapu R Thorat
Polymers Chemistry
Dr. Bapu R Thorat
Department of Chemistry,
Government of Maharashtra,
Ismail Yusuf Arts, Science and Commerce College, Mumbai
2.1. Introduction
2.1.1. What are polymers
2.1.2. Structural Features of a Polymer
2.1.3. Classification of polymers
2.1.3.1. Origin
2.1.3.2. Thermal response
2.1.3.3. Depending on the structure of polymers
2.1.3.4. Tacticity
2.1.3.5. Plastics, Elastomers, Fibers and Liquid Resins
2.1.3.6. Addition and condensation Polymers
2.1.3.7. Organic and Inorganic Polymers
2.1.4. Copolymer and its types
2.2. Types of polymerization
2.2.1. Addition polymerization
a. Ionic polymerization
b. Free radical polymerization
2.2.2. Condensation polymerization
2.2.3. Degree of polymerization
2.3. Elastomers or Rubbers
2.3.1. Natural rubber
2.3.1.1. Gutta Percha
2.3.1.2. Vulcanization of rubber
2.3.2. Synthetic Rubbers
2.3.2.1. Styrene Rubber (Buna-S)
2.3.2.2. Nitrile Rubber (Buna-N/NBR)
2.3.2.3. Neoprene (GR-M)
2.3.2.4. Butyl Rubber (GR-I)
2.3.2.5. Polysulphide Rubber (GR-P)
2.3.3. Diene polymerization: 1,2- and 1,4- addition
2.3.3.1. Polymerization of isoprene
2.3.4. 1,3-Butadiene-styrene copolymer
2.4. Stereochemistry of polymers
Edited by Dr. Bapu R Thorat
A notes of Dr. Bapu R Thorat

2.4.1. Ziegler-Natta catalyst
2.5. Preparation and uses of polymers
2.5.1. Addition polymers
2.5.1.1. Polyethylene
2.5.1.2. Polypropylene
2.5.1.3. PVC
2.5.1.4. Polystyrene
2.5.1.5. Polyacrylonitrile
2.5.1.6. Polyvinylalcohol
2.5.1.7. Teflon
2.5.2. Condensation polymers
2.5.2.1. Polyesters
2.5.2.2. Polyamides
2.5.2.3. Polyurethanes
2.5.2.4. Phenol-formaldehyde resin
2.5.2.5. Epoxy resin
2.5.2.6. Polycarbonates
2.6. Recyclable polymers
2.6.1. Biodegradable polymers and their uses
2.6.2. Biomedical use of polymers
2.7. Additives to polymers
2.7.1. Plasticizers
2.7.2. Stabilizers
2.7.3. Fillers
2.1.
Introduction:
The macromolecular or chain molecular concept found wide acceptance and appreciation soon
after it was propounded by Staudinger in 1920. He advanced long chain structural formulas
for natural rubber, cellulosics such as cellulose nitrate, and polystyrene. Long sequences of
simple chemical units interlinked with covalent bonds came into recognition as the basic
structural feature for all polymer molecules.
Staudinger was not initially certain about the nature or identity of the terminal points or end
groups of the long chain polymer molecules. He was initially of the view that there was no need
to saturate the terminal valences and suggested that no end groups were needed or necessary.
Development and elucidation of the chain reaction theory of vinyl and related polymerization

by Flory and others, however, clearly established that polymer materials consisted of long
chain molecules with well characterizable end groups.
Polymer science is one of the most active and promising field of the science used to study the
various topics from natural origin or polymers (such as proteins, nucleic acids, cotton, wool,
silk, cellulose, leather, etc) that are of prime importance for living systems and synthetic high
polymers (such as plastics, rubbers, resins, films, fibers, surface coating materials, etc) that have
significant role in human economy and modern civilization.
1. Polymers have replaced metals and wood by light structural molecules in cars, aeroplanes,
furniture, building materials, etc.
2. They are used in modern dresses, transportation, communication, water management,
fisheries, public health, electrical and textile industries, storage purpose, medicine and
surgery, agriculture, and many more due to their unique and versatile properties. Some of
them are mention belowa. Superior heat resistance (polyamides).
b. Low temperature flexibility (polybutenes).
c. Adhesiveness (polycyanoacrylates).
d. Good lubricants (polyfluorocarbons).
e. Water repellency (silicones).
f.
Rigidity (moulded phenolics).
g. Flexibility (cispolybutadiene).
h. Low thermal conductivity (polyurethrene foam).
i.
2.1.1.
Magnetic properties (barium ferrite filled vinyl plastisols), etc.

What are polymers:
A polymer is large molecule build up by the repetition of small, simple units which are joined
by covalent bonds, sometimes referred as mers. The small simple repeating unit is called as
monomer. The word polymer is derived from the Greek word poly = many and mers = parts.
The functionality of a monomer is the number of sites it has for bonding to other monomers
under the given conditions of the polymerization reaction. Thus, a bifunctional monomer, i.e.,
monomer with functionality two, can link to two other molecules under suitable conditions

forming linear polymer while a polyfunctional monomer is one that can react with more than
two molecules under the conditions forming cross linked polymer.
These units can be extremely simple, as in addition polymerization, where a simple molecule
adds on to itself or other simple molecules. e.g. Polyethylene: It is polymer containing small
repeating unit ethylene joined to each others by covalent bond. Ethylene is called as monomer.
n H2C CH2
Polymerisation
Ethylene
C C
H2 H2
n
Polyethylene
The major alternative type of polymer is formed by condensation polymerization in which a

simple molecule is eliminated when two other molecules condense. In most cases the simple
molecule is water, but alternatives include ammonia, an alcohol and a variety of simple
substances.
The addition polymers formed by the polymerization of a single monomeric species are known
as homopolymers whereas the polymers made by addition polymerization from two different
monomers are termed as copolymers. For example, Buna-S rubber which is formed from 1, 3-
butadiene (CH2=CHCH=CH2) and styrene (C6H5CH=CH2) is an example of copolymer.

The number of repeating units (n or x) in the chain so formed is called the degree of
polymerization (DP = n). Polymers with a high degree of polymerization are called high
polymers and those with low degree of polymerization are called oligopolymers (short chain
polymers or oligomers). Polymers do not exhibit strength for n < 30 and that the optimum
strength of most of the polymers is obtained at n around 600. The useful range of n is from 200
to 2000.
Polymers are complex high molecular weight molecules (called macromolecules having weight
in the range 10,000 to 10,00,000). The polymers and macromolecules are two different terms
because polymers are consisting by repeating units liked by covalent bond whereas
macromolecules are may or may not be composed by repeating units. Most of the polymers are
used in plastics, rubber, or fibers.
2.1.2.
Structural Features of a Polymer:

The word polymer literally means many (poly) units (mer). A small, simple chemical unit
appears to repeat itself a (very) large number of times in the structure of a polymer molecule or
macromolecule. The so called repeat unit may consist of a single atom, say, sulfur atom, S,
exemplified by the well known plastic sulfur (SSSSSSSS)n, or more commonly a small
group of atoms, such as in polystyrene, mentioned in the preceding section, with the distinctive
feature that the repeat units are successively linked to one another on each side by covalent
bonds.
The simple molecular species from which a chain polymer molecule may be obtained or to
which a polymer molecular system may be degraded is called the monomer. Some common
polymers and structural representation of the respective monomers and repeat units are listed
in following Table.
Sr. No.
Polymer
Monomer
Repeat Unit
01
-(CH2 - CH2)n Polyethylene
CH2=CH2
Ethylene
-CH2 - CH2 -
02
H
Cl n
Polyvinyl chloride
03
CH3 n
Polypropylene
OAc n
Polyvinyl acetate
H
Ph
Cl
CH3
H
OCOCH3
Vinyl acetate
OCOCH3
H
Ph
Styrene
Ph
H
n
H
CH3
Propylene
H
05
H
Cl
Vinyl Chloride
04
Polystyrene
06
F
F n
poly (tetrafluoroethylene)
F
F
Tetrafluoroethylene

07
CN n
pol Acrylonitrile
H
CN
Acrylonitrile
08
CN
H
H n
Polybutadiene
2.1.3.
H
H
1,3-Butadiene
Classification of polymers:
The polymers were classified based on origin, thermal response, tacticity, etc.
Basis of classification Polymer Types
1. Origin
Natural
(as
Examples
available
in
Natural rubber, natural silk, cellulose,
nature)
proteins, starch etc.
Semisynthetic (Man made)
Hydrogenated, halogenated and cyclo

(natural) rubber; cellulosics (cellulose
esters/ethers), etc.
Synthetic (Man made)
Polyethylene,
polypropylene,
poly-
styrene, polybutadiene, nylon polyamides,
polycarbonates,
phenolics,
amino resins, epoxy resins etc.

2. Thermal response
Thermoplastics (they soften or Polyethylene,

melt on heating and harden styrene,
on cooling over many cycles
nylon
polypropylene,
poly-
polyamides,
linear
polyester [poly(ethylene terephthalate)],
of heating and cooling and etc.

retain
solubility
and
fusibility).
Thermosetting (they usually Phenolic resin, amino resins, epoxy
soften or melt initially on
resins,
diene
rubbers
(vulcanized),
heating, but fast undergo unsaturated polyesters.

chemical changes to finally
turn insoluble and infusible).

3.
Mode
of Chaingrowth or addition
formation
Polyethylene and other polyolefins,

Polystyrene and related vinyl polymers
etc.
Stepgrowth or condensation
Polyesters
and
polycarbonates,
melamine)
polyamides,
phenol
(urea,
formaldehyde
resins,
epoxy resins etc.

4. Line Structure
Linear (having no branches)
High density polyethylene (HDPE),

polyvinyls, bifunctional (polyesters and
polyamides) etc.
Branched (having branches)
Low
density
polyethylene
(LDPE),
higher poly (-olefins), phenolic resoles

and
resitols,
poly
(3-hydroxy
alkanoates) etc.
Cross linked or network (having Phenolic C-stage (resite) resin, C-stage
a complex network structure)
amino (urea / melamine-formaldehyde)

resins,
cured
epoxy
resin
and
unsaturated polyester resin etc.

5. Application and Rubbers (showing long
Natural rubber, (1, 4 cis poly isoprene)
Physical properties
synthetic rubbers (polybutadiene, SBR,
range elasticity)
nitrile rubber, polychloroprene rubber,

polylacrylate
rubber,
polyurethane
rubbers, silicone rubbers etc.)

Plastics (shapable under
Polyethylenes,
pressure, aided by heat)
(isotactic),
polypropylene
polystyrene,
poly
(vinylchloride), nylon polyamides linear

aromatic polyesters and polyamides,
polycarbonates, acetal resins etc.
Fibres (available in fibrillar or
Cotton (cellulose), natural silk, artificial
filamentous form)
silk
(rayons),
poly
(ethylene
terephthalate) fiber, nylon polyamide

fibers etc.
6. Tacticity
Isotactic (stereoregular)
Poly (-olefins) and all vinyl and related
Syndiotactic (alternative)
polymers.
Atactic (stereo irregular)

7. Crystallinity
Crystalline
Polyethylene
(crystallinity, > 50%)
polypropylene
(HDPE
and
(isotactic),
LDPE),
stretched
nylon polyamides, polyoxymethylene

etc. cellulose (cotton) fiber.
Semi crystalline
Polybutene, cellulosics (cellulose esters
(Crystallinity, 30 50%)
(rayons) particularly if stretched), Gutta

percha (1,4-trans polyisoprene) etc.
Amorphous or non-crystalline
Natural rubber and most synthetic
(Crystallinity < 25%)
rubbers, N-alkylated(>15% alkylation)

nylon polyamides, poly (methacrylates
and acrylates) poly (vinyl acetate),
polystyrene etc.
2.1.3.1.
Origin:
The polymers were classified as natural and synthetic polymers. The polymers isolated from
natural resources were called as natural polymers. The examples of natural polymers were proteins and enzymes, the polysaccharides, natural rubber, natural gums, natural silk and other
natural fibers, cellulosic and lingo-cellulosic, cotton (cellulosic), and jute, ramie, flax, hemp,
sisal, coir etc.
Semi-synthetic (modified natural) polymers and synthetic polymers are also called man made
polymers. The polymers synthesized from low molecular weight compounds or monomers are
called synthetic polymers. Examples of synthetic polymers were - PVC, polystyrene,
polyethylene, synthetic rubber, PVA, polyacrylonitrile, etc.
2.1.3.2.
Thermal response: Thermoplastic and Thermosetting Polymers:
Some polymers soften on heating and can be converted into any shape that they can retain on
cooling. The process of heating, reshaping and retaining the same on cooling can be repeated

several times. Such polymers, that soften on heating and stiffen on cooling, are termed
thermoplastics. Polyethylene, PVC, nylon and sealing wax are examples of thermoplastic
polymers.
Some polymers, on the other hand, undergo some chemical change on heating and convert
themselves into an infusible mass. They are like the yolk of egg, which on heating sets into a
mass, and, once set, cannot be reshaped. Such polymers, that become infusible and insoluble
mass on heating, are called thermosetting polymers.
Themoplastic polymers
Linear Polymers.
Thermosetting polymers
Cross-linked polymers.
Weak van der Waals intermolecular forces Chemical cross-linking make them infusible
and thus soften/melt on heating.
materials. Do not melt on heating.
Molten polymer can be moulded in desired Cross-linking is usually developed at the

shape. It can be remoulded by heating again.
time of moulding where they harden

irreversibly.
Examples are polystyrene, PVC, SBR, Teflon, Examples are Glyptals, epoxy polymers,
PMMA terylene.
2.1.3.3.
formaldehyde resins.
Depending on the structure of polymers:
a. Linear polymer:
A molecule of a linear polymer may be schematically represented by a simple line of finite
length (straight or zigzag, but usually wavy). These linear polymers are well packed and
therefore, have high densities, high tensile (pulling) strength and high melting points. For
example, polyethylene, nylons and polyesters are examples of linear polymers.
b. Branched polymer:
A molecule of a branched polymer may, however, be represented by a line of finite length with
short or long finite length branches attached to some of the repeat units in the chain molecule.
These branched chains polymers are irregularly packed and therefore, they have lower tensile
strength and melting points than linear polymers. For example, low density polyethene,
glycogen, starch, etc.
c. Cross linked polymer:

A cross linked polymer can be represented by a network structure that may be a planar network
as in graphite or space network, as in diamond. These are polymers in which long polymer
chains are cross linked together to form a three dimensional network. These polymers
are hard, rigid and brittle because of the network structure. E.g. Bakelite, melamine and
formaldehyde resin are some examples of this type.
A linear polymer is best exemplified by high-density polyethylene (HDPE), while a branched

polymer is exemplified by low-density polyethylene (LDPE) or poly ( olefins). Linear and
branched polymers are commonly thermoplastics, that are soluble and fusible, while the
network resins or polymers are examples of thermosetting resins or polymers that turn
ultimately insoluble and infusible.
2.1.3.4.
Tacticity:
A vinyl and related polymer (CH2CHR) is characterized by an asymmetric carbon atom

(marked with a little asterisk on it) in each of the repeat units of its chain molecules and a type
of stereochemical difference that may arise in the segments of the chain is d , l isomerism.
Considering head to tail linkage of the repeat units, the stereo sequences may be all d or all
l , etc sequences, identified in terms of tacticity or spatial disposition of the substituent group,
R.
a. Isotactic:
If all substituents are present on the same side of the carbon skeleton (all substituted methylene
having same configuration either d- or l-). e.g.:- Polystyrene.
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
b. Syndiotactic:

If all the substituents are alternatively arranged in a polymer chain (all substituted methylene
having alternative configuration; alternate appearance of d and l sequences) is called as
syndiotactic polymers. e.g.:- Polystyrene.
Ph
Ph
Ph
Ph
Ph
-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2- CH-CH2-CH-CH2-CH-CH2-CH-CH2
Ph
Ph
Ph
Ph
Ph
c. Atactic:
If the substituents are arranged randomly in a polymer chain (all substituted methylene having
random configurational arrangement) is called as atactic polymers. e.g.:- Polystyrene.
Ph
Ph
Ph
Ph
Ph
Ph
-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2- CH-CH2-CH-CH2-CH-CH2-CH-CH2
Ph
Ph
Ph
Ph
The stereoregularity (e.g.:- isotaxis and syndiotaxis) usually forces the polymer chain into a
certain conformational order (e.g.:- helix or planar zig-zag), at least in solid state in some cases
also in dissolved or molten state.
Isotactic sequence is distinctive as being very regular, while atactic sequence is one that is
highly irregular. Syndiotactic sequence may be viewed as regularly irregular or vice versa.
Isotactic and syndiotactic polymers are considered as stereospecific or stereoregular while
atactic polymers are viewed as random or stereoirregular. The overall molecular symmetry
and crystallinity are in the order isotactic syndiotactic >> atactic. Isotactic polymers are
generally characterized by high melting temperature (Tm) and high mechanical properties with
relatively high resistance to solvents and chemicals.
2.1.3.5.
Plastics, Elastomers, Fibers and Liquid Resins:
Depending on its ultimate form and use, a polymer can be classified as plastic, elastomers, fibre
or liquid resins.
a. Plastic:
These are linear polymers with very few cross linkages or no cross linkages at all. The
polymeric chains are held by weak van der waal forces and slide over one another. Due to lack
of cross linkages these polymers soften on heating and harden or become rigid on cooling. Thus
they can be moulded to any shape. Polythene, PVC, polystyrene are addition type polymer and

Terylene, nylon are condensation type polymers. When, e.g., a polymer is shaped into hard and
tough utility articles by the application of heat and pressure, it is used as a plastic.
Certain plastics do not soften much on heating. These can be easily softened by the addition of
some organic compounds which are called plasticizers. For example, polyvinyl chloride (PVC)
is very stiff and hard but is made soft by adding di-n-butyl phthalate (a plasticizer). Some other
common plasticizers are dialkyl phthalates and cresyl phthalate.
b. Elastomers or Rubber:
Typical examples are natural rubber, synthetic rubber, silicone rubber. In these elastomeric
polymers, the polymer chains are held together by the weakest intermolecular forces such as
van der waals forces. These weak binding forces permit the polymer to be stretched. A few
crosslinks are introduced in between the chains, which help the polymer to retract to its
original position after the force is released as in vulcanized rubber. When vulcanized into
rubbery products exhibiting good strength and elongation, polymers are used as elastomers.
c. Fibres:
If drawn into long filament like material whose length is at least 100 times its diameter,
polymers are said to have been converted into fibre e.g. nylon and terylene. Fibres are the
thread forming solids which possess high tensile strength and high modulus. These
characteristics can be attributed to the strong intermolecular forces like hydrogen bonding or
dipole-dipole interaction. Because of the strong forces, the chains are closely packed, giving
them high tensile strength and less elasticity. These strong forces also lead to close packing of
chains and thus impart crystalline nature.
d. Resins:
Polymers used as adhesives, potting compound sealants, etc. in a liquid form are described
liquid resins. Commercially available epoxy adhesives and polysulphide sealants are typical
examples.
2.1.3.6.
Addition and condensation Polymers:
There are two types of polymers according to the synthesis procedure used as (i) addition
polymer, and (ii) condensation polymer.
The addition polymer is one in which the monomers are molecules with multiple bonds which
undergo sequence of true addition reactions with each other and forming polymer, e.g.,
Polystyrene, PVC, polyethylene, polychlorostyrene etc. are the examples of addition polymers.
This kind of reaction yields linear polymers without cross-links, i.e. thermoplastic polymers.
Cross linking agents for addition polymers are molecules that contain two or more double
bonds per molecule, for example divinylbenzene. Cross-linking of linear chain polymers causes
them to stiffen and retain their shape, and also makes them insoluble in solvents that dissolve
the linear chain polymer. Note that the repeat unit of addition polymers, such as polyethylene,
contains the same number of atoms as the monomer. The molecular weights of addition
polymers can be very high. The different substituents (e.g., the benzene ring in polystyrene, the
chlorine atom in PVC, etc.) added to the linear polymer backbone have a profound effect on the
physical properties of these materials, which is why polyethylene is a flexible polymer whereas
PMMA and PVC are rather stiff.
The condensation polymer is one in which a small molecule (usually water) is eliminated in the
condensation of any two monomer units. It is clear, therefore, the monomers for condensation
polymers must be (at least) bifunctional molecules in which one function on one monomer
molecule reacts with the other function on another molecule. Examples are polyamides, made
by reacting a diacid with a diamine, and polyesters, made by reacting a diacid with a diol (a
diol is a molecule containing two terminal OH groups).
2.1.3.7.
Organic and Inorganic Polymers:
A polymer whose backbone chain is essentially made of carbon atoms is termed as organic
polymer. The atoms attached to the side valencies of the backbone carbon atoms are, however,
usually those of hydrogen, oxygen, nitrogen, etc. The majority of synthetic polymers are
organic.
In fact, the number and variety of polymers are so large thats why we refer to polymers on the
other hand, generally contains no carbon atom in their chain backbone are referred as inorganic
polymers. Glass and silicone rubber are examples of inorganic polymers.
2.1.4.
Copolymer and its types:
The synthesis of macromolecules composed of more than one monomeric repeating unit was
important to control the essential properties of the resulting material. In this respect, it is useful
to distinguish several ways in which different monomeric units might be incorporated in a
polymeric molecule. The following examples refer to a two component system, in which one
monomer is designated A and the other B.
Statistical copolymers: Also called random copolymers. Here the monomeric units are
distributed randomly, and sometimes unevenly, in the polymer chain:
~ABBAAABAABBBABAABA~.
Alternating copolymers: Here the monomeric units are distributed in a regular alternating
fashion, with nearly equimolar amounts of each in the chain:
~ABABABABABABABAB~.
Block copolymers: Instead of a mixed distribution of monomeric units, a long sequence or
block of one monomer is joined to a block of the second monomer:
~AAAAA-BBBBBBB~AAAAAAA~BBB~.

Graft copolymers: As the name suggests, side chains of a given monomer are attached to the
main chain of the second monomer:
~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.
2.2.
Types of polymerization:
There are two main types of polymerization addition and condensation polymerization.
2.2.1.
Addition polymerization:
Addition polymerization, is essentially a chain reaction, and may be defined as one in which
only a small initial amount of initial energy is required to start an extensive chain reaction
converting monomers, which may be of different formulae, into polymers. This process
involves the addition of monomer units to themselves to form a growing chain by a chain
reaction mechanism. A chain reaction consists of three stages, initiation, propagation and
termination.
The mechanism of polymerization can be divided broadly into two main classes, free radical
polymerization and ionic polymerization.
a. Ionic polymerization:
Ionic polymerization was divided into cationic and anionic polymerizations. Cationic
polymerization depends on the use of catalysts which are good electron acceptors. Typical
examples are the FriedelCrafts catalysts such as aluminium chloride AlCl3 and boron
trifluoride BF3. Monomers that polymerise in the presence of these catalysts have substituents of
the electron releasing type. They include styrene C6H5CH=CH2 and the vinyl ethers
CH2=CHOCnH2n+1.
In cationic vinyl polymerization, the initiator is a cation, which is an ion with a positive
electrical charge. A pair of electrons from the carbon-carbon double bond will be attracted to
this cation, and will leave the carbon-carbon double bond to form a single bond with the
initiator. This leaves one of the former double bond carbons at a loss for electrons, and carrying
a positive charge. This new cation will react with a second monomer molecule in the same
manner as the initiator reacted with the first monomer molecule. This happens over and over
until a high molecular weight is reached, that is, a molecular weight at which the polymer is
useful for something.
Anionic initiators include reagents capable of providing negative ions, and are effective with
monomers containing electronegative substituents such as acrylonitrile CH2=CHCN and methyl
methacrylate CH2=C(CH3)COOCH3. Styrene may also be polymerised by an anionic method.
Typical catalysts include sodium in liquid ammonia, alkali metal alkyls, Grignard reagents and
triphenylmethyl sodium (C6H5)3C-Na. Ionic polymerization is not of interest in normal aqueous
polymerization since in general the carbonium ions by which cationic species are propagated
and the corresponding carbanions in anionic polymerizations are only stable in media of low
dielectric constant, and are immediately hydrolyzed by water.
The modern methods of polymerization are the ZieglerNatta catalysts and group transfer
polymerization catalysts.
b. Free radical polymerization:
A free radical may be defined as an intermediate compound containing an odd number of
electrons, but which do not carry an electric charge and are not free ions. The decomposition of
oxidizing agents of the peroxide type, as well as compounds such as azodiisobutyronitrile
(AIBN) which decomposes into two radicals of (CH3)2C-CN and nitrogen (N2). These free
radicals were used as initiator for the addition reaction.
Initiation: The first stage of the chain reaction, the initiation process, consists of the attack of the
free radical on one of the doubly bonded carbon atoms of the monomer. One electron of the
double bond pairs with the odd electron of the free radical to form a bond between the latter

and one carbon atom. The remaining electron of the double bond shifts to the other carbon atom
which now becomes a free radical.
Propagation: During a chain reaction, most of the time is spent in the propagation phase as the
polymer chain grows. In the propagation phase, the newly-formed activated monomer attacks
and attaches to the double bond of another monomer molecule. This addition occurs again and
again to make the long polymer chain.
Termination: The final stage is termination, which may take place by one of several processes.
One of these is combination of two growing chains reacting together; an alternative is
disproportionation through transfer of a hydrogen atom and chain transfer. Chain transfer may
take place via a monomer, and may be regarded as a transfer of a proton or of a hydrogen atom.
Most common solvents are sufficiently active to take part in chain transfer termination, the
aliphatic straight-chain hydrocarbons and benzene being amongst the least active.
Example: Polymerization of ethane to polythene consists of heating or exposing to light a
mixture of ethene with small amount of benzoyl peroxide as the initiator.
2.2.2.
Condensation polymerization:
In this, the monomers condensed with each others with the elimination of a small molecule like
H2O, ROH or NH3, etc. The reaction is called (step growth) condensation polymerization and
the product formed is called condensation polymer. The process involves the elimination of by
product molecules; therefore, the molecular mass of the polymer is not the integral multiple of
the monomer units.
Polyester (e.g., terene or terelene or dacron) is prepared by the condensation polymerization of
dicarboxylic acid with dihydroxy alcohols.
The aliphatic polyamides are generally known as NYLONS. There are different types of nylons
and are usually indicated by a numbering system. This number gives the number of carbon
atoms present in the monomer molecules. Aliphatic Nylon have M.P. of 250-300C.
e.g. Nylon-6,6: It is obtained by the polymerization of adipic acid with hexamethylene diamine.
Addition polymerization
Involves
unsaturated
monomer
Condensation polymerization
like Involves
substances
with
at
least
ethylene, vinyl groups like chloride, styrene functional ethylene glycol (2-OH groups),

etc.
adipic acid (2-COOH groups).
Fast addition of monomers.
Step-wise slow addition.
At any instant, only monomer and polymers No monomer. Mixtures of dimers, trimers
are present.
Initiator
is
and tetramers etc. are present

necessary
to
catalyze
the Catalyst is not necessary.
polymerization.
No small molecules are eliminated.
Small molecules like H2O, HCl, CO2, CH3OH

are often eliminated.
Polymers
made
are,
for
example, Polymers made are, for example, terylene,
polyethene, polypropylene, polybutadiene, nylon, Formaldehyde-resins, silicones.

polyvinylchloride.
2.2.3.
Degree of polymerization:
The length and molecular weight of the polymer depends on the number of repeating units
(monomers) present in the chain. The total number of monomers present in the polymer chain
is called as degree of polymerization. It is denoted by later Dp.
The molecular weight of the polymer will be then, the product of degree of polymerization and
molecular weight of repeating (monomer) unit.
Molecular weight
of polymer
Molecular weight
of monomer
Dp
e.g. Polyethylene, Dp = 1000, molecular weight of ethylene monomer = 28.

Molecular weight of polyethylene = 1000 x 28 = 28,000.
Due to high molecular weight of polymers, they behaves differently than the common organic
compounds. e.g. Organic compounds have sharp melting or boiling point whereas polymer
does not melt sharply at one particular temperature. They are first become soft and then turn
into very viscous, tacky molten mass, further heating it get decomposed. Some polymers
decomposed directly by heating.
2.3.
Elastomers or Rubbers:

An elastomer is a linear polymer which exhibits elasticity and other rubber-like properties.
Rubbers are of two types:
(i) Natural rubber, and
(ii) Synthetic rubber.
2.3.1.
Natural rubber:
Natural rubber is obtained in the form of latex from rubber trees (Hevea brasiliensis). The latex
normally contains 30-60% rubber. It can be used, as such, in the latex form or the solid rubber
can be coagulated from the latex using 1% acetic acid solution. Natural rubber is a highly soft
and elastic material. Natural rubber is a polymerized form of isoprene (2-Methyl-1,3-butadiene):
Isoprene is synthesized from propylene, as follows:
Polymerization of isoprene yields polymers containing varying degrees of cis-1,4- and trans-1, 4
as well as 1, 2 or 3, 4-vinyl units in the molecule, depending upon the initiator and the solvent
systems employed. Under controlled conditions, polyisoprene containing up to 96% cisconfiguration can be obtained by using a lithium alkyl initiator and anhydrous oxygen free
aliphatic hydrocarbon solvents.
2.3.1.1.
Gutta Percha:
It is obtained from the mature leaves of dichopsis gutta and palagum gutta trees. Gutta percha
may be recovered by solvent extraction, when insoluble resins and gums are separated.
Alternatively the mature leaves are ground carefully; treated with water at about 70C for half
an hour and then poured into cold water. When gutta percha floats on water surface and is
removed. The structure of gutta is as follows:
Both the cis- as well as trans-varieties occur in nature as natural rubber and gutta-percha,
respectively. Natural rubber is a highly soft and elastic material. It is soluble in carbon
disulphide and petrol. Whereas, Gutta-percha is a hard thermoplastic solid and dissolves in
petrol only on heating and get separated from solution when cooled. Structurally, gutta-percha
is trans-polyisoprene; whereas natural rubber is cis-polyisoprene.
2.3.1.2.
Vulcanization of rubber:
Natural rubber becomes soft at high temperature (>335 K) and brittle at low temperatures (<283
K) and shows high water absorption capacity. It is soluble in non-polar solvents and is nonresistant to attack by oxidizing agents. To improve upon these physical properties, a process,
called vulcanization is carried out. This process consists of heating a mixture of raw rubber with
sulphur and an appropriate additive at a temperature range between 373 K to 415 K. On
vulcanization, sulphur forms cross links at the reactive sites of double bonds and thus the
rubber gets stiffened. In the manufacture of tyre rubber, 5% of sulphur is used as a crosslinking
agent. The probable structures of vulcanized rubber molecules are depicted below:
2.3.2.
Synthetic Rubbers:
It is also known as artificial rubber. Synthetic rubbers are of following types:

a. Styrene rubber (GR-S or Buna-S)
b. Nitrile rubber (GR-A or Buna-N)
c. Neoprene (GR-M)
d. Butyl rubber (GR-I)
e. Polysulphide rubber (GR-P or Thiocol)
f.
Polyurethane rubber (isocyanate rubber)
g. Chlorosulphonated Polyethylene rubber (Haplon)

h. Silicone rubber.
2.3.2.1.
Styrene Rubber (Buna-S):
Styrene butadiene rubber (SBR) is prepared by the copolymerization of butadiene (75%) and
styrene (25%) in an emulsion system at 50C in the presences of catalyst such as cumene
hydroperoxide. SBR is also known as Buna-S or GR-S. Styrene rubber have high abrasion
resistance, high load bearing capacity, low oxidation resistance, swells in oil and solvents, like
natural rubber SBR also vulcanized and produce cold rubber, which has greater tensile strength
and greater abrasion resistance.
SBR is used in motor tyres, shoes soles, footwear components, insulation of wire and cables,
carpet backing, gaskets, adhesives, etc.
2.3.2.2.
Nitrile Rubber (Buna-N/NBR):
It is a copolymer of acrylonitrile and butadiene. It is prepared by the copolymerization of

acrylonitrile and butadiene in emulsion systems.
Nitrile rubber (GR-A) has low swelling, low solubility, goods tensile strength and abrasion
resistance even after imersion in gasoline or oils. It has good heat resistance. It is used in fuel
tanks, gasoline hoses, as an adhesive and in the form of latex for impregnating paper, teather
and textiles.
2.3.2.3.
Neoprene (GR-M):
Neoprene, also known as polychloroprene. It is prepared by the free radical polymerization of

chloroprene (2-chloro-l, 3-butadiene) in an emulsion system.

Neoprene can be vulcanized to a considerable extent by heat alone. Its physical properties are
enhanced by compounding it with metallic oxides, such as ZnO or MgO. They have a higher oil
resistance than many rubbers including nitrile rubbers. Due to the Trans-1,4-structure, it is
therefore, an easily crystallisable elastomer. The vulcanized products are found to have
excellent tensile strength.
This elastomer is principally used for providing oil resistant insulation coatings to wires and
cables and for producing shoe soles, solid tyres, gloves and industrial hoses, tubing for carrying
corrosive gases and oils.
2.3.2.4.
Butyl Rubber (GR-I):
Butyl rubber, also known as polyisobutylene, is prepared by the copolymerization of isobutene

with isoprene in methylchloride as solvent.
Butyl rubber is amorphous under normal conditions but gets crystallized on stretching. It has
excellent resistance to heat, abrasion, ageing, chemicals (such as H2SO4, HNO3, HCl or HF),
polar solvents (like alcohol and acetone) but is soluble in hydrocarbon solvents like benzene.
Butyl rubber is used as inner tubes because its superior impermeability to gases. It is used for
wire and insulation. It is used in the production of tyres.
2.3.2.5.
Polysulphide Rubber (GR-P):
Polysulphide rubber, also known as Thiokol, is prepared by the reaction between sodium
polysulphide (Na2S) and ethylene dichloride (CH2ClCH2Cl).
Thiokols are those elastomers in which sulphur forms a part of the polymer chain. It has
extremely good resistance to mineral oils, fuel oxygen, ozone and sunlight. It is also
impermeable to gases. It cannot be vulcanized and hence does not form hard rubber. It has poor
strength and abrasion resistance.

Polysulphide rubbers are mainly used to make sealants, gaskets, balloons, fabric coatings and
gasoline hoses. Polysulphides form excellent fuel material and, upon mixing with inorganic
oxidisers such as ammonium perchlorate, they become solid propellants for rockets.
2.3.3.
Diene polymerization: 1,2- and 1,4- addition:
When there are unsaturated sites along a polymer chain, several different isomeric forms are
possible. 1,3-butadiene can be polymerized to give 1,2-poly(1,3-butadiene) or either of two
geometric isomers of 1,4-poly(1,3-butadiene). The numbers preceding the poly prefix designate
the first and last carbon atoms of the backbone repeating unit. 1,2-poly(1,3-butadiene) has a
vinyl-type structure, where the substituent group (ethene) contains an unsaturated site; therefore,
this geometric isomer can be atactic, syndiotactic, or isotactic. In the case of the commercially
more important 1,4-poly(1,3-butadiene), all four carbons in the repeating unit lie along the chain.
Carbons 1 and 4 can lie either on the same side of the central double bond (i.e., cisconfiguration) or on the opposite side (i.e., trans-configuration). The structure of polybutadiene
used in SBR rubber (i.e., a copolymer of styrene and butadiene) is principally the trans-1,4
isomer
2.3.3.1.
Polymerization of isoprene:
Polyisoprene, polymer of isoprene (C5H8) that is the primary chemical constituent of natural
rubber, resins balata and gutta-percha, and of the synthetic equivalents of these materials.
Depending on its molecular structure, polyisoprene can be a resilient, elastic polymer
(elastomer), as in the case of natural rubber and isoprene rubber, or a tough, leathery resin, as in
the case of natural and synthetic balata or gutta-percha.
The chemical structure of isoprene can be represented as CH2=C(CH3)CH=CH2. As the
repeating units of polyisoprene, the four isomers have the following structures:

Isoprene has a conjugated diene moiety, and its polymerization can provide various isomeric
polymers (cis-1,4-; trans-1,4-; iso-, syndio-, or atactic 3,4-), depending upon how the C-C double
bonds react. Therefore, it is critical to control the regio- and stereospecificities, in addition to
molecular weight in order to obtain a high-quality polyisoprene having desirable properties.
Of these four isomers, the most important are the cis-1,4 polymer and the trans-1,4 polymer.
Isoprene rubber (IR) is manufactured by the polymerization of synthetic isoprene, which is
obtained from the thermal cracking of the naphtha fraction of petroleum. Polymerization is
conducted in solution, using both anionic and Ziegler-Natta catalysts. The product is at most 98
percent cis-1,4 polyisoprene, and its structure is not as regular as natural rubber in other
respects.
Unlike the cis-1,4 polymer, however, the trans-1,4 polymer is highly crystalline, so balata and
gutta-percha are tough, hard, and leathery materials properties that led in the 19th century to
their use as sheathings for underwater cables and golf balls. The trans-1,4 polymer can also be
synthesized with Ziegler-Natta catalysts, yielding a synthetic balata of similar properties that
also is employed in golf-ball covers as well as in orthopedic devices such as splints and braces.

2.3.4.
1,3-Butadiene-styrene copolymer:
It is a type of polymerization reaction in which a mixture of more than one monomeric species
is allowed to polymerize and form a polymer called copolymer. Copolymer contains multiple
units of each monomer. For example: 1, 3-Butadiene and styrene can undergo copolymerization
to form butadiene styrene copolymer.
Styrene-butadiene rubber is prepared from the free-radical copolymerization of one part by

weight of styrene and three parts by weight of 1,3-butadiene. The butadiene is incorporated by
both 1,4-addition (80%) and 1,2-addition (20%). The configuration around the double bond of
the 1,4-adduct is about 80% trans. The product is a random copolymer.
2.4.
Stereochemistry of polymers:
To discussing the shape of polymeric molecules, one must distinguish carefully between the
configuration and confirmations. Configurations of molecules are sterric arrangement which are
symmetrically related to one another and can not change from one to another without breaking
the chemical bond. e.g.:- Cis- and trans- isomers of unsaturated compounds, cyclopropanes
derivatives, and D- and L- configurations of a molecules containing asymmetrical carbon atoms
or other centers of chirality.
The confirmations are sterric arrangements that can occurs through rotations about the single
bonds, and are due the fact that certain orientations have lower energies than the others. e.g.:Gauche and trans configurations of -substituted paraffines and two forms of cyclohexane.

The conformations in macromolecules in both solid and solution state is observed due to
specific short range and long range interactions between different regions with in the molecules.
Such effect gives symmetric arrangement otherwise it is coil such as staggered forms, etc. the
possibilities of intramolecular interactions are depends on the basic configuration of monomer
molecule/molecules.
e.g.:- The conformation is determined by hydrogen bonding is the -helical structure of
polypeptides discovered by Pauli and Carey in 1951. But some polypeptides does not having
the -helical structure due to sterric repulsion, electrostatic interactions or other reasons.
In some polymer (protic) molecules, some part of molecules is helical whereas other parts form
a random coil.
The macromolecules are synthesized by Zieglar-Natta synthesis having predetermined
stereochemical configurations. e.g.:- Synthesis of natural rubber (a product of the Hevea
brasiliensis). Rubber is poly-cis-isoprene. A different type of tree e.g.:- Palaguium, oblongifolia,
produces gutta-percha a plastic substance but not an elastomer which has the structure of polytrans-isoprene. All the synthesis gives mixture of poly-cis and poly-trans isoprene upto 1955 by
free radical mechanism. But by using Ziegler-Natta catalyst, stereospecific molecules are
synthesized.
Another type of stereoisomerism in polymers are observed due to presence of asymmetric or
pseudo-asymmetric carbon atoms. e.g.:- In polybutadiene.
-CH2-CH=CH-CH2-
If substituent is present at any CH2- carbon atom, it becomes asymmetric in nature. Therefore,
it is classified into a three different classes according to the nature of substituent Isotactic,
Syndiotactic and Atactic (discussed above).
2.4.1.
Ziegler-Natta catalyst:
These are a special type of coordination catalysts, comprising two components, which are
generally referred to as the catalyst and the co-catalyst. The catalyst component consists of
halides of IV-VIII group elements having transition valence and the co-catalysts are organo-

metallic compound such as alkyls, aryls and hydrides of group I-IV metals (Zeigler-Nata
Catalysts). Although there are organo aluminium compounds such as triethyl aluminium
(AlEt3) or diethyl aluminium chloride (AlEt2Cl) in combination with titanium chloridesboth
tri and tetra (TiCl3 and TiCl4)are, by far, the most commonly used.
Aluminium alkyls act as the electron acceptor whereas the electron donor is titanium halides
and the combination, therefore, readily forms coordination complexes. The complex formed is
insoluble in the solvent and is, hence, heterogeneous in nature. Many structures have been
proposed for these complexes are:
The active centres, from where the polymer chain growth propagates are formed at the surface
of the solid phase of the catalyst complex, and the monomer is complexed with the metal ion of
the active centre before its insertion into the growing chain.
The complex formed, now acts as the active centre. The monomers then attached towards the
TiC bond (C from the alkyl group R) in the active centre, when it forms a -complex with the
Ti ion.
The bonds between R and Ti opens up producing an electron deficient Ti and a carbanion at R.
The Ti ion attracts the -electrons pair or the monomer and forms -bond. This transition state
now gives rise to the chain growth at the metal carbon bond, regenerating the active centre:
Repeating the whole sequence, with the addition of second monomer molecule, we will get the
structure of the resultant chain growth as:
The five coordinated titanium ions on the surface of the catalyst is assumed to have a vacant
orbitals as shown at 6 in the following structure:
After the chemisorption of aluminium alkyl on the TiCl3 crystal, Ti3+ is alkylated by an exchange
mechanism, as follows:
Once the active catalyst is formed, the monomer is attached towards the vacant orbital which
then forms a transition complex with the Ti.
The transition state quickly gives rise to the growth of the polymer chain by the monomeric
insertion at the Ti-Et bond.
2.5.
Preparation and uses of polymers:
2.5.1.
Addition polymers:
2.5.1.1.
Polyethylene:
It was synthesized from ethylene.
There are two types of polythene as given below:

(i) Low density polythene: It is obtained by the polymerization of ethene under high pressure of
1000 to 2000 atmospheres at a temperature of 350K to 570K in the presence of traces of dioxygen
or a peroxide initiator (catalyst). The low density polythene (LDP) obtained through the free
radical addition and H-atom abstraction has highly branched structure. Low density polythene
is chemically inert and tough but flexible and a poor conductor of electricity. Hence, it is used in
the insulation of electricity carrying wires and manufacture of squeeze bottles, toys and flexible
pipes.
High density polythene: It is formed when addition polymerization of ethene takes place in a
hydrocarbon solvent in the presence of a catalyst such as triethylaluminium and titanium
tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and under a pressure of
6-7 atmospheres. High density polythene (HDP) thus produced, consists of linear molecules
and has a high density due to close packing. It is also chemically inert and more tough and
hard. It is used for manufacturing buckets, dustbins, bottles, pipes, etc.
2.5.1.2.
Polypropylene:
The monomer units are propylene molecules. It is generally manufactured by passing

propylene through n-hexane (inert solvent) containing Ziegler-Natta catalyst (a mixture of
triethyl aluminium and titanium chloride).
Polypropylene can be made with different tacticities. Most polypropylene we use is isotactic.
This means that all the methyl groups are on the same side of the chain. But sometimes we use
atactic polypropylene. Atactic means that the methyl groups are placed randomly on both sides
of the chain.
It is a strong, stain and impact-resistant, lightweight polymer with high heat resistance (melting
point=160 degrees C). Because of these properties, there are many uses for polypropylene; it is
used in containers (barrels, tanks, etc.), fabrics, sinks, ducts, and as a chemical resistant lining.
Polypropylene can sometimes use cross-linkage to bond to other polymers of polypropylene,
but it depends on its environment. Polypropylene is used for packing of textile material and
food, lining of bags, gramophone records, ropes, carpet fibres, etc. Polypropylene fibers are
resistant to solvents and other chemicals, to bacteriological growth and to abrasion.
2.5.1.3.
PVC:
The monomer units are vinyl chloride molecules. PVC is prepared by heating vinyl chloride in
an inert solvent in the presence of dibenzoyl peroxide.
PVC is a hard horny material. However, it can be made to acquire any degree of pliability by
the addition of a plasticizer. It is resistant to chemicals as well as heat. It is used for making rain
coats, hand bags, toys, hosepipes, gramophone records, electrical insulation and floor covering.
PVC fibers have medium tenacity, high elongation, and high degree of shrinkage (up to 40%) at
relatively low temperature (100C). They have virtually zero moisture regain and excellent

resistance to corrosive chemicals. PVC fibers are also photostable and intrinsically
nonflammable. Coloration is however a problem, and they are soluble in chlorinated
hydrocarbons and aromatic solvents, rendering them unsuitable for dry cleaning.
2.5.1.4.
Polystyrene:
Polystyrene, also known as polyvinyl benzene has the following structure:
Polystyrene is prepared by the free radical addition polymerization of styrene monomer

(dissolved in ethyl benzene) in the presence of benzoyl peroxide as a catalyst.
It is transparent, light, excellent moisture resistant. It can be nitrated and sulphonated by

fuming nitric acid and cone. H2SO4 respectively. It yields water soluble emulsion at 100C. It is
highly electric insulating, highly resistant to acids and goods and is chemical resistant. It has
low softening range (90-100C) and brittle. However, it has the unique property to transmitting
light through cured sections.
It is used in moulding of articles like comb, toys, buttons, buckels, radio and television parts,
refrigerator parts, battery cases, high frequency electric insulators, lenses, etc.
2.5.1.5.
Polyacrylonitrile:
Polyacrylonitrile (PAN), also known as polyvinyl cyanide, has the following structure:
Acrylonitrile can be made either by the direct catalytic addition of HCN to acetylene, or by the
addition of HCN to ethylene oxide to give ethylene cyanohydrin, followed by dehydration.
It can also be produced by ammonoxidation of propylene:
PAN has a remarkable resistance to heat up to around 220C and exhibits very good mechanical
properties. PAN is used to produce fibres known as PAN fibres. The copolymers of PAN with
butadiene (nitrile rubber) are a material of great industrial importance.
2.5.1.6.
Polyvinylalcohol:
Polyvinyl Alcohol is generally known as PVA. It is most commonly used in adhesive products
and for making other polymers. Unlike other vinyl polymers, polyvinyl alcohol is not
synthesised via polymerisation of the vinyl alcohol. They are produced by the polymerization of
the stable vinyl actetate monomer, where subsequent hydrolysis of polyvinyl acetate yields the
polyvinyl alcohol polymer.
PVA is pretty inert; does not react very much/easily. It has excellent film forming, emulsifying
and adhesive properties. It is resistant to oil, grease and solvent. PVA is fully degradable and is a
quick dissolver. The degradation of PVA is influenced by its crystalline structure and molecular
weight. It is used in water transfer printing process. It is used in eye drops and hard contact lens
solution as a lubricant. When eyes become dry due to a reduced production of mucin by the
conjunctiva, PVA reduces the surface tension of the tears and also has similar properties to the
mucin. The PVA fibres were used as reinforcement fibres in concrete. PVA is also used in PET
bottles as carbon layer because it helps to degrade when the bottle thrown away.
PVA fibers are normally water soluble. However, subsequent acetylation of the OH groups or
an after-treatment with formaldehyde renders PVA fibers resistant to boiling water. PVA fibers
have generally poor elastic recovery and wrinkle easily. They do not burn easily and have a
good chemical and biological stability. PVA fibers exist in a wide range of tenacity.
2.5.1.7.
Teflon:
Teflon is manufactured by heating tetrafluoroethene with a free radical or persulphate

catalyst at high pressures. It is chemically inert and resistant to attack by corrosive
reagents.
Teflon is a very tough material and is resistant towards heat, action of acids or bases. It is bad
conductor of electricity. Teflon is used for coating utensils to make them non-sticking, making
seals and gaskets which can with stand high pressures, insulation for high frequency electrical
installations.
2.5.2.
2.5.2.1.
Condensation polymers:
Polyesters:
Polysters have the structure with ester linkages as follows:
Where, R and R are aliphatic.

They are prepared by a polycondensation reaction between a dicarboxylic acid and a diol.
Aliphatic polysters were not of much industrial importance, mainly because of their low M.P.
e.g., the polyester with a degree of polymerization comparable to the commercial polyethylene
melts somewhere in the range of 50-80C, whereas the M.P. of polyethylene is around 120C.
This problem of low M.P. was overcome by introducing aromatic rings into the polyester chain.
This is evident from the following examples:
Polyester (e.g., terene or terelene or dacron) is prepared by the condensation polymerization of

dicarboxylic acid with dihydroxy alcohols.

Polyester is a good fibre forming material. This is due to the presence of numerous polar groups
and symmetrical structures. Such fibres have high stretch resistance. Polyethylene terephthalate
(PET) is highly resistant to mineral and organic acids but is less resistant to alkalis.
It is used in making synthetic fibres like terelene, dacron etc., for blending, with wool to provide
better crease and wrinkle resistance. It is also used as glass reinforcement material in safety
helmets, battery boxes, etc.
2.5.2.2.
Polyamides:
Polyamides are prepared by the melt polycondensation between dicarboxylic acids and
diamines. They have the general structure as follows:
Where, R is CH2- or Ar- group.

The aliphatic polyamides are generally known as nylons. There are different types of nylons
and are usually indicated by a numbering system. This number gives the number of carbon
atoms present in the monomer molecules. Aliphatic Nylon have M.P. of 250-300C.
1. Nylon-6,6: It is obtained by the polymerization of adipic acid with hexamethylene
diamine.
2. Nylon-6: It is prepared by the self condensation of -amino caproic acids.
3. Nylon-6:10: It is prepared by the reaction between hexamethylene diamine and sebacic

acid. The product formed is hexamethylene diammonium sebacate (Nylon-6:10) which
on further polymerization forms ribbon of Nylon-6:10. This is not used as a fibre. It is
used in brushes, bristles, sports equipment, etc.
4. Kelvar: It is a aromatic polyamide similar to nylons, but in benzene rings rather than
aliphatic chains linked to the amide groups CONH. It is prepared by the
condensation polymerization of terephthalic acid dichloride and 1,4-diaminobenzene.
Kelvar is exceptionally strong. This is due to the stronger intermolecular forces between
neighboring chains. It also has high heat stability. Kelvar is used in tyres, brakes, clutches
linging and other car parts, bullet proof vests, motor cycle helmets, aerospace and aircraft
industries.
2.5.2.3.
Polyurethanes:
Polyurethane is a polymer composed of a chain of organic units joined by carbamate (urethane)

links. Polyurethanes (PUs) properties depend both on the method of preparation and the
monomers used. In general, PUs can be prepared in one shot process or more commonly by a
two step method, especially for the case of segmented polyurethanes (SPUs). These materials
are thermoplastic block copolymers of the (AB)n type consisting of alternating sections of hard
segments, composed of a diisocyanate and soft segments, a low molecular weight diol chain
extender, generally composed of various types of polyols, also called macrodiols.
In the two steps method for SPU synthesis, a prepolymer is first obtained and then chain
extended. In the first step, an excess of the diisocyanate reacts with the soft segment polyol to
form the prepolymer. Here, the characteristic urethane linkages are formed through the reaction
between the isocyanate groups and the hydroxyl-terminated end groups of the polyol. In the
second step, the low molecular weight chain extender is used to link the prepolymer segments
yielding a high molecular weight polymer. During this stage, additional urethane functional
groups are formed when using a diol chain extender whereas ureas are produced when a
diamine is used.
The physical properties, as well as the chemical structure, of polyurethane depend on the
structure of the original reactants, in particular the alkyl groups in both isocyanide and diol.
The important properties of polyurethanes are Water repellent, autoahderente, light weight,
chemical resistance, fire resistance, etc. Most of the polyurethanes are thermosetting polymers
that do not melt when heated, thermoplastic polyurethanes are also available. Polyurethanes
can be found in liquid coatings and paints, tough elastomers such as roller blade wheels, rigid
insulation, soft flexible foam, elastic fibre or as an integral skin, rigid foams, chemical resistance
coatings, etc.
2.5.2.4.
Phenol-formaldehyde resin:
Phenol - formaldehyde polymers are the oldest synthetic polymers. These are obtained by the
condensation reaction of phenol with formaldehyde in the presence of either an acid or a base
catalyst.
The reaction starts with the initial formation of o-and/or p-hydroxymethylphenol derivatives,
which further react with phenol to form compounds having rings joined to each other through
CH2 groups. The initial product could be a linear product Novolac used in paints.
Novolac on heating with formaldehyde undergoes cross linking to form an infusible solid mass
called bakelite. It is used for making combs, phonograph records, electrical switches and
handles of various utensils.
These resins are hard, rigid, water resistant, heat resistant and can be mixed with wide range of
materials for the industrial and residential uses. The phenolic resins are chemical such as acids,
salts, organic solvents resistant, stable in harsh marine environment, low weight and high
strength, flammable resistance, less toxic, etc. They are easily attacked by alkalies due to
presence of free hydroxy groups. It possesses electrical insulating properties due to low thermal
conductivity.
The phenolic resins are used in adhesives, coatings, and molding compounds. They were used
to fabricate insulators, plugs, switches and also used as cation exchanger resin in water
softening.
2.5.2.5.
Epoxy resin:
Epoxy resins are defined as polymer molecules containing more than one epoxy groups. The
epoxy group also termed as oxirane or ethoxyline group. There are two main categories of
epoxy resins, namely the glycidyl epoxy and non-glycidyl epoxy resins. The glycidyl epoxies
are further classified as glycidyl ether, glycidyl ester and glycidyl amine. Glycidyl ether epoxies

such as, diglycidyl ether of bisphenol-A and novolac epoxy resins are most commonly used
epoxies.
By varying the relationship between bisphenol A and epichlorohydrin, various molecular
weights are obtained for the completed epoxy resin. A low molecular epoxy resin with a mean
molecular weight of 380 is fluid at room temperature, while an epoxy resin with a mean
molecular weight of 1000 is solid at room temperature. The low molecular can be handled
without solvent additives, which evaporate and are therefore used for casting, thick coatings,
gap-filling glues, etc. The high molecular epoxy resins dissolved in organic solvents to be
manageable, which limit usage to paints and lacquers.
These resins are thermosetting polymers and are used as adhesives, high performance coatings,
potting and encapsulating materials. These resins have excellent electrical properties, low
shrinkage, good adhesion to many metals and resistance to moisture, thermal and mechanical
shock. The applications of epoxy resins were extended as electronic material and in the
aerospace industry by improving its flame and thermal resistance.
2.5.2.6.
Polycarbonates:
The polycarbonates are the polyester of phenol and carbonic acid. It was synthesized by the
condensation of diphenols in which the two OH groups are on separate aromatic rings such as
bisphenol A and aliphatic derivative of carbonic acid such as phosgene (COCl 2) or a carbonate
diester [CO(OR)2].
This is a polymer that combines transparency, lightness and strength with just enough
flexibility not to be brittle. It is resistant to water and many organic compounds. It is transparent

plastic so used for the manufacturing of different articles such as safety goggles, safety shields,
telephonic parts, etc.
2.6.
Recyclable polymers:
Plastics are usually disposed of in one of three ways: discarded, combusted, or recycled. Of the
three options, recycling is least implemented. Because the disposal or combustion of plastics
leads to detrimental health and environmental effects, short and long term solutions need to be
established. A potential short-term solution would be the development of new technology to
boost recycling rates. The current recycling system requires a labor-intensive sorting step which
contributes to the low amounts of plastic being recycled. Technology that eliminates the sorting
process could potentially increase recycling rates. However, because all plastics cannot be
recycled indefinitely, a long-term solution is also needed. The advancement of biopolymers that
will degrade faster than regular plastic polymers that end up in landfills would decrease
environmental pollution while providing compost for plant nutrition.
2.6.1.
Biodegradable polymers and their uses:
A large number of polymers are quite resistant to the environmental degradation processes and
are thus responsible for the accumulation of polymeric solid waste materials. These solid wastes
cause acute environmental problems and remain undegraded for quite a long time. In view of
the general awareness and concern for the problems created by the polymeric solid wastes,
certain new biodegradable synthetic polymers have been designed and developed.
Plastics derived from natural materials, such as cellulose, starch and hydroxycarboxylic acids
are more easily decomposed when exposed to oxygen, water, soil organisms and sunlight than
are most petroleum based polymers. The glycoside linkages in polysaccharides and the ester
groups in polyesters represent points of attack by the enzymes of microorganisms that facilitate
their decomposition. Such biodegradable materials can be composted, broken down and
returned to the earth as useful nutrients. The two natural polyesters that are finding increasing
use
as
replacements
polyhydroxyalkanoates
for
petroleum
(PHA),
the
based
latter
plastics
most
are
commonly
polylactide
as
(PLA)
copolymers
and
with
polyhydroxybutyrate (PHB). Structures for these polymers and their monomer precursors are
shown below.
1. Starch: It is polymer of glucose. It is a chief food reserve of plants.

2. Cellulose: It is also a polymer of glucose. It is a chief structural material of the plants.
Both starch and cellulose are made by plants from glucose produced during
photosynthesis.
3. Proteins: These are polymers of amino acids. They have generally 20 to 1000 amino acids
joined together in a highly organized arrangement. These are building blocks of animals
and constitute an essential part of our food.
4. Nucleic acids: These are polymers of various nucleotides. For example, RNA and DNA
are common nucleotides. These biopolymers are very essential for our life.
These polymers contain functional groups similar to the functional groups present in
biopolymers. Aliphatic polyesters are one of the important classes of biodegradable polymers.
Some important examples are given below:
a. Poly -hydroxybutyrateco--hydroxy valerate (PHBV):
It is obtained by the copolymerization of 3-hydroxybutanoic acid and 3-hydroxypentanoic acid.
PHBV is used in specialty packaging, orthopaedic devices and in controlled release of drugs.
PHBV undergoes bacterial degradation in the environment.
b. Nylon 2nylon 6:
It is an alternating polyamide copolymer of glycine (H2NCH2COOH) and amino caproic acid
[H2N-(CH2)5-COOH] and is biodegradable.
2.6.2.
Biomedical use of polymers:

Biomedical polymers are natural origins such as polysaccharides, protein and bacterial
polyesters. These polymers possesses some properties such as flexibility, resistance to
biochemical attack, biodegradable, non-toxic, highly porous, good biocompatibility, light
weight, available in a wide variety of composition, encouraging of cell attachment & growth,
and can be easily manufactured into products with the desired shape.
These polymers are classified as natural and synthetic polymers. The natural biopolymers were
derived from living creatures. E.g. Collagen, Cellulose, Alginates, Dextrans, Chitosan, etc.
Collagen was used in surgery, drug delivery, prostetic implants and tissue engineering of
multiple organs. The chitosan was used in the engineering of cartilage, nerve and liver tissue,
wound dressing and drug delivery devices. Alginate was used in liver, nerve, heart, cartilage
and tissue engineering.
The synthetic polymers having the properties such as biocompatibility, sterilizability, physical
property, and manufacturability. These polymers were used for medical disposable supplies,
prosthetic materials, dental materials, implants, dressings, polymeric drug delivery, and tissue
engineering products. E,g, polytetrafluoroethylene, polyethylene, polypropylene, poly (methyl
methacrylate), etc.
The synthetic polymers were classified as biostable, bioerodible, water soluble and others. The
biostable polymers should be physiological inert, strong, resistant to impact, stable chemically
& thermally and stable during the exposure to hydrolytic or oxidative conditions and used in
artificial organs blood pumps, blood vessel prostheses, heart valves, skeletal joints, kidney
prostheses. The bioerodible polymers will serve short term purpose in the body and then
decompose to small molecules that can be metabolized or excreted, sometimes with the
concurrent release of drug molecules. Most bioerodible polymers used as surgical sutures,
tissue in growth materials, or controlled release of drug. Water soluble polymers were used for
the improvement in the behavior of pharmaceuticals, used in synthetic blood substitutes as
viscosity
enhancers
or
as
oxygen
transport
macromolecules.
e.g.
silicon
rubber,
poly(tetrafluoroethylene), polyurethanes, epoxy resins, vinyl resins, vinyl polymers, nylon,

cellophane, PMMA, polycarbonate or cellulose fibers, etc.
2.7.
Additives to polymers:

Additives are combined with the basic resins and polymers to obtain the various properties: as
extenders, to facilitate their processing, and/or to produce wished colour and finish. Thousands
of chemicals and mixtures are used in production and are commercially available. The large
volume plastic additives are plasticizers, colorants and blowing agents. Flame retardants, heat
stabilizers and lubricants are also important. Under development are additive chemicals which
allow setting of the time span for use and degradation to the plastic product.
The most widely used additives may be divided into following classes:
Plasticizers
flame retardants/smoke suppressants
stabilizers: heat stabilizers, UV stabilizers/light absorbers
antioxidants
blowing/foaming agents
initiators
lubricants and flow control agents
antistatic agents
curing agents
colorants
fillers and reinforcements
solvents
optical brighteners
preservative materials, such as antifouling agent
2.7.1.
Plasticizers:
Plasticizers are usually high boiling organic liquids or low melting solids. Polymers are often
inherently rigid and brittle. Plasticizers are added to improve flexibility, softness and suitability
for different processing applications. Plasticizers are chemically and thermally stable; their
addition also enhances the stability and reduces the degradation of the host polymers. They are
of various chemical types, some being used in specified products only. Plasticized polymers can
be moulded, sprayed, and used in a coating in an uncured liquid form. Calendaring, extrusion
and moulding of the polymer melt are other methods used in processing. Polyvinyl chloride
accounts for about 80% of plasticizer production and use since it is especially suitable for

plasticizing. Plasticizers can also be applied to cellulose-based, polyvinyl acetate, urethanes and
acrylic formulations. The principal function of a plasticizer is to reduce the Tg of a polymer so as
to enhance its flexibility over expected temperatures of application.
Phthalates, such as di(2-ethylhexyl)phthalate, trimellitates, benzoates and terephthalates are
monomeric plasticizers and examples of the hundreds of different chemicals used as
plasticizers. Some polymeric plasticizers are high performance special products.
Coating is a special case in applying plasticizers. Plasticizers are in a solution or latex emulsion
with resins to prevent the thin film of coating becoming brittle. The amount of the plasticizer in
formulations can vary considerably; 50% by weight is used in some applications. Phthalate,
terephthalate, adipate, and phosphate esters are generally referred to as monomeric plasticizers.
2.7.2.
Stabilizers:
Stabilizers are needed to protect the structure of polymers and pigments against degradation
induced by physical conditions, such as heat and light, or chemical attacks, such as that of
atmospheric oxygen. Heat stabilizers can be organotin compounds, metal salts, epoxies,
pentavalent phosphorous compounds, and their mixtures. Chemicals that absorb ultraviolet
light include benzophenones, benzotriazoles, salicylates, acrylates, and organonickel
compounds.
Heat stabilizers: PVC polymers and co-polymers have poor resistance to heat, which is a major
disadvantage. The stabilizers used in PVC formulations are organic compounds of metals.
Commonly used heat stabilizers are tin compounds, such as dibutyltin bis(alkyl maleate) and
dibutyltin (isooctyl mercaptoacetate), used for plastics which come into contact with food
products, and lead compounds, such as dibasic lead stearate and dibasic lead phosphite. In
some countries the use of stabilizers containing cadmium are banned because of their toxicity.
UV stabilizers: Hindered amine light stabilizers (HALS) can be used in pigmented polymers
and are specifically suitable for the protection of white or blue PP fibres. They also act as
antioxidants. A high concentration of titanium dioxide can also serve as a stabilizer against the
degrading effects of UV light.
2.7.3.
Fillers:

The need to meet exacting end-use requirements and at the same time reduce costs is
stimulating a broad spectrum of product development involving the use of fillers and
reinforcements to upgrade product performance rather than the development of new and
usually more expensive resins. For example, because of their advantageous light weight, high
strength, fatigue life, and corrosion resistance, structural composites have been used
successfully and admirably in aircraft and in numerous industrial and consumer applications in
place of conventional materials like metals. Polymers, thermoplastics, and thermosets can be
reinforced to produce quite frequently a completely new kind of structural materials.
Different types of fillers are employed in resin formulations; the most common are calcium
carbonate, talc, silica, wollastonite, clay, calcium sulfate, mica, glass structures, and alumina
trihydrate. Fillers serve a number of purposes. Inert materials like wood flour, clay, and talc
serve to reduce resin costs and, to a certain extent, improve processability and heat dissipation
in thermosetting resins. Both alumina trihydrate and talc improve flame retardance. Mica is
used to modify the electrical and heat-insulating properties of a polymer. Parts molded from
composites containing phlogopite mica as a reinforcement exhibit little or no warpage on
demolding or subjection to elevated temperature. A variety of fillers, e.g., particulate fillers like
carbon black, aluminum flakes, and metal or metal-coated fibers may be used to reduce mold
shrinkage as well as to produce statically conductive polymers, shielding of electromagnetic
interference/radio frequency interference (EMI/FMI).
Particulate fillers such as carbon black or silica are used as reinforcing fillers to improve the
strength and abrasion resistance of commercial elastomers. Fibers such as asbestos, glass,
carbon, cellulosics, and aramid are used principally to improve some mechanical
property/properties such as modulus, tensile strength, tear strength, abrasion resistance,
notched impact strength, and fatigue strength as well as enhance the heat-deflection
temperature. Fibers are available in a variety of forms. For example, carbon fibers are obtained
from the pyrolysis of organic materials such as polyacrylonitrile (PAN) and rayon for long
fibers and pitch for short fibers.
The most important form of filler is E-glass, which is used typically to reinforce thermoset
polyester and epoxy resins. E-glass is boroaluminosilicate glass having low alkalimetal context
and containing small percentages of calcia (CaO) and magnesia (MgO). For special applications

such as in the manufacture of aerospace materials, fibers of boron, Kevlar, PBT, and especially
carbon are generally preferred.

Polymer Chemistry

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Polymer Chemistry

Hochgeladen von

Copyright:

Verfügbare Formate

A notes of Dr.

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

Rigidity (moulded phenolics).

Magnetic properties (barium ferrite filled vinyl plastisols), etc.

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

The major alternative type of polymer is formed by condensation polymerization in which a

butadiene (CH2=CHCH=CH2) and styrene (C6H5CH=CH2) is an example of copolymer.

Structural Features of a Polymer:

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

-(CH2 - CH2)n Polyethylene

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

Natural rubber, natural silk, cellulose,

proteins, starch etc.

Semisynthetic (Man made)

Hydrogenated, halogenated and cyclo

Synthetic (Man made)

styrene, polybutadiene, nylon polyamides,

amino resins, epoxy resins etc.

Thermoplastics (they soften or Polyethylene,

polyester [poly(ethylene terephthalate)],

of heating and cooling and etc.

heating, but fast undergo unsaturated polyesters.

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

Polyethylene and other polyolefins,

epoxy resins etc.

Linear (having no branches)

High density polyethylene (HDPE),

Branched (having branches)

higher poly (-olefins), phenolic resoles

amino (urea / melamine-formaldehyde)

unsaturated polyester resin etc.

Natural rubber, (1, 4 cis poly isoprene)

synthetic rubbers (polybutadiene, SBR,

nitrile rubber, polychloroprene rubber,

rubbers, silicone rubbers etc.)

pressure, aided by heat)

(vinylchloride), nylon polyamides linear

Cotton (cellulose), natural silk, artificial

terephthalate) fiber, nylon polyamide

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

Poly (-olefins) and all vinyl and related

Atactic (stereo irregular)

(crystallinity, > 50%)

nylon polyamides, polyoxymethylene

Polybutene, cellulosics (cellulose esters

(rayons) particularly if stretched), Gutta

Natural rubber and most synthetic

(Crystallinity < 25%)

rubbers, N-alkylated(>15% alkylation)

Thermal response: Thermoplastic and Thermosetting Polymers:

Edited by Dr. Bapu R Thorat

A notes of Dr. Bapu R Thorat

materials. Do not melt on heating.

Molten polymer can be moulded in desired Cross-linking is usually developed at the

time of moulding where they harden

Depending on the structure of polymers: