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Subject Name: Engineering Chemistry
Subject Code: BT-101
Semester: 1st
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UNIT IV: POLYMERS
POLYMERS
The word 'polymer' is derived from the classical Greek words poly meaning 'many' and ‗meres‘ meaning
'parts'. Simply stated, a polymer is a molecular compound with high molecular mass, ranging into
thousands and millions of gram. It is composed of a large number of repeating units of identical structure
called monomers. For example, polythene is a polymer formed by linking together of a large number of
ethene molecules.
nCH2 = CH2 (CH2-CH2)n

Ethene Polyethene
(Monomer) (Polymer)
Certain polymers, such as proteins, cellulose, and silk are found in nature and hence are called natural
polymers, whereas, a number of polymers are produced by synthetic routes and are called synthetic
polymers. In some cases, naturally occurring polymers can also be prepared synthetically. For e.g. rubber,
which is also known as polyisoprene?
Both natural and synthetic polymers impinge on every aspect of our existence. The idea is often
expressed that we live in "a plastic age". The range of polymeric materials is so wide that they have found
applications in practically every branch of industry. About 80% of today's chemists, including
biochemists, work with polymers.
The number of repeating; units in a chain formed in a polymer, is known as the "degree of
polymerization". Polymers with high degree of polymerization are termed as "high polymers" and those
with low degree of polymerization are called oilgopolymers.
CLASSIFICATION OF POLYMERS
Synthetic polymers have been classified into various groups, in various manners.
CLASSIFICATION OF POLYMERS
Homopolymer
(i) On the basis of Chemical structure
Copolymer
Linear
(ii) On the basis of Polymeric structure Branched
Crosslinked
Block copolymers
(iii) On the basis of arrangement of monomers
Graft copolymers
Isotactic polymer
(iv) On the basis of tacticity Syndiotactic polymer
Atactic polymer
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UNIT IV: POLYMERS
Thermoplastic
(v) On the basis of thermal behavior
Thermosets
Plastic
(vi) On the basis of ultimate form Elastomers
Fibers
(i) On the basis of the chemical structure of their backbone, polymers are of two types:
Homopolymer: If a polymer consists of identical monomer, the polymer is termed as
homopolymer.
Copolymer: If the polymer is a mixture of more than one type of monomer it is termed as
copolymer.
(ii) On the basis of their polymeric structures, the polymers can be classified as linear,
branched or Crosslinked.
(iii) Depending upon the arrangement of the monomers in the case of copolymers, the
polymers are divided into block copolymers and graft copolymers.
Block Copolymers: Linear polymers in which the identical monomeric units occur in
relatively long sequences are called block co-polymers.
-A–A–A–B–B–B–A–A–A–B–B–B-
Block Copolymer
Graft Copolymers: Graft copolymers are branched copolymers in which the backbone is
formed from one type of monomer and branches are formed of the other, i.e., the monomer
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segments on the branches and backbone are not the same.
(iv) Depending upon the orientation of monomer units in a polymer molecule: With respect to
the main chain the polymers are classified as:
Isotactic polymer: If the side groups of the monomers lie on the same side of the chain, it
is called an ―isotactic‖ polymer.
Syndiotactic polymer: If the side groups are arranged in an alternate fashion, it is called
syndiotactic polymer.
Atactic polymer: If the side groups are arranged in irregular fashion on randomly around
the main chain, it is called atactic polymer.
(v) If the main chain is composed of the atoms of the same specie, the polymer is called
homochain and if the main chain is made up of different atoms then they are called
heterochain polymers.
~C–C–C–C–C-~
~C–C–O–C–O–C ~
(vi) According to their behavior on heating, the polymers are divided into two groups.
Thermoplastics: Those polymers, which soften on heating and become plastic so that they
can be converted to any shape by moulding, are known as thermoplastics.
Thermosets: Those polymers which change irreversibly into hard and rigid materials on
heating and cannot be reshaped, once they are set are called thermosets. They form
infusible and insoluble mass on heating.
Plastics: All the synthetic polymers (other than elastomers) are usually referred to as
plastics. The polymers, which are shaped into hard and tough utility articles by the application
of heat and pressure, are called plastics. At some stage of manufacture, these are in plastic
condition (Plasticity is the property by virtue of which a material undergoes permanent
deformation under stress).
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Elastomers: The polymers which are capable of being stretched rapidly at least 150
percent of their original length without breaking and return to their original shape on
release of stress is known as elastomers. Synthetic rubbers constitute important of this
group.
FUNCTIONALITY
The functionality of a molecule is the number of reactive sites it has. For a substance to act as a
monomer, it must have two reactive sites. In other words, they should have functionality of at
least two. A compound assumes functionality because of the presence of reactive functional
groups present in a compound defines its functionality. For example –
Compound Chemical Formula Functionality

Acetic Acid CH3 COOH 1
Molonic acid HOOC CH2 COOH 2
Ethyl alcohol C2 H5 OH 1
Ethylene glycol HOCH2 CH2 OH 2
Lactic acid CH3 CH (OH) COOH 2
Tartaric acid HOOC (CHOH)2 COOH 4
There are some other compounds in which the presence of easily replaceable hydrogen
atoms imparts functionality. For example, phenol, it has got –OH groups as a functional group
but can also undergo substitution reaction at these three sites replacing its three hydrogen
atoms. For example, in reaction (i), phenol exhibits mono functionality and in reaction (ii), it
exhibits a functionality of three.
Depending on the functionality of the monomers used, we get linear, branched or three
dimensional cross-linked polymers.
TYPES OF POLYMERIZATION
There are two types of polymerization processes:
1. Addition Polymerization,
2. Condensation Polymerization.
Addition Polymerization
Addition polymerization is characterized by self-addition of the monomer molecules to each
other, without the loss of any material. The product is an exact multiple of the original
monomeric molecule.
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MECHANISM OF ADDITION POLYMERIZATION

Addition polymerization is a typical chain reaction and consists of three important steps:
(i) Initiation of the formation of active centers.
A A* (Excited monomer)
(ii) Chain propagation

A* + A A – A*
A - A* + A A- A- A* (Activated growing chain)
(iii) Chain termination or removal of active centre.

-~- A — A — A* -~- A — A — A (Inactivated chain)
The process of addition polymerization can be brought about by three methods:
1.Free radical mechanism
2.Ionic mechanism (Anionic and Cationic)
3.Coordination mechanism
The three types of mechanisms for addition polymerization, depending upon the active centres
formed, are discussed below.
1. Free Radical Addition Polymerization: The free radical addition polymerization involves
the formation of free radicals in the initiation step, which can be produced by
decomposition of compounds called initiators. The free radical polymerization has three
principal steps:
(i) Initiation: Initiation in a free radical polymerization consists of two steps. The first is the
'generation of the free radical species, followed by the second step which involves the
addition of a single monomer molecule to the free radical.
The generation of free radical takes place as a result of homolytic dissociation of an
initiator, which may take place in the presence of heat energy, light energy or catalysts.
A number of low molecular weight compounds, comprising mainly of azo compounds,
peroxides, hydroperoxides, peracids and peresters are useful as initiators. An important
example of a free radical initiator is benzoyl peroxide which dissociates as:
O O O
|| || ||
C6H5C — O— O—C —C6H5 ► 2C6H5 —C —O
In general, the dissociation of the initiator (R-R) to form free radical specie can be
represented as
R–R 2R*
(Initiator) (Free radicals)
In the second step of initiation, the free radical so formed gets attached to the monomer
molecule (M) to form the chain initiating species
R* + CH2 = CH2 R-CH2-CH2
(free radical) Monomer
(ii) Propagation: In the next step, additional monomer units are added to the initiated
monomer species, as
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In this reaction the original growing chain is terminated whereas the new chain gets initiated by
the solvent free radical, hence this is called termination by chain transfer.
Certain chemical compounds, which are capable of inhibiting or completely stopping the chain
growth process, are called radical inhibitors. Phenolic compounds are widely used as
inhibitors, because phenolic hydrogen can be easily abstracted by the polymer chain. The
phenolic free radical so formed is highly stabilized and no further reaction is possible.
Hydroquinone is often added as inhibitor.
Polythene, polypropylene, styrene etc. are some of the polymers that can prepare by tree
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radical polymerization. Branching and cross linking during the free-radical addition
polymerization.
2. Ionic Addition Polymerization: Ionic polymerization follow the same basic steps as free-
radical addition polymerization i.e. initiation, propagation and termination, in this
process, the initiation step involves the formation of carbonium ion or the carbanion as
the active site and hence the polymerization can be termed as cationic or anionic
polymerization respectively.
(i) Cationic Polymerization
Cationic polymerization takes place in the presence of catalyst that is regenerated at the
end of polymerization (in contrast to free radical and anionic polymerization where the
catalyst added become incorporated into the terminated Dolymer chain)
Polymerization of vinyl monomers with an electron-donating group (such as – OC2H5 -
OCH3 - C6H5 etc.) may take place by a cationic mechanism which involves the
following steps.
Initiation: This step involves the formation of a carbonium ion by the attack of a proton
on the monomer. Any strong Lewis acid like BF3, A1Cl3 etc can be used as a catalyst.
In this case a cocatlyst like water is required to provide the proton source.
H+ is the initiator and [F3 BOH]- is the counter ion.

The H+ now attacks the n electron of the monomer and forms the carbonium ion. The
counter ion [F3 BOH]- anion faces the growing chain end.
Propagation: The propagation reaction involves the addition of monomer units and
simultaneous transfer of the charge to the newly added monomer unit.
More and more units are added up and the chain keeps on growing. The electron pair of
the adding monomer units are pulled in a direction opposite to the growth of the chain and the
positive charge keeps on moving in the direction of the chain growth. The counter ion [BF3
OH]-, moves along the positive charge all the time.
Termination: Termination takes place when the growing polymer chain having C+ collides with
an anion, which may be added deliberately or with the counter ion. The possible reactions may
be:
(a) Donation of a portion to the counter by the growing polymer chain. This results in the
formation of a double bond at the end of growing polymer molecule.
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In this case also the regeneration of the initiator takes place.

Examples of the monomers that can undergo cationic polymerization are isobutylene,
styrene methyl styrene and many vinyl others. Cationic
More and more styrene molecules are added and the charge is simultaneously
transferred to the newly added monomer unit.
Termination: Termination takes places by donation of a proton to the counter ion by
growing polymer chain forming a double bond
(ii) Anionic Polymerization

Anionic polymerization involves the formation of the carbanion in the initiation step.
Polymerization of vinyl monomers with an electron withdrawing group can proceed by an
anionic mechanism, involving the following steps:
Initiation: The initiators or the catalysts used in anionic addition polymerization are strong
bases such as organo alkali compounds (alkyl or aryl derivatives of alkali metals) like n-butyl
lithium, ethyl sodium etc. Alkali metal amides, hydroxides etc. can also be used.
The electron pair in this case is pushed to the end of the molecule forming the
carbanion. Li+ is the counter ion.
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Propagation: The carbanion formed, propagates the chain growth by attacking the second
monomer PAI unit, pushing its electron pair further away to the end and forming a sigma bond
with the new monomer unit.
In the case of anionic polymerization the movement of the PAI electrons is towards the
direction of the chain growth (in cationic polymerization, the movement of the PAI electrons is
opposite to the chain growth).
Termination: The termination in anionic polymerization is not a spontaneous process. If the
starting reagents are pure and no impurities are present, propagation can proceed indefinitely or
until all the monomer is consumed. Termination is generally accomplished by the transfer of
negative charge to a species which is not directly involved in the reaction. For example CO2,
methanol, water etc.
3. Coordination Polymerization: Polymerization reactions, taking place in the presence of

organometallic compounds as catalysts, are termed as coordination polymerizations.
Zeigler (1953) and Natta (1955) discovered that in the presence of a catalyst which is a
combination of a transition metal halide (like TiCl4 or TiCl3) with organo-metallic compounds
(like triethyl aluminium), stereoregular polymers can be prepared. The combination is often
referred to as, ZeigherNatta catalyst. The commonly used Zeigler-Natta is trhethylaluminium
in combination with titanium trichloride.
In the formation of the monomer catalyst complex, a co-ordinate bond is involved
between a carbon atom of a monomer and metal atom of the catalyst that is why, this type of
polymerization is known as coordination polymerization. The co-ordinate metal-carbon bond
formed in the monomer-catalyst complex acts as an active center from where propagation
starts.
Mechanism of coordination polymerization can be illustrated as follows:
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Coordination polymerization is used to prepare sterospecific polypropylene; polydiene etc.

polypropylene of nearly 90% isotacticity can be prepared. The exact mechanism of
coordination polymerization is still unclear.
Condensation Polymerization
Condensation polymerization is brought about by monomers containing two or more reactive
functional groups with the elimination of small molecules like O, HCl etc. For example, It is
seen from the above reaction that the polymer formed still contains both the reactive functional
groups at its chain ends and hence, is ‗active‘ and not ‗dead‘. In the above example, the
different type of reactive functional groups, viz. –NH2 and -COOH are present on two different
monomers. In some cases, both the reactive groups may be present on the same monomer and
hence lead to self-condensation reaction. For example, polycondensation of amino acids.
Some polycondensation reactions leading to different types of polymers are:
(i) Polycondensation of dihydric alcohols and dicarbodxylic acids leads to the
formation of polyesters.
(ii) Polycondensation of dicarboxylic acids and diamines to give polyamides.
(iii) Polycondensation of dihydric alcohols and methyl esters of dicarboxylic acids to
give polyesters.
(iv) Self condensation of –hydrogen acids yields polyesters.
(v) Self condensation of amides to form polyamides.
(vi) Polycondensation of bisphenol A and phosgene to form polycarbonate.
COPOLYMERIZATION
Commonly available nature and synthetic polymer suffer from many disadvantages and
therefore cannot be used for special purposes. However, it is possible to modify a number of
natural and commercially available synthetic polymers to give products which can be utilized
for performing desired functions.
Copolymerization is the most general and powerful method of affecting modification in
polymers and is widely used in the production of commercial polymers. It provides a technique
to combine the properties of two or more different polymers into a single polymer.
Copolymerization can be defined as any process whereby two or more monomers are
copolymerized to form a single polymer. The resulting high molecular weight compound is
known as copolymer. For example, butadiene any styrene, copolymerize to form butadiene-
styrene rubber.
Depending upon the sequence in which different polymeric units are arranged, copolymers are
of following types:
(a) Random copolymers
(b) Alternating copolymers
(c) Block copolymers
(d) Graft copolymers
(a) Random copolymers: In random copolymers the two monomers A and B are
distributed randomly along the polymer chain.
nA + nB [A – A – B – B – A – B – A - A]n
(b) Alternating copolymers: In block copolymers, a sequence or block of one
monomer is followed by the block of the other monomer.
nA + nB [A – B – A – B – A – B – A]n
(c) Block copolymers: In block copolymers, a sequence or block of one monomer is
followed by the block of the other monomer.
nA + nB [A – A – A – B – B – B – A – A – A]
Block Block
(d) Graft copolymer: Graft copolymers are branched polymers and contain main chain
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or backbone consisting of one monomer and branches formed from the other
monomer:
nA + nB [A A A A A]n
B B
B B
B B
PLASTICS
As was discussed earlier, plastics area group of artificially synthesized materials, which can be
moulded into any desired form, when subjected to heat and pressure in the presence of a
catalyst.
The resins are the basic binding materials, which form the major part of the plastics and
determine the type of treatment needed in the moulding operations.
From engineering point of view there are two types of resins –
(i) Thermoplastic resins.
(ii) Thermosetting resins.
(i) Thermoplastics: Thermoplastics or resins soften on heating and become plastic sc that
they can be converted to any desired shape by moulding. On cooling, they become hard
and rigid but their hardness is a temporary property subject to change with increase or
decrease in temperature. In thermoplastic resins, the chemical structure or the molecular
weight are not changed during the heating or moulding operations, because the changes
involved are of physical nature. Only the secondary bonds between the individual
molecular chains are broken on heating which results in their softening. On cooling, these
secondary bonds are again formed and hence they become hard again. Some common
examples of thermoplastics are polyethene, polypropylene, polystyrene, polyvinyl
chloride, teflon, polyacrylonitrile etc.
Plasticizer: Sometimes, the substances called plasticizers are added to improve plasticity
and flexibility of the plastics. A variety of organic materials arc used as plasticizers
including non-drying vegetable oils, tributyl phosphate, triphenyl phosphate, triacetin
camphor, esters of oleic or stearic acid.
(ii) Thermosetting resins: Thermosetting resins are those, which upon heating, change
irreversibly into hard and rigid materials on heating. After cooling, if the set article is
again heated, it will not soften again. The thermosetting resins during moulding acquire
three-dimensional cross-linked structures with predominantly covalent bonds, which retain
their strength even on heating. Thus, the three dimensional network structure joined by
strong covalent bonds make the thermosetting resins harder, stronger and more brittle than
thermoplastic resins, if heating of a thermoset resin is prolonged, these undergo change in
chemical composition to give a hard, infusible and insoluble mass. Some common
examples include phenol formaldehyde, malamine formaldehyde, alkyds, epoxy resins etc.

UNIT IV: POLYMERS
Difference between Thermoplastics and Thermosetting Resins

Thermoplastic Thermosetting Resin
1. They are generally long chain linear polymers. They have three dimensional crosslinked network
structure joined by strong covalent bonds.
2. On heating, they soften readily because They do not soften on heating because cross links
secondary forces between the chain can be and strong covalent bonds retain their strength on
easily broken. heating. They can, however, be charged on strong
heating.
3. They can be softened, reshaped and even They can not be reshaped and reused because they
reused by reheating to a suitable temperature. do not soften on heating and retain their shape and
structure.
4. They are generally weak, soft and less brittle. They are usually hard, strong and more brittle.
5. They can be reclaimed from waste. They can not be reclaimed from waste.
6. They can dissolve in some organic solvents. They are insoluble almost in all organic solvents
because of the presence of cross linking and strong
covalent bonds.
COMMERCIALLY IMPORTANT THERMOPLASTICS

1. Polyethene: Ethylene, one of the most important petrochemicals, may be polymerized by a
number of methods to produce thermoplastic polymer, polyethene.
nCH2 = CH2 ( CH2 – CH2 )n

ethene Polyethene
The starting material (monomer) is obtained either by dehydration of alcohol or by the

cracking of petroleum. There are two varieties of polyethylenes, viz., low density polyethylene
(LDPE) and high density polyethylene (HDPE).
(a) LDPE : Low density polyethylene is prepared by polymerizing ethylene at high pressures
(1000-5000 atm) at a temperature of 2500 C in the presence of oxygen as a free radical
initiator. LDPE consists of highly branched structure, which does not allow the polymeric
chains to pack close together and hence results in low density (0.91 to 0.925 g/cm 3) of the
polymer.
Properties:
(i) Low-density polyethylene melts at 110-1250C and is only 40-50% crystalline.
(ii) It has low density (0.91 g/cm3).
(iii)It is a transparent polymer having moderate tensile strength and high tonghness.
(iv) It is chemically inert, slightly flexible and poor electrical conductor.
(v) Its elasticity is preserved even at lower temperatures
(vi) It is moisture resistant.
Uses:
(i) LDPE films are mainly used for packing and wrapping frozen food, textile products etc
because of their flexibility, chemical and moisture resistance.
(ii) The non-polar nature of the polymer makes it suitable for insulation for electric wires
and cables.
(iii)Its inertness to chemicals and resistance to breakage makes it a useful material for the
manufacture of 'squeeze bottles' and in many attractive containers.
(iv) It is also used for making pipes for agricultural, irrigation and cold water plumbing and
chemical plants,

UNIT IV: POLYMERS
(b) HDPE: High-density polyethylene is prepared by polymerizing ethylene at low pressure

(3200-2000atm) and at a temperature of 180-200°C in the presence of metal oxide
catalysts. HDPE can also be produced by using Ziegler Natta catalyst by coordination
polymerization. In this second method ethylene is heated to 60-200°C under a pressure of
6-7 atmospheres in the presence of a catalyst consisting of triethylaluminium and titanium
tetrachloride (Zieglcr-Natta catalyst). The polyethene so produced consists of linear chains
of polymer molecules which pack close together resulting in high density polyethene (0.97
g/cm3).
Properties:
(i) High density polyethene has melting point in the range of 145-150° C and is 90%
crystalline,
(ii) It possesses density in the range of 0.941 to 0.965 g/cm3.
(iii) It is much stiffer than LDPE and has higher tensile strength and hardness.
(iv) It is chemical resistant and has significantly lower gas permeability.
(v) Insulating and moisture resistant properties are similar to LDPE.
(vi) Due to high crystallinity, it has low gas and water vapour permeability.
Uses:
(i) HDPE is used in the manufacture of toys, crates closures, caps, buckets etc because it is
more tough and stiffer than LDPE.
(ii) Its greaseproof nature and chemical inertness makes it suitable for wrapping material for
food products.
(iii) Low gas permeability makes it suitable for domestic gas piping.
(iv) It is also used for manufacturing bottles for milk, household chemicals and drug
packaging.
(v) It is used in the manufacture of overhead tanks for water storage.
Whenever high tensile strength and stiffness are required HDPE finds better use than
LDPE.
2. Polypropylene: Polypropylene is probably the lightest known industrial polymer and can be
prepared in isotactic, syndiotactic or atactic forms. The monomer propylene is obtained as a
byproduct from gasoline refineries. Polypropylene (isotactic) is produced by polymerizing
propylene in the presence of Ziegler-Natta catalyst [Al (C2H5)3 – TiCl4)]
Properties:
(i) Polypropylene is stereoregular (isotactic) and highly crystalline polymer (slightly
lower than HDPE).
(ii) Isotactic polypropylene (IPP) melts at 160-170° C.
(iii) It exhibits high stiffness, hardness and tensile strength,
(iv) Its moisture resistance is comparable to that of polyethylene.
(v) Polypropylene is resistant to many chemicals such as alkalies, acids and oils. But
due to presence of methyl groups attached to alternate carbon atoms, it is
susceptible to oxidation.
(vi) Its electrical properties are similar to polyethylene.
(vii) Films of polypropylene are impermeable to a number of vapours and gases.
Uses:
(i) The higher melting point of polypropylene allows it to be used in products that must
be steam sterilized such as baby bottles, flasks etc.
(ii) Its fibres are extremely strong by weight and hence are used in making ropes and
filaments; it is also used for the manufacture of drinking glasses.

UNIT IV: POLYMERS
(iii) Polypropylene films are used to: packaging due to high clarity and their
impermeable nature to a number of vapours and gases. It is also used for wrapping
confectionary items (bread, biscuits etc) and potato chips.
(iv) Due to high strength, rigidity and temperature and chemical resistance it is used for
the production of chemical process equipments such as pipes and tanks.
(v) It is used for the preparation of textile machinery parts (bobbins, spools, spindles
etc), when blended with suitable elastomer it is widely used for making bumpers,
radiator grills etc.
(vi) It is also used as an insulating material for electrical wires.
3. Polystyrene: Polystyrene is also known as polyvinyl benzene. The monomer styrene is
produced from ethylene and benzene. When ethylene is passed into benzene in the
presence of AIC13 catalyst, ethyl benzene is formed, which on passing over iron oxide
catalyst at high temperatures is converted into styrene.
Properties:
(i) Polystyrene is transparent and has high
refractive index (1.6) which gives it
high brilliance.
(ii) It has got low heat distortion temperature (85° C) and hence articles made of polystyrene
cannot be sterilized with steam.
(iii) It consists generally of linear chains and is chemically inert and resistant to most alkalies,
oxidising and reducing agents and acids.
(iv) It is susceptible to photooxidative degradation, which results in brittleness and yellowing.
(v) It has got excellent moisture resistance.
(vi) It has good electrical insulating properties.
(vii) It can be dyed to different colors.
(viii) It has the unique property of transmitting light of all wavelengths through curved sections.
(ix) Polystyrene is attacked by a number of solvents.
Uses:
(i) Polystyrene is widely used in the manufacture of articles such as lids, jars, bottles,
combs, brush handles, radio and television cabinets.
(ii) It is used for preparing synthetic ion exchange resins in combination with p-divinyl
benzene.
(iii) An important use of polytyrene is the manufacture of foam and bead for insulation and
packaging material. The polymer is foamed by using blowing agents, usually pentane.
(iv) High-impact polystyrene (HIPS), produced by combination of polystyrene with
rubbery material such as polybutadiene (SBR). Contributes to improved impact properties
and is used for door liners, inner liners of refrigerators, etc.
(v) Polystyrene copolymerized with acrylonitrite and butadiene (ABS), due to its high
impact resistance and high dimensional stability at elevated temperatures is used in the
manufacture of door handles, radiator grills, loudspeaker housings etc.
(vi) Styreneacrylonitrile (SAN) copolymer is a transparent plastic with very good impact
strength and is used for moulding crockery items and machine components.

UNIT IV: POLYMERS
4. Polyvinyl Chloride (PVC): Polyvinyl chloride is one of the cheapest and most widely used
plastic globally. The monomer vinyl chloride is a gas, boiling at-14°C. Polyvinyl chloride is
prepared by the polymerization ofvinyl chloride by heating its water emulsion in presence of a
small amount of benzoyl peroxide.
Properties:
(i) It is colourless, odourless and non-inflammable.
(ii) PVC is partially syndlotactic and has low crystallinity.
(ii) PVC is thermally not very stable and degrades above 200° C, with the evolution of
HCL.
(iv) It is resistant to atmospheric oxygen, inorganic acids and alkalies.
(v) It has greater abrasion and flex resistance compared to leather.
(vi) It is water proof and washable
(vii) It is less brittle and lighter when compared to glass.
Uses: (Rigid PVC)
(i) Rigid PVC or unplasticized PVC has superior chemical resistance and high rigidity but
is brittle. It is used as sheets for tank linings, safety helmets, and mudguards.
(ii) It is used for making window frames as a substitute for wood because the frames do not
corrode.
(iii) It is used for-the manufacture of containers for detergents, cosmetics, mineral water.
(iv) Because of its oil-resistant property, it is used for storing consumable liquids like
edible oils, fruit squashes, table wine etc.
(Plasticized PVC)
(i) Plasticized PVC is used as an insulating material.
(ii) Because it is washable and has greater abrasion resistance therefore it is used for
making ladies-handbags, bathroom curtains, kitchen upholstery.
(iii)Used for upholstery for seats in public transport vehicles,
(iv) In the film form it is used in membrane separation technology.
5. Polyvinylacetate (PVA): Polyvinyl acetate is produced by heating vinyl acetate In the
presence of small amount of benzoyl peroxide.
Properties
(i) Polyvinyl acetate is a solid, clear resin, and has no taste or odour and is soft sticky
material.
(ii) It is insoluble in water and is saponified with great difficulty and hence is not
absorbed by the digestive system. Moreover if at all saponification takes place, the
products polyvinyl alcohol and acetic acid are not harmful. Due to the above-slated
reasons, polyvinyl acetate is used as a basic material for chewing gums and surgical
dressings.

UNIT IV: POLYMERS
(iii) It is resistant to atmospheric oxygen, water and chemicals.

Uses
(i) Polyvinyl acetate is used for the manufacture of lacquers, paints and adhesives.
Polyvinyl acetate adhesives are-used for bonding of textile to textile, leather to
leather/paper to paper, paper to textile, leather to wood etc.
(ii) It is used as a basic material for chewing gum and surgical dressings.
(iii) It is also used for finishing of textile fabrics.
(iv) On copolymerization with polyvinyl chloride, it is converted into a polymer having
varying degree of softness. For example, vinylite, which is a copolymer of
polyvinyl acetate and polyvinyl chloride, is especially useful as a surface coating
material for metals.
(v) It is mainly used for the manufacture of polyvinyl alcohol.
Polyvinyl butrayal is tough and elastic and is used for laminating safety glass. It holds the
broken pieces of glass in case of accident and thus minimizes the danger from flying glass
fragments.
5. Polymethylmethacrylate (PMMA): Polymethyl methacrylate (PMMA) is one of the
important thermoplastic from commercial point cf view, because of its outstanding optical
properties. It is prepared by the polymerization of methytmethacrylate in presence of free
radical initiator such as peroxides.
Properties
(i) It is a colorless transparent plastic with an excellent outdoor life period and good
strength.
(ii) Owing to the presence of bulky side groups, it is amorphous in nature.
(iii) It can be depolymerized to yield back the monomer.
(iv) It has high softening point of about 130-1400C but it becomes rubber-like at a
temperature above 65°C.
(v) The main feature of this plastic is its high optical transparency and capacity of
transmitting light accurately, even in curved sections.
(vi) It has good mechanical properties but has poor scratch resistance as compared to
glass.
(vii) It has low chemical resistance to hot acids and alkalies.
(viii) It has excellent weathering properties.
Uses
(i) PMMA is the nearest alternative to glass as it does not shatter and can be moulded
into any shape. Infact, PMMA sheets known as plexiglass or lucite are used as an
alternative to glass.
(ii) PMMA finds major use in automotive industry (e.g. housing for rear lamps, profiles,
light fittings, ceiling lighting signal-light etc).
(iii) It is used for making hard contact lenses due to its high transparency.

UNIT IV: POLYMERS

(iv) It is used as composite materials for kitchen sinks, basins and bathtubs because it
provides wide range of colour and are cheap and light.
(v) PMMA is also used for making windscreens T. V. screens etc. The fragments
formed after cracking are less sharp and hence less harmful.
(vi) It is also used for decorative purposes such as in jewellery etc. (vii) It is also used in
bone splints, artificial eyes, dentures etc.
6. Polytetraflouro Ethylene (Teflon) (PTFE): Polytetra flouroethylene is prepared by the
polymerization of tetraflouroethylcne ( CF2= CF2 ), under high pressure in presence of beczoyl
peroxide as catalyst.
The polymerization is associated with the release of large quantities of heat and if sufficient
precautions are not taken, this can result in violent explosions.
Properties
(i) PTFE has a highly regular structure and is highly crystalline.
(ii) Due to the presence of highly electronegative fluorine atoms and regular configuration
of PTFE molecule there are very strong attractive forces between different chains,
which give the material extreme toughness.
(iii) PTFE has high softening point of about 327° C. above 400°C ft decomposes without
changing into vapour.
(iv) It is extremely resistant to attack by chemicals such as strong alkalies and acids. Only
hot alkali metals and hot flourine can attack PTFE.
(v) PTFE is highly dense polymer (2.1 to 2.3 g/cm) having excellent mechanical properties.
(vi) It can be machined, punched and drilled.
(vii) It has a very low coefficient of friction
(viii) It has extremely good electrical insulating properties.
(ix) It is slippery and waxy to touch.
(x) It does not mell like other thermoplastics and hence behaves somewhat like a
thermosetting polymer.
(xi) It has non-adhesive characteristics.
Uses
(i) Due to its chemical inertness, it is used in chemical carrying pipes, tubing‘s, stop-cock
for burettes,
(ii) Its extreme inertness and stability to temperature makes it a suitable material for
making gaskets and seals.
(iii) It is used as an insulating material for transformers, cables, wires, fittings etc.
(iv) Because of its low coefficient of friction, it is used in non-lubricating bearings.
(v) Its most important application is, as non-stick coming for Dots and pan:,. PTFE is
applied as a coating over the rollers and mixing equipments used for preparing sticky
materials such as adhesives and jams.
(vi) Its fiber is used to form belts, filter cloth etc.
(a) Polyamides: Polyamides are a group of polymers which contain the amide
(-CONH-) linkage in the main polymer chair.. Polymers of this type are the synthetic

UNIT IV: POLYMERS

linear aliphatic polyamides, which are capable of fibre formation.
Nylon is the generic name fcr synthetic polyamides capable of forming fibres.
Polyamides (nylons) are prepared by the polycondensation between dicarboxylic acids and
diamines. Nylons are designated by two numbers, the first representing the diamine.
Polyamides of commercial importance are Nylon 6.6; Nylon 6, 10, Nylon 6 etc.
(i) Nylon 6.6: Nylon 6,6 is prepared by the polycondensation of hexamethylene diamine
with adipic acid.
Properties of Nylons
(i) Nylons are characterized by a combination of high strength, elasticity, tonghness and
abrasion resistance.
(ii) They have very good moisture resistance.
(iii)They are insoluble in common solvents.
(iv) The molecular chains are held together to each other by hydrogen bends having linear
structure, permitting side-by-side alignment.
(v) They are very flexible and retain their original shape after use.
(vi) Nylons provide excellent resistance to wear and abrasion
(vii) Due to the presence of hydrogen bonding, all nylons are water sensitive. Water acts as
plasticizer, which reduces tensile strength and dimensional stability.
Uses
(i) Nvlon 6.6 is used as a plastic as well as a fibre. It‘s most important fibre applications
include automobile tire cords, ropes, threads, cords having high tenacity and good
elasticity.
(ii) Nylon 6.6 is also used to make textile fibres for use in dresses, undergarments, socks
etc.
(iii) Nylon 6.6 being a tough plastic is used/as a substitute for metals in gears and bearings
etc. Nylon 6.6 can be moulded in one piece whereas similar item in metal require
assembling of several parts. Moreover, nylon bearings and gears perform quietly and
need little or no lubrication.
(iv) It is also used in making rollers, slides and door latches.
(v) Nylon 6. 10 is not used much as synthetic fibre, but is used to manufacture articles like
brushes and bristles.
(vi) Nylon 11, is used as textile fibre.
(vii) Due to its good barrier properties, nylon-6 film is used for packaging some oxygen
sensitive food.
(viii) Due to its high tenacity, nylon is suitably used for parachute fabric.(ix) Nylons are
also used in making transmission belting, ribbons for electric-typewriters, spindle
bands on textile spinning machines etc because of its high durability, (x) Nylon is also
used for making insect screens because of their biological resistance.
Aromatic poiyamides, often called aramids have been produced to improve the heat and
fiamma-bility resistance of nylons. These polymers have very high melting points (greater
than 500°C). One such nylon is Kevlar. It is prepared by polycondensation between aromatic
dichioride and aromatic diamines.
Keviar is exceptionally strong and decomposes only above 500° C It is 5 times stronger than
steel and it is used as a substitute for steel in belted radial tires as well as in bullet resistant
vests. It is also used in making car parts such as tyres, brackes, clutch linings etc.

UNIT IV: POLYMERS

COMMERCIALLY IMPORTANT THERMOSETTING RESINS
1. Polyesters: Polyester resins are the condensation products of dicarboxylic acid with
dihydroxy alcohols. The industrially most important polyester is poly (ethylene
terephthalate) (PET), with the trade name Teryelene or Dacron. PET can be prepared from
terephthalic acid and ethylene glycol, either by direct esterification or by catalyzed ester
inter change.
Nowadays, dimethyl terephthalate is used instead of terephthalic acid. This is because of the
fact I thai terephthalic acid is nonvolatile and is very slightly soluble in most of the solvents.
The reaction takes place in two successive stages:
The enihyiene giycoi so formed is distilled off at such high temperature.
Properties
(i) PET is resistant to heat and moisture.
(ii) It is strongly resistant to both weak acids and bases at room temperature but readily
attacked by strong acids and bases.
(iii) Presence of numerous polar groups results in powerful dipole attractions in it.
(iv) It has good mechanical strength up to I75°C.
(v) It is resistant to almost all kinds of insect attacks.
(i) It can be dyed at i00° C or in presence of a carrier.
(ii) The fibre has good wrinkle resistance due to good elasticity,
(iii) PET fibres are abrasion and oxidation resistant.
Uses:
(i) PET is mostly used for making synthetic fibres like Terylene, Dacron etc. Garments
made from its fibres resist the formation of wrinkles and have many desirable properties
such as warmth to touch, low moisture absorption (and hence dry rapidly), crease
resistance, shape retention, and mildew proof. Moreover, these may be blended with other
fibres, such as wool end cotton.
(ii) PET is also useful for making films because of its high strength, resistance to tearing
durability, transparency etc. PET is used in making the transparencies of overhead
projector.
(iii) Due to its impermeability to a number of organic and inorganic gases it is used in the
manufacture of plastic bottles for carbonated beverages (barrier to C02 and water)
(iv) It is also used to make magnetic recording tapes.
(v) Due to their high dielectric strength thev are used for electrical insulation.
(vi) Glass reinforced PETis used for the manufacture of housings-for coffee machines, car
heaters, toasters.
2. Phenolic Resins: Phenol formaldehyde resins are the most important and extensively used
synthetic plastics and perhaps the oldest synthetic plastics. In these resins one of the
monomers is always a phenol molecule. One of the most important member of this class is

UNIT IV: POLYMERS

phenol formaldehyde resin.
The phenol formaldehyde reaction is catalyzed by alkalies and acids. The nature of the
product depends on several factors, the major one being the nature of the catalyst and the
proportion of the reactans (phenol formaldehyde ratio). The formation of phenol formaldehyde
resin comprises of the following steps:
(i) Methylolation: When phenol and formaldehyde react together, the first step is the
entry of methylol (CH2 OH) groups in ortho and para positions to the hydroxy group.
The reaction takes place in the presence of acid or alkali. Depending upon phenol
formaldehyde ratio, various phenol-alcohols may be formed.
(ii) Novolac formation: Depending upon the ratio of phenal formaldehyde (P/F)
different resins, namely novolac and resol resins are obtained. In the presence of acid
catalyst, when the P/F ratio is greater than unity, the methvloi derivatives condense
with phenol to form a linear polymer with little mcthyloJ groups. The product is
thermoplastic in nature and is known as novolac.
(iii) Rescole formation: In the presence of alkaline catalysts with P/F ratio less than
3,the methylol phenols condense to form linear structure called resoles. The resoles
are soluble in the reaction mixture and have excess of methvloi groups capable of
further reaction during continued heating. Resols, therefore have limited shelm-life.
However, the reaction may be stopped at the desired step by cooling.
(iv) Resile formation: On further heating, resoSe is transformed into a three dimensional
polymer, calied resile, due to the presence ofsctive groups and mobile hydrogens
Resite is an infusible and insoluble material.
Properties
(i) Phenol formaldehyde moulding resins have excellent heat resistance.
(ii) These have high dimensional stability.
(iii) To improve the properties further, fillers such as wood, flour, mica, asbestos etc arc
added to them.
(iv) Phenolic resins have good dielectric properties.
(v) These have remarkable adhesive properties and bonding strength.
(vii) They are however attacked by alkalies, because of the presence of free hydroxy
groups.
(vii) They are hard, rigid and scratch-resistant.
Uses Phenolic resins have wide applications.
(i) The main use of phenolic resin is in moulding applications. They are widely used in
making telephone parts, cabinets for radio, television and automobile parts

UNIT IV: POLYMERS

(ii) Due to their adhesive properties and bonding strength, they are used for producing
brake linings, abrasive wheels and sand paper.
(iii) They are used for making electric insulator parts like switches, plugs, switch boards,
heater-handles etc,
(iv) Phenolic resins are used for impregnating paper, wood and other fillers.
(v) These are also used in varnishes, paints and protective coatings.
(vi) These are used in the production of ion exchange resin for water softening.
4. Amine Resins: Amino resins or amino plasts are prepared by the reactions of
formaldehyde with nitrogen compounds such as urea, melamine and other amino
compounds. Because of their attractive light colours, these resins have great commercial
importance.
(a) Urea formaldehyde resins: This is prepared by the condensation reaction between
urea and formaldehyde in neutral or alkaline conditions. The first products formed
during the formation of resin are monomefhylol and dimethyol ureas.
(ii) Polymerization can take place from mono or dimethylol urea, or possibly through both,
with the formation of long chains.
(iii) Thermosetting of the resin takes place during the moulding process. For moulding, the
methylol derivatives are compound with fillers, plasticizers, pigments etc. and then are
subjected to heat and pressure, resulting into a hard, infusible product.
Properties
(i) The urea formaldehyde resins are light in colour and enable the production of light or
pastel coloured objects.
(ii) Their heat and moisture resistance are lower than those of phenolic resins.
(iii)They have good electrical insulating properties.
(iv) They are resistant to oxidation to oil, grease and weak acids.
(v) They are hard, resist abrasion and scratching.
(vi) They have good adhesive properties.
Uses
(i) Urea-formaldehyde resins are widely used to make moulded articles like vacuum flask
cups jugs buttons, bottle caps etc where the darker colour of phenolics may be
objectionable.
(ii) They are also used for adhesive applications for the production of plywood and
laminating.
(ii) They are used for the manufacture of cc .ted abrasive paper and binder for foundry

UNIT IV: POLYMERS

cores.
(iv) They are used for the manufacture of cation exchange resins.
(v) These also find use In the manufacture of electrical switches, plugs and insulating
foams,
(vi) Their applications also include the treatment of textile fibers for improving their
shrink and crease resistance.
(b) Melamine-formaldehyde resin: Melamine formaldehyde resins are another class of amino
resins. They are produced by the condensation of melamine (2. 4, 6 triamino – 1, 3, 5
triazine), trimer of dicyandiamidc with formaldehyde, exactly in the same manner as in the
formation of urea formaldehyde resin. The reaction takes place under mild alkaline or
neutral conditions.
Properties:
(i) The melamine resins have better hardness, heat resistance, and moisture resistance
than the urea - formaldehyde resins. However these are expensive. Rest of the
properties is similar to urea-formaldehyde resins.
Uses
(i) Typical applications of urea formaldehyde resins include the production of
decorative plastic ware, laminated worktops.
(ii) They are used in electrical fittings.
(iii) They are used for resin bonded grinding wheels.
(iv) They are used for textile finishing providing crease resistance, stiffness, water
repellency etc.
(v) They are also used in automotive finishes.
(vi) Melamine resins are also used as a tanning material for leather. The presence of
small amount of this resin in the tanning material improves the strength of the
leather.
(vii) They are also used for the preparation of lacquer
RUBBERS (ELASTOMERS)
It was discussed in the beginning of the chapter that depending on the ultimate form and use a
polymer car, be classified into two broad categories: Plastics and Elastomers (rubbers).
Elastomers arc (he polymers which are capable of being stretched rapidly a! least 150 precent
of their original length without breaking and return to their original shape on release of stress
For example, rubber band is a typical elastomeric material When stretched, it is elongated to
many times its length. But when the force is released it gets back to its original length.
The properties of typical elastomers are defined by the following:
• They must stretch rapidly and considerably when stretched, reaching high elongations
(500-1000%).
• They must exhibit high tensile strength and high stiffness when fully stretched.
• They must snap back to their original length once the stretching force is withdrawn or the

UNIT IV: POLYMERS

stress is released.
These criteria are met with the materials which:
• Have high molecular mass (high polymers).
• Are above their glass transition temperature.
• Are amorphous.
• Contain a network of crosslinks to restrain gross mobility of its chains.
Columbus on this voyage to America found the native of West Indies v-ere playing with the
solid mass collected from the exudate of a tree. Years later, Joseph Priestly showed that this
solid mass could rub off pencil marks from paper and hence the material was called rubber.
The main source of natural rubber is the species of tree known as ‗Hevea Basiliensis‘ even
today, which account for multibillion-dollar rubber industry. Rubber or elastomers can be
obtained naturally or synthetically. Consequently we have natural rubber and synthetic rubber.
NATURAL RUBBER
Natural rubber of nearly same characteristics occur in the inner bark and to a lesser extent in
the leaves and roots of a number of tropical plants But the latex from the tree ‗Hevea
Basiliensis‘ is proved to be the main source of rubber. Latex is an emulsion of poly
hydrocarbon droplets in an aqueous solution and looks like milk. The negatively charged
particles of polyhydrocarbons, a colloidal dispersion, stabilize the emulsion.
Processing
The latex is collected by making small incisions in the trees in such a manner so as to allow the
latex to accumulate in small cups. The percentage of rubber in it is 25-35%. A fully grown tree
gives about 5 gm of rubber in a day.
The average composition of the latex is:
Water = 60%; Rubber = 35%; Proteins, enzymes and nucleic acid = 3%; fatty acids and esters
= 1% and inorganic salts = 0.5%.
In these trees, the rubber is formed from polymerization of isoprene i.e. (2-methyl-1, 3-
butadiene) to produce poly-(cis)isoprene by a biochemical reaction in which a particular type
of enzyme acts as a catalyst.
CH2 = C—CH = CH2
CH3
Isoprene (2 – methyl – 1, 3 – butadiene )
The latex is first sieved to remove the impurities such as leaves, bark etc. From 25-35% dry
rubber content the latex is diluted to contain about 15-20% of rubber content. The rubber is
then separated from the latex by the process of coagulation. The acetic acid or formic acid is
added as coagulants and the rubber is coagulated to soft white mass. About 1 g of acetic
acid/formic acid is added per 2G0 kg of rubber material. This coagulated mass is the crude
rubber and consists of 90-95% rubber, 2-4% proteins and 1-2% resins. The crude rubber is
wached and treated for producing the following types of rubber depending upon the process.
1. Crepe Rubber: Crepe rubber is prepared by adding a small amount of sodium bisulphite
(NaHSO3 ) to the coagulated mass to bleach the rubber. Then the rubber is passed through a
creping machine. The creping machine is rolling machine which consists of two rollers
having longitudinal grooves. Thus, after passing through it, the spongy rubber is converted
into a sheet having a rough surface which resembles the crepe paper and hence the name.
2. Smoked Rubber: The smoked rubber is produced by carrying out the coagulation of latex in
the tanks provided with vertical grooves on sides and fitted with metal plates which run

UNIT IV: POLYMERS

across the width of the tank. First the diluted latex is poured into the tanks, with the metal
plates removed. Then the coagulant is added (acetic or formic acid) and the plates are
inserted. The tanks are kept undisturbed for 15-16 hours. The tough slabs are formed. These
slabs are passed through a series of rolling machines and finally rubber sheets having ribbed
pattern are obtained. The ribbed surface prevents the sticking of the rubber with each other.
These sheets are then dried in smoke houses at about 50CC in the smoke obtained from
burning wood or coconut shells. The smoked rubber so obtained is translucent and ambre
coloured.
GUTTA PERCHA
Gutta percha is another variety of natural rubber; it is obtained from the mature lea\cs of
dichopsis gutta and palagum gutia trees. The hevea rubber and gutta percha, both are composed
of isoprene units with structures shown in the figure? But natural rubber is ci:;-isomer where
a bending back of successive isoprene units take place giving the molecule a coiled structure.
The gutta percha. on the other hand is a trans-isomer which consist of straight chains, giving a
rod like structure to the molecule. The rod-like structure results into close packing of adjacent
chains. Thus gutta percha is more crystalline.
Processing of Gutta Percha
The mature leaves obtained from the trees Dichopsis gutta or palagum gutta are carefully
ground in mills and are then treated with water maintained at 70°C for about half an hour when
the gutta percha is extracted in water. The solution is dropped into cold water and gutta percha
floats on the surface. Alternatively, gutta percha can be recovered by solvent extraction.
Properties of natural (Hevea)rubber and gutta percha:
Natural Rubber (Hevea rubber) Gutta Percha
1. Natural rubber is highly Gutta percha is a hard thermoplastic material at room
soft and elastic material temperature but it softens and becomes tacky at about
1000°C
2. It is soluble in carbon It is soluble in petrol,
disuphid-: and petrol.
3. It Is cis poiyisioprene It is transpolyisoprene.
Drawbacks of Raw Rubber: Raw rubber has a number ot drawbacks when put to use. Some
of the drawbacks are:
(i) Crude rubber is soft at high temperatures but becomes brittle at low temperatures. So it can
be used in a limited temnerature range.
(ii) It is too" weak with a tensile strength of 200 kg/cm2
(iii) It is not resistant to mineral oils, organic solvents.
(iv) It has large water absorption capacity.
(v) Due to oxidation in air. it deteriorates and hence is durability its decreased.
(vi) It is also attacked by the oxidizing agents like nitric acid, Conc. sulphuric acid, chromic
acid etc.
(v) It undergoes permanent deformation when stretched. This may be due to stretching the
individual chains slip past each other and get separated resulting in the breakage of the
material.
(vi ) However the above drawbacks can be overcome by improving the properties by the
addition of suitable materials and further heat treatments.
Some of the processes for improving the properties of rubber are discussed below:
PROCESSES FOR IMPROVING THE PROPERTIES OF RUBBER

UNIT IV: POLYMERS

The desired properties in rubber can be obtained by compounding it with certain chemicals.
The compounding of rubber is generally facilitated by a process called mastication.
Mastication: When rubber is subjected to mechanical stresses arising from say, high-speed
stirring or milling, it undergoes considerable molecular degradation or fragmentation. The
process is called mastication. The mastication converts hard and tough rubber into a soft,
supple and semisolid mass. The CH2 – CH2 links between the isoprene units in the rubber are
weak and hence break when subjected to mechanical stresses. The net effect is that the big
molecule is broken into small fragments. After mastication is complete the compounding
agents are added to the rubber.
Compounding: The process involving the incorporation of chemicals such as plasticizers,
vulcanizing agents, stabilizers, fillers, fillers etc., into the rubber industry was discovered by
Charles Goodyear in 1839. the process by which a network of crosslinks is introduced into an
elastomers is called vulcanization. Charles Goodyear used sulphur to crosslink polyisoprene
molecules in natural rubber. The added sulphur combines chemically at the double bonds
bringing about changes in its properties profoundly. Vulcanization transforms elastomers
which are a weak thermoplastic mass of no use into a strong, elastic and tough rubber. The
tensile strength, stiffness, durability, resistance to changes in temperature, elasticity and
chemical resistance of a vulcanized rubber are increased manifolds as compared to
unvulcanized rubber.
The introduction of sulphur links in between the polymer chains restrict the
intermolecular movement which brings about stiffening of rubber.
The extent of stiffness of vulcanized rubber depends upon the amount of sulphur added.
For example, a rubber may contain 3 to 5% sulphur whereas Vulcanite or ebonite (hard rubber)
contains about 32% sulphur. The extensive Crosslinking in hard rubber makes it so stiffer tat
there is practically no elasticity in it. Fig. shows the effect of vulcanization on rubber. Ordinary
rubber molecules are bent and convoluted (a) When stretched the molecules can slip past one
another. But vulcanization introduces crosslinks between these and hence on stretching the
molecular chains cannot slip past each other.
(a) (b) (c)
Unvulcanized Rubber Vulcanized Rubber (Unstretched) Vulcanized Rubber
(Stretched)
Chemistry of Vulcanization
The addition of sulphur develops crosslinks, thereby improving the processibility and utility of
rubber. But the mechanism of vulcanization is quite complex and is still not known in detail.
Both free radical and ionic intermediates have been postulated. Sulphur exists as S 8 i.e. cyclo
octasulphur. The probable mechanism can be:
 Sulphur (S8) dissociates into S S
+ -
+ -
S8 S S
Where m and n are the numbers of sulphur atoms.
 The sulphur cation Sm reacts with a diene molecule of rubber to give l.
+
 This cation adds to other polymer molecule to give ll and carbonium ion iii
 The arlylic carbonium ion reacts with S8 to form IV which adds to polydiene to form
sulphur bridges (V). This can further react with S8 and the cycle goes on
It must be emphasized that neither heat nor sulphur is essential for the vulcanization
process. Vulcanization can even be carried out by number of other substances. Hence
vulcanization can be of two types:
(a) Sulphur Vulcanization: As stated earlier, in this process the rubber is heated with
sulphur or CS2.

UNIT IV: POLYMERS

(b) Non-sulphur Vulcanization: Non-sulphur vulcanization is achieved through a free
radical.
 Free radical can be generated from a curing agent such as benzoyl peroxide or as a step
in the oxidative degradation of rubber.
 This free radical abstracts a hydrogen atom from one of the –methylene groups.
 The rubber free radical so formed attacks a double bond in an adjacent polymer chain
resulting into crosslink (vulcanization) and regeneration of a free radical.
This cross linked free radical will further attacks more C=C bonds to form a large
number of cross linkages leading to vulcanization.
Further, the compounds such as Se, Te, ZnO, benzoyl, chloride, trinitrobenzene, etc.,
are also used as vulcanizing agents.
Advantages of Vulcanization
Vulcanized rubber has got ideal elastomeric properties which increase its utility manifolds. The
main advantages of vulcanized rubber are:
1. Tensile strength: Tensile strength is the measure of the ability of a polymer to
withstand pulling stresses. Vulcanized rubber has got good tensile strength and
extensibility. The tensile of the raw rubber is 20 kg/cm2, which increases to 2000
kg/cm2 on vulcanization.
2. Resilience: It is the property of a elastomers to return to its original shape on the

release of stress. Resilience of vulcanized rubber improves manifolds as compared to
raw rubber.
3. Water Absorption Capacity: The water absorption capacity of vulcanized rubber is
greatly reduced.
4. Vulcanized rubber is resistant to organic solvents such as benzene CCl4, fats and oils.
Though it swells in these solvents but to a lesser extent than raw rubber.
5. Insulation Properties: Vulcanized rubber has better insulation properties than raw
rubber. Raw rubber vulcanized with 32% sulphur (ebonite) has extremely good
insulating properties.
6. Elasticity: The elasticity of vulcanized rubber is greatly reduced. The elasticity of the
vulcanized rubber depends upon the extent of vulcanization. If 30-50% of sulphur is
present in vulcanized rubber then a rigid, non-elastomeric plastic (ebonite or hard
rubber) is formed.
7. The working temperature range for vulcanized rubber is -40°C to 100°C as compared to
raw rubber, which has working temperature range of 10°C to 60oC.
8. It is resistant to abrasion, ageing and reactivity with oxygen and ozone.
A comparison of raw rubber and vulcanized rubber is given in the following table:
Table: Comparison of properties of Raw, Vulcanized Rubber, Reinforced Vulcanized Rubber.
Property Raw Rubber Vercanized Rubber Reinforced Valcanized Rubber

1. Tensile strength (psi) 300 3000 4500
2. Elongationat break (%) 1200 800 600
3. Elasticity Very high Low, depends upon Very low, depends upon extent
extent of vulcanization of vulcanization and
reinforcement
4. Water absorption Large Small Small
5. Solvent resistence Sluble Swells only Swells only
(hydrocarbons)
6. Chemical resistance Poor Much better Much better

UNIT IV: POLYMERS

Other Compounding Techniques
Though vulcanization improves the properties of natural lubber to a great extent but even
vulcanized rubber do not exhibit satisfactory properties for various utility items. These
propenies can be enhanced by other compounding techniques discussed below:
(i) Reinforcing Fillers: To give strength and rigidity to the rubber, fillers are added. Fillers
are of two types: (a) inert fillers, such as clay which make the rubber mixture easy to
handle before vulcanization, but have no effect on the physical properties, and (b)
reinforcing fillers which greatly improve the properties of rubber or vulcanized rubber.
Common fillers include carbon black, zinc oxide, magnesium carbonate, barium, sulphate,
calcium carbonate etc. Carbon black is remarkable reinforcing filler for both natural and
synthetic rubbers. Table gives the comparison of raw rubber and non-reinforced vulcanized
rubber and reinforced vulcanized rubber. In vulcanization, though the long range
movement of the polymer molecules is restricted, still movement of local chains is high.
Reinforcement of vulcanized rubber restricts this local freedom of movement, making the
polymer stiffer and tougher.
(ii) Plasticizers or Softeners: Plasticizers are added to rubber to improve flow and therefore,
processability-plasticizers also reduce the brittleness of the product. The common
plasticizers used are hydrocarbon oils, resins, waxes, etc. The oil serves as a plasticizer and
a softener by reducing the melt viscosity of the rubber to the levels required Compounding.
(iii) Antioxidants: Rubbers that retain double bonds in their vulcanized structure are
sensitive to heat, light and particularly oxygen. Thus rubber deteriorates in presence of light
and air due to oxidation and as a result becomes soft and degrades. Antioxidants" are
substances that protect the polymer by preventing oxidation. In many cases these also
prevent undesirable reactions promoted by oxygen. Common antioxidant is complex
organic amines like phenyl p-naphthylamine, phenolic substances and phosphates. The
structures of two common antioxidants are given below:
Antioxidants
(iv) Accelerators: Vulcanization takes place by heat and in presence of sulphur, but the
process is very slow. The process can be speeded up by addition of small amounts or
organic or inorganic compounds known as accelerators. The inorganic accelerators include
lime, magnesia and white lead whereas organic accelerators are complex organic
compounds such as aldehydes, amines, thicarbonates and 2-mercaptol benzothiozole.
Sometimes accelerators require the presence of still other chemicals known as activators or
promoters. These activators are usually metallic oxides such as zinc oxide. The best
combination for efficient vulcanization include sulphur, an organic accelerator, a metallic
oxide and a soap.
(v) Colouring Agents: Several dyes and pigments are used to impart colours to elastomers.
Common colourants for polymers include:
Appearance Chemical used
White TiO2, BaSO4
Yellow Lead Chromate
Red Ferric oxide
Crimson Antimony sulphides
Blue Ultramarine
Green Chromium trioxide
Silver metallic effect Flake Aluminimum
Pearlescence Lead carbonate and mica.
The oil-soluble dyes or which have small particle size and refractive index near that of the

UNIT IV: POLYMERS

plastic (organic pigments such as phthalocyanins) are added to get transparent coloured
products from transparent plastics. The inorganic pigments impart opacity to the plastic.
SYNTHETIC RUBBERS
The polymers possessing similar physical properties as that of natural rubber are called
synthetic rubbers. As natural rubber suffers from many disadvantages, attempts to find out a
substitute for natural rubber began very early.
Greville William (1860) was first to isolate isoprene as a decomposition product by
heating rubber to a high temperature. This gave a clue that rubber can be synthesized by the
polymerization of monomers like isoprene. By the end of 19th century the fact was confirmed
when polymerization of isoprene yielded rubber like product.
Since then attempts were on to prepare synthetic rubber by other monomers as well.
Synthetic rubbers have been produced by the polymerization of a large number of conjugated
dienes resembling isoprene. The foremost of all is, Buna Rubber (polymer of butadiene) which
was prepared by the action of sodium on butadiene. That is why synthetic rubber is known as
Buna rubber—'Bu' for Butadiene and 'Na' for sodium. However, the product prepared had poor
tensile strength, and ageing characteristics. Improvements in properties were made by
developing copolymers of butadiene. Several types of synthetic rubber are available today and
some of them are described below:
1. SBR or Buna-s Rubber
Styrene-butadiene rubber (SBR) is the first commercially made synthetic rubber. It is a
copolymer obtained by the free-radical polymerization of two monomers, styrene and
butadiene. The two components are allowed to react in a mixing vessel containing an aqueous
solution of an emulsifying agent in presence of free radical initiator such as. cumene
hydroperoxide or p-menthane hydroperoxide.
According to the temperature used, two processes have been developed, the hot process
(at 50°C) and the cold process. In the cold process the temperature is kept in the range -18°C
to 5°C. The rubber is known as cold rubber. Cold process is more efficient than the hot process
because chain length can be controlled more efficiently. The SBR copolymer contains about
75% butadiene and 25% styrene and is a random copolymer. Both type of rubbers 'cold' as
well as 'warm rubbers" can be vulcanized by conventional methods using sulphur. A
reinforcing filer is added to achieve good physical properties.
Properties
(i) SBR possesses high abrasion loses resistance and high load bearing capacity,
(ii) At elevated temperatures SBR almost 2/3 of their tensile strength whereas natural
rubber only loses 1/4th.
(iii) Its resilience is poorer than that of natural rubber, which restricts its use in tire
industry.
(iv) The weather ability of SBR is better than that of natural rubber.
(v) 'Cold' SBR is superior to the standard product because it contains less chain
branching and crosslinking.
(vi) SBR gets easily oxidized in presence of traces of ozone present in atmosphere.
(vii) It swells in oils and solvents.
Uses
Of all the synthetic elastomers; SBR enjoys the major share of the market. SBR has the

UNIT IV: POLYMERS

following applications:
(i) The principal use of SBR is in the production of tires and tire, products which are
typically blends of both natural and synthetic rubbers. SBR is used for lighter duty
tyres but is inferior to the natural rubber in its use for truck tyres.
(ii) For many mechanical goods, it is superior to natural rubber and is used because of its
easier processing.
(iii) It is used for making hose, shoe soles, gaskets, floor tiles, carpet backing, tank
linings etc.
(iv) It is widely used for electrical insulation, although its properties are not good as those
of butyl rubber.
2. Buna-N or Nitrile Rubber (NBR) or GR-A
The nitrile rubbers are polymers of butadiene and acrylonitrile in the ratio of 75% and 25%
respectively. !f is prepared by emulsion polymerization using cumene hydroperoxide as
initiator. Hydrogen peroxide and ferros sulphate can also be used as initiators. Vulcaniza ion is
done by conventional means by adding sulphur.
CH2=CH—CH = CH2 - CH2-CH—CN

Butadiene Acrylonitrile
CH2 – CH = CH – CH2 – CH – CH2
CH
(i) Nitrile rubbers are noted for their oil resistance. However the oil resistance varies with
composition. If the acrylonitrile content is between 18% then the rubber has fair oil
resistance and if it is more than 40% then it is extremely oil resistant.
(ii) It possesses excellent resistance to heat, sunlight, acids and salts.
(iii) Because of the presence of cyano groups (-CN). it is less resistant to alkalies than natural
rubber.
(iv) it has good tensile strength and abrasion resistance.
(v) The rubbers are less resilient than natural rubbers.
(vi) It has good heat resistance and if properly protects by antioxidants, it snows resistance to
oxidative degradation as well.
Uses
(i) Nitrile rubber is used primarily for its oil resistance. These are extensively used for
fuel tanks, gasoline hoses, gaskets, printing rollers and high attitude aircraft
components.
(ii) They can be used in contact with water and antifreeze solutions.
(iii) They are also used in the form of latex for impregnating paper, textile and leather.
(iv) It can also be used as blend component in tyre manufacture.
3. Neoprene or GR-M Rubber
This is also known as polychloroprene or pclychlorobutadiene or duprene. Neoprene was
the first synthetic rubbers developed in the United States.
Preparation: Neoprene or polychloroprene is prepared by polymerization of

UNIT IV: POLYMERS
chloroprene, which is 2-chloro-1, 3 butadiene.

The preferred configuration produced during the polymerization is trans 1-4
polychloroprene. The polymerization of chloroprene takes place through emulsion
polymerization.
The starting material, chloroprene is manufactured by the addition of hydrogen
chloride to vinyl acetylene, which inturn is prepared by dimerization of acetylene.
The vulcanization of neoprene is different from that of other elastomers in that it can
be vulcanized by heat alone. Although some types are polymerized in presence of sulphur
which introduces crosslinks in the polymer. Neoprene can also be vulcanized using zinc
oxide or magnesium oxide.
Properties: Neoprene is closely related to the natural rubber and can replace rubber
because similarly in the properties of the two. Some of the properties of Neoprene are:
(i) As H atom in the natural rubber is replaced by Cl atom in Neoprene, Neoprene
has superior resistance to vegetable and mineral oils.
(ii) It is superior to natural rubber as far as ageing and effects of high temperatures
are concerned.
(iii) Neoprene is soluble in polar solvents due to the presence of chloro-group.
(iv) Vulcanized neoprenes have high tensile strength (3500-4000 psi) in the
absence protected.
(v) Vulcanized neoprene is extremely resistant to oxidative degradation if suitably
protected.
(vi) It has good weathering and ozone resistance.
(vii) It has got excellent oil resistance, though inferior to Nitrile rubber but better
than natural rubber or SBR.
Uses
Neoprene is used for:

(i) It is used in oil resistant wire and cable coatings, industrial hoses, shoe holes.
(ii) Its latex is used for the manufacture of gloves and coated fabrics.
(iii) It is used for making tubings for carrying corrosive gases and oils.
(iv) It is used for the manufacture of sponges, conveyer belts, linings of reaction
vessels etc.
4. Butyl Rubber (GR-I)
Butyl rubber belongs to the class of elastomers which do not have unsaturated chain
structure. However, a small amount of diene monomer that provides a site for
vulcanization is included by means of copolymerization.
Preparation
Butyl rubber or polyisobutylene are prepared by the copolymerization of isobutylene with

a small amount (1.5 to 4.5%) of isoprene. Isoprene is added to render them vulcanizable.
It is prepared by low temperature cationic polymerization using Friedal-crafts catalyst at

UNIT IV: POLYMERS
–80oC.
Properties
The absence or low concentrations of double bonds in the main chain of butyl rubber
results in high resistance to attack by a number of chemicals. It has the following
properties.
(i) Polyisobutylene or butyl rubbe ris amorphous under normal conditions but
crystallize on stretching.
(ii) It exhibits outstanding resistance to attack by oxygen and ozone due to low
concentration of double bonds. It is less sensitive to oxidative ageing as
compared to other elastomers except silicons.
(iii) Butyl rubber becomes soft on oxidative degradation.
(iv) It exhibits low gas permeability due to closepacked linear paraffinic chains.
(v) It has high ozone and acid resistance.
(vi) Due to very low unsaturation, it cannot be hardened much on vulcanization.
(vii) Unstabilized polyisobutylenes are degraded by light or heat to sticky low-
molecular weight products. Therefore usual rubber antioxidants should be
added to stabilize the polymer.
(viii) It has excellent insulating properties as predicted from its non-polar, saturated
nature.
(ix) It is soluble in hydrocarbons such as benzene.
(x) The tear resistance of butyl rubber is quite good and is retained well at high
temperature and for long times, in contrast to natural rubber.
Uses
(i) Butyl rubber is used for inner tubes for tires because of its impermeability to
gases.
(ii) It is used for wire and cable insulation.
(iii) It is used for linings of tanks, hoses etc.
5. Polysulphide Rubber (Thicol or GR-P)
Polysulphide Rubbers are the condensation products of ethylene dihalides and alkali
sulphides. These are linear condensation polymers.
Preparation
Polysulphide rubber is obtained by the reaction between sodium polysuhphide and
ethylene dichloride. Thus sulphur forms the part of the polymer chain. During the
reaction NaCl gets eliminated. Vulcanization cannot be achieved by sulphur because
polymer chain is not unsaturated. Hence it is not a hard rubber. However vulcanization
can be achieved by reacting with ZnO which reacts with sulphur links forcing crosslinks.
Properties
The properties of the materials depend on the length of the aliphatic groups and the

UNIT IV: POLYMERS
number of sulphur atoms present in it. With four sulphur per monomer, the product is
rubbery, whereas if only two sulphur atoms are present per monomer, the polymer do not
behave as elastomer. In that case at least four methylene groups are needed in the dihalide
to induce elastomeric properties to the products. Some of the important properties are:
(i) Thiokol is resistant to swelling.
(ii) It is resistant to oils and solvents. Fuel oils, lubricating oils, gasoline and
kerosene have no effect on Thiokol.
(iii) Thiokol films are impermeable to gases to a large extent.
(iv) It cannot be vulcanized and hence does not form hard rubber.
Thiokol rubbers from many disadvantages:
(i) It has disagreeable odour (mercaptan odour).
(ii) It has poor heat resistance, poor abrasion resistance and low tensile strength.
(iii) It tends to lose its shape under continuous pressure.
However, recent developments of Thiokol have overcome these disadvantages.
Uses
(i) Polysulphides or Thiokol is used to make sealants, gaskets, balloons, fabric coating.
(ii) Due to low permeability it is used to make gasoline hoses.
(iii) Liquid Thiokol can be cured at room temperature to tough solvent-resistant rubbers.
These liquid compounds are used as gasoline tank sealants and liners for aircraft
and in variety of other sealing applications.
(iv) The liquid polymers, when combined with oxidizers burn with great intensity and
generate large volume of gas. Thus it can be used in solid-fuel rocket propellants.
6. Polyurethane (PU)
Polyurethanes are polymers containing the group (carbonate group) these are known as
urethane linkages
Preparation: The polyurethanes are formed through the reaction diisocyanate with the
compound containing at least two active hydrogen atoms such as diols or diamines. The
reaction of diisocyanate with glycol is represented as:
The properties of the final product depend upon the type of monomers and their chain
length. A wide variety of polymers can be prepared ranging from rigid to elastic
polymers. Crosslinking takes place through isocyanate groups which are capable of
reacting with hydrogen atoms attached to the polymers leading to vulcanization. The
polyurethanes can be produced in the form of fibers, elastomers or foams.
The foamed plastic can be obtained by blowing air/gas through molten polyurethane.
This foamed plastic is also known as thermocol.
Note: Thermocol is also prepared by blowing air/gas through polystyrene.
Alternatively, for the production of foamed polyurethane little water is mixed with the
reaction mixture, which reacts with isocyanate group to evolve CO2. The CO2 produced
foams the polymer as it sets.
O = C = N – R – N = C = O + 2H2O H2N – R – NH2 + 2CO2
Properties
(i) Polyurethanes have high strength, good resistance to gas and aromatic
hydrocarbons.
(ii) They have excellent resistance to ozone and oxygen but are susceptible to microbial
attack.
(iii) The polyurethanes can be prepared in different forms varying from hard coatings to

UNIT IV: POLYMERS
flexible rubbers and rigid foams each having different properties.

Coatings: Coatings are hard, glassy and solvent resistant. They have good flexibility
and impact resistance.
Elastomers: Elastomers have excellent abrasion resistance and are resistant to oils,
greases and solvents.
Fibers: Fibers are obtained by reacting di-isocyanate with long chain glycols
which are usually polyesters or polyethers.
Foams: Foams can be flexible or tough depending upon the polymer and the type
of Crosslinking produced. They are light, tough and resistant to heat.
Uses
(i) The polyurethane foams have found the widest use. The flexible foams are
used as upholstery material for furniture, insulation and crash pads.
(ii) The rigid polyurethane foams are used as core material as insulation cover in
refrigerated appliances and vehicles.
(iii) Flexible polyurethanes can also be used for coating rubber articles to give them
additional resistance to abrasion, such as in gymnasium and dance floors.
(iv) Polyurethane resin is used to insulate the wires polyurethane coated wires can
be soldered directly.
(v) Polyurethane fibers with unusually high elasticity are used in foundation
garments and swim wear. They have replaced rubber latex thread in this use.
(vi) Flexible urethane foams are used as cushions for furniture and automobiles and
have replaced rubber foams in these applications because of improved strength,
lower density and easier fabrication.
(vii) Polyurethanes are also used in making mattresses and pillows.
(viii) As they are radiation resistant, they are also used in encapsulation for
integrated-circuit devices.
(ix) Its applications in medical field include its use in dental materials, artificial
heart and skin.
7. Chlorosulphonated Polyethylene Rubber (Hypalon)
Preparation: When polyethylene is treated with a mixture of chlorine and sulphur
dioxide, chlorosulphonated polyethylene is formed. The chlorosulphonation can be
carried out either on the solid material or in solutions.
Properties
The chlorosulphonylation of ethane provides two modifications:
(a) The chlorine atoms break the regularity of polyethene chain structure changing the
crystalline polyethylene to an elastomer.

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UNIT IV: POLYMERS

nCH2 = CH2 (CH2-CH2)n

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segments on the branches and backbone are not the same.

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Compound Chemical Formula Functionality

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MECHANISM OF ADDITION POLYMERIZATION

(ii) Chain propagation

(iii) Chain termination or removal of active centre.

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H+ is the initiator and [F3 BOH]- is the counter ion.

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In this case also the regeneration of the initiator takes place.

(ii) Anionic Polymerization

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3. Coordination Polymerization: Polymerization reactions, taking place in the presence of

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Coordination polymerization is used to prepare sterospecific polypropylene; polydiene etc.

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Difference between Thermoplastics and Thermosetting Resins

COMMERCIALLY IMPORTANT THERMOPLASTICS

nCH2 = CH2 ( CH2 – CH2 )n

The starting material (monomer) is obtained either by dehydration of alcohol or by the

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(b) HDPE: High-density polyethylene is prepared by polymerizing ethylene at low pressure

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(iii) It is resistant to atmospheric oxygen, water and chemicals.

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