Unit-1

INTRODUCTION TO POLYMERS

Monomers, Oligomers, Polymers and their characteristics. Classification of polymers: Natural,

synthetic, linear, cross linked and network, Plastics, elastomers, fibers, Homopolymers and Co-
polymers. Bonding in polymers: Primary and secondary bond forces in polymers, cohesive energy.
Determination of Molecular mass of polymers: Number Average molecular mass (Mn) and weight
average molecular mass (Mw) of polymers.

Introduction
1. What are polymers?

Polymers are high molecular weight compounds whose structures are made up of a large number of simple
repeating units. The interlinking of many units has given the polymer its name‘Poly’ means many,mers means
units=polymers. Small molecules are combined to form a big molecule i.e., polymers.it Can be formed from one
or more chemical compounds.

Eg: Butadiene (CH2=CH-CH=CH2)

butadiene+butadiene+…. +→polybutadiene (m.w-54)(4000 times)

1.1 DEGREE OF POLYMERISATION:

The number of repeating units in a polymer is known as degree of polymerization.

• If n =low, Mol.Wt = 500 – 5000 Dalton units, it is Oligo polymer.

• If n = High, Mol.Wt = 10,000 – 2,00,000 Dalton units, it is High polymer.

1.2 Monomer:
The repeating units are usually obtained from low molecular weight simple compounds referred to as
monomers.The reaction by which monomers are converted into polymers is known as polymerization.The
formation of polyethylene from ethylene is an example of polymerization reaction.

Fig1.2 Example of ethylene monomer

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1.2.1Requirements of monomer

• It should possess at least

a) two bonding sites (multiple bonds) or b) reactive functional groups.

1.3 Oligomers:Oligomers are low molecular weight polymers comprising a small number of repeating units.This
process of formation is called as oligomerization. Oligomers are significantly dependent on the length of the chain.It
is the intermediate of the polymerization reaction.

• Types of oligomers:

• 1.Homo oligomers (multiple copies of same subunits)

• 2.Hetero oligomers (different protein chains).

1.4Characteristics of polymers:

Polymers are having Low density,Economical,Good mould ability,Corrosion resistance,Poor tensile strength,
Poor temperature strength, Non-toxic in nature, Low cost.

1.5Types of polymerization

The reaction in which monomers combine to give polymers is known as polymerization. It can be broadly classified
into three categories as

• addition polymerization:Monomers having multiple bonds (double or triple bond) undergo addition
polymerization. Monomers combine to give polymer through addition reaction without elimination of any
smaller molecules. Therefore, the molecular weight of the resulting polymer will be an integral multiple of
the molecular weight of monomers.Eg:Ethylene to polyethylene.

•
• condensation polymerization:Monomers having same or different types of functional groups undergo
condensation polymerization. The polymerization proceeds by step wise reaction between reactive functional
groups and small molecules are eliminated. Eg: polymerization reaction of nylon66.

•
Copolymerization:. It is a special kind of polymerization, otherwise known as “Joint polymerization”.
The product is known as ‘Co-polymers’. This is superior to other polymerization because it is used to alter the hardness,
strength, rigidity and crystallinity of the monomers.

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 • The differences between two major polymerization methods are tabulated as follows:

S. No Addition Polymerization Condensation Polymerization

1 Eg. PVC Eg. Nylon 6,6
2 Otherwise known as “Chain growth Otherwise known as “Step wise
Polymerization”. Polymerization”.
3 Monomers are adding together to form polymers. Monomers are condensed to form polymer.
4 No elimination of other molecules. Elimination of smaller molecules occur.
5 At least one multiple bond presence is essential Monomers must have two or more functional
condition. groups.
6 Homo polymers are formed. Hetero polymers are formed.
7 Thermoplastics are formed. Thermo set plastics are formed.
8 Molecular weight of the polymer is the integral Need not be so.
multiple of monomers.
9 Monomers disappear slow and steadily. Monomers disappear at the initial stage of the
reaction.
10 Longer processing time is needed to increase Longer time is essential for increasing
yield. molecular weight.

1.2Classification of polymers:

Based on origin of source:

Natural polymers:Depending on their origin, polymer can be grouped into natural or synthetic.Those isolated from
natural materials are called natural polymers.Example: cotton, wool, silk and rubber. It is also non-toxic.

Advantages:Readily and abundantly available,Comparatively inexpensive,Nontoxic products,Biodegradable.

Synthetic polymers:Polymers synthesized from low molecular weight compounds are called synthetic polymers.
Example : polyethylene ,nylon, PVC and terylene

Based on the structure:

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 Linear polymer:In these polymers’ monomers are linked with each other and form a long straight chain. These
polymer chains do not consist any side chains. A linear polymer can be schematically represented by a single
line. Example: polyethylene

-A-A-A-A-A-A-A-A-A-A- a polymer made of A atoms.

nCH2=CH2 →-CH2-CH2-→-(CH2-CH2-)n

Cross linked polymer:They have long straight chain with different branched side chains.Molecules are irregularly
packed. Example:polyethyleneHDPE-High Density polymer LDPE-Low Density polymer

Network polymers:Network polymers have trifunctional monomeric units that are formed by many
interconnected polymer chains.They are giant molecules in which movement of individual monomeric unit
is prevented by strong cross links.It is having three active covalent bonds. It should be in three-dimensional
network.Eg: Bakelite, urea formaldehyde, melamine formaldehyde,etc.

1.3Plastics:The term plastic or plastic material, is given to “organic materials of high molecular weight, which
can be moulded into any desired form,when subjected to heat and pressure in the presence of a catalyst’.The term
plastics are differentiated from the resin.resins are the basic binding materials which form a major part of the
plastics,and which actually has undergone polymerization and condensation reactions,during this preparation.

1.3.1Thermoplastic polymers:

These polymers are linear,long chain polymers, which can be softened on heating and cooling reversibly.This is
called thermoplastics’.,their hardness is a temporary property, subject to change with rise or fall of
temperature.Eg:polythene,polypropylene (PP), polyvinylchloride (PVC), PTFE.,etc.

1.3.2Thermosetting polymers(thermosets):Thermosets are those polymers, which during moulding (by heating)get
hardened and once they have solidified i.e.they are permanent polymers.Such polymers during moulding acquire
three-dimensional cross-linked structure,with strong covalent bonds.

Thus,a thermosetting polymer once moulded cannot be reprocessed.

Eg: polystyrene (terylene), Bakelite, epoxy resin, melamine, urea formaldehyde etc.

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Differences between Thermoplastics and thermosetting plastics

S.No THERMOPLASTICS THERMOSETTING PLASTIC

1 Eg.PVC , Polyethylene Polyester, Bakelite
2 Plastics which are melted at high They cannot be remoulded after their first
temperature, solidified at low temperature usage.
They can be remelted and remoulded into
any desired shapes for any number of times.
3 Scrap can be used again. Scrap cannot be used again.
4 Formed by addition polymerization Formed by condensation polymerization
5 The bond strength is low The bond strength is high
6 Molecular weight is low Molecular weight is high
7 Soluble in organic solvents. Insoluble in organic solvents.
8 Prepared by Injection moulding Prepared by compression moulding.
9 They have linear structure They have complex 3D structure.

1.4 Elastomers:Elastomer are high polymers, which have elastic properties in excess of 300%.An
elastomer(rubber)is any vulcanisable man-made rubber-like polymer. when vulcanized into the rubbery products
exhibiting good strength and elongation, polymers used as elastomers. An elastomer molecule is not straight
chained eg: polyethene, nylon etc.,but in the case of coil,it can be stretched like a spring.Natural rubber consists
of basic material latex, which is a dispersion of isoprene.The isoprene molecules polymerize to form,long –coiled
chains of cis –polyisoprene.Structure of natural rubber:

1.4.1Fibres: are those polymers whose chains are held by strong intermolecular forces like hydrogen bonding.They
are crystalline in nature and of high tensile strength,due to strong intermolecular forces.

Eg: nylon,polyester

1.5Homopolymers:When all the repeating units in a particular polymer have the same structure,that polymer is called
a homopolymer.Eg: vinyl chloride

1.5.1Copolymers:When different repeating units make up the polymer chain ,the polymer is called a copolymer.A-
A-B-B-B-A-B-A-A-B—

Types of copolymer:

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 • Alternating copolymers(A-B-A-B-A-B-)

• Block copolymers (A-A-A-A-B-B-B-B)

• Random copolymers(A-B-B-B-A-A-B-B-)

• Eg:poly[vinyl chloride –vinyl acetate ]copolymers

1.5.6Bonding in polymers:A molecule is connected by covalent bonds.Chemical reactions are required to form
or break covalent bonds. Weaker attractions often form between molecules, encouraging them to stick together
in groups. The weaker attractions are called secondary bonds or intermolecular forces. These can be overcome
by adding heat or dissolving in a liquid. the functional groups on a polymer determine the type and strength of
its secondary bonds.

• Types of interactions present in bonding of polymers:

Polar interactions:The valence electrons moving around a molecule may not be symmetrically distributed. The
nonmetallic elements closest to the right top corner of the periodic table - nitrogen, oxygen, fluorine and chlorine
- tend to shift shared electrons away from carbon and hydrogen. When there is a functional group with one of
those elements, it has a slight negative charge and the rest of the molecule (carbon and hydrogen) is slightly
positive. The molecule is polarized. Its positive sections are attracted to negative sections of neighboring
polymers.eg: PET (Poly (ethylene terephthalate).it has oxygen containing functional groups make it
polar.Positive and negative charges can be localized on a covalent molecule since they have no path for
conduction of electrons. The carbon atoms in the backbone always follow the octet rule with four covalent bonds,
so can't pass extra electrons along the chain. If polymer fibers are rubbed together, they can build up a static
electricity charge.

• Hydrogen bonds:Molecules with either -N-H or -O-H groups will form strong secondary bonds. Eg:hydrogen
bonding in water.This phenomenon is responsible for the relative high boiling point of water, and for the fact
that its solid form (ice) is less dense than its liquid form. Polymers with hydrogen-bonding groups will soak up
water.

Non-polar interactions:As valence electrons move around the nuclei in a nonpolar polymer, like polyethylene or
polyfluoroethylene, they can become temporarily imbalanced. So,one part of a molecule would be negative, another
part positive; it is temporarily polar. These occasional imbalances are enough to allow nonpolar molecules to attract
each other, but the interaction is much weaker than that observed for polar or hydrogen bonding polymers.

eg: Polyfluoroethylene is nonpolar (not polar) because it is completely covered with fluorine atoms; there is no
exposed positive section to interact with a neighboring molecule's negative section.

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MOLECULAR WEIGHT OF POLYMERS
The molecular weight of polymers is not unique like small molecules. Since polymeric molecular weights are in the range, it is
always given as average molecular weight.
NUMBER AVERAGE MOLECULAR WEIGHT (𝐌 ̅ n)
It is the ratio of sum of molecular weights of individual molecules to the total number of molecules in the mixture.
It is obtained by measuring the colligative properties.
It is a good index of physical properties such as impact and tensile strength.
Consider a polymer mixture which contains
n1 molecules are with molecular weight M1
n2 molecules with molecular weight M2 and so on.,
If ni molecules are with molecular weight Mi then,
̅ n= n1M1 +n2M2 + …. + niMi
M
n1 + n2 + ….+ ni
̅ n = ΣniMi / Σ ni
𝐌
̅ w)
WEIGHT AVERAGE MOLECULAR WEIGHT (𝐌
It is the ratio of sum of molecular weights of individual molecules to the total weight of molecules in the mixture. It
is obtained by light scattering and ultra-centrifugation techniques.
Consider a polymer mixture which contains
w1 is the weight of polymer with molecular weight M1
w2 is the weight of polymer with molecular weight M2
and so on.,
Let wi molecules are with molecular weight Mi, Then,
̅ w=
M w1M1 + w2M2 +wiMi
w1 +w2 + …..+ wi
̅w
𝐌 = ΣwiMi / Σ wi
But, number of moles n = w / M
So, w = nM
We can replace w1 by n1M1, w2 by n2M2 and wi by niMi
̅ w=n1M1M1
M + n2M2M2 + ….+niMiMi
n1M1+n2M2+…. +niMi
̅w
𝐌 = ΣniMi2 / Σ niMi
POLYDISPERSITY INDEX (PDI)
̅ w to number average molecular weight M
The ratio of weight average molecular weight M ̅ n is known as polydispersity index or
distribution ratio.
Polydispersity index= ̅w / 𝐌
𝐌 ̅n
i. For monodispersed system, M ̅w = M ̅n
If a polymer contains molecules of same molecular weight, such system is known as monodispersed system. But it
is unreal condition. Such possibility is available only in simple chemical compounds like water, alcohol etc.,

ii. For polydispersed system, M ̅ w>M

̅n
If a polymer contains molecules of different molecular weight, it is polydispersed system. The deviation of ratio from
the unity is taken as a measure of polydispersity of the polymer sample. For all synthetic polymers, PDI is higher
than 1.
iii. Higher values of the ratio indicate greater polydispersity. It means all the molecules of the polymers will not have
identical molecular weight.

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Cohesive energy:
Cohesive energy density Since polymers have negligible vapor pressure, the most convenient method of determining
is to use group molar attraction constants. These are constants derived from studies of low-molecular-weight
compounds that lead to numerical values for various molecular groupings on the basis of intermolecular forces. Two
sets of values (designated G) have been suggested, one by Small, derived from heats of vaporization and the other
by Hoy, based on vapor pressure measurements.

Reference:

Textbook of polymer chemistry., Gowrikar,Vishwanathan.,

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 UNIT-2

MECHANISM OF POLYMERIZATION

Chain growth polymerization: Cationic polymerization-anionic polymerization –free radical

polymerization. Stereo regular polymers: Ziegler Natta polymerization, Step growth
polymerization.

Chain growth polymerization

• Chain growth polymerization is characterized by a self –addition of the monomer molecules, very rapidly
through a chain reaction. In this polymerization no byproduct is formed. The bifunctionality is provided by
the double bonds present in the monomer.i.e. compounds containing reactive double bonds undergo chain
growth polymerization. Eg: vinyl,allyl, dienes, olefins. Chain polymerization mainly consists of three major
steps, namely,

• Initiation

• Propagation

• termination

followed by the process is, Free radical cationic and anionic polymerization reaction.

• 1.1Free radical polymerization:The initiation of the polymer chain is brought about by free radicals
produced by the decomposition of compounds called initiators.Chain growth means continuous addition of
the monomer units to form polymer chain.

• Initiation:free radicals contains lone pair of electrons.A free radical is highly reactive and can attack any
molecule which has a lone pair of electrons this process is calledinitiation. Eg:benzoyl peroxide,azobis
isobutyronitrile.

• STEP1: Initiators is thermally unstable compounds and decompose into products called free radicals.

• The initiators can be written as R: R

When heat is supplied in this compound, the molecule is split into two symmetrical components.

R…. R → R°R°+M →M

• STEP2: Propagation:In this propagation step, the radical site at the first monomer unit attacks the double
bond of a fresh monomer molecule.This results in the linking up of the second monomer to the first and the
transfer of the radical site from the first monomer unit to second, by the unpaired electron transfer process.
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• M1°+M → M2°

• M2°+M → M3°

• Mn°+m → Mn+1

• STEP3: Termination:This process involves coupling of the two lone electrons, this kind of termination is
called as termination of coupling.

• There are two types of coupling reactions.

1.disprpotitionation 2. dead polymer

1.2 Ionic polymerization:

• The ionic mechanism of chain polymerization also involves an attack on the pi electron pair of the monomer.It
is a positive or negative ion.

• Two types of ionic polymerization.

1.cationic polymerization

2.anionic polymerization

1.2.1 Cationic polymerization:The proton pulls the pi electron pair towards it and positive charge of the
proton is transferred to the end of the monomer molecules, forming carbonium ion. In this process, a
sigma bond is formed between the proton and the monomer unit and the polymer chain growth initiated.
The carbonium ion is attacks the pi electron of the second monomer molecules and pulls it over. the
positive charge is transferred to the second monomer unit.
Three steps are involved in this process.
Initiation
Propagation
termination
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 • 1.2.2 Anionic polymerization:Monomer is done by negatively charged ion,an anion.Such a system has
electrons and extra electrons and the resultant negative charge attacks the pi electron pair pushing it ,to the
end of the molecule.It forms sigma bond with the monomer molecules. next carbanion is formed and now
propagates the chain growth by attacking the second monomer unit followed by termination process.

Stereo regular polymers (stereo specific polymers):

• Each monomer segment is in a regular configuration giving a definite structural regularity to the polymer
molecules. The structural regularity in a polymer are termed as Optical and geometrical isomerism of the
main chain atoms or substituent’s in the polymer molecule.

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 • 1.3.1 Ziegler –Natta polymerization:Ziegler-Natta process for the polymerization of olefins used as a
catalyst formed from TiCl4 to TiCl3 and Al (C2 H5) The rate of polymerization reaction is proportional to the
total amount of TiCl3 (Al (C2 H5) reduces to TiCl4 to TiCl3 and in the presence of the olefin and is
independent of AlEt3 concentration.

• These are special type of coordination catalyst comprising two components as against single -component
organometallic compounds.

• The two components are generally referred to as the catalyst and the co-catalyst. The monomer is complexes
with the metal ion of the active center before its insertion into the growing chain. When the catalyst and
cocatalyst components are mixed there occurs a chemisorption of aluminum alkyl on the titanium chloride
solid surface, resulting in the formation of an electron deficient bridge complex of the structure.

• This complex now active center. The monomer is then attracted towards the TI-C bond is the active Centre.
When it forms a 𝑝𝑖𝜋complex with the 𝜋.the bond between R and olefins up producing an electron deficient
Ti and a carbanion at R.

•
Step growth polymerization:

• The polymer buildup proceeds through a reaction between functional groups of the monomers. Organic
functional groups can be made use of this polymerization. Step growth polymerization are mostly
accompaigned by the elimination of small molecules.

• Polycondensation reaction: This is brought about by monomers containing two or more reactive functional
groups condensing with each other. Basic reactions the same as between various functional groups in low
molecular weight organic compounds. Forexample, the reaction between a hydroxyl group and a carboxylic
group, giving an ester and a water molecule.

• Step polymerization regarding,

• That monomers should have two functional groups for polymerization to proceed.
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• That polymerization proceeds by step wise reaction between functional groups. that only one type of reaction

• The polymer formed still contains both the reactive functional groups at its chain ends and it also active and
dead as in chain polymersation.

• Example polycondensation reaction of polyethylene terephthalate.

•
• Polyaddition reaction: This is brought about by migration of atoms from one another, or to the intermediate
product.

• Vinyl monomers as well as monomers pairs with reactive functional groups can undergo polyaddition
polymerization.

• Styrene, for example can be polymerized in the presence of perchloric acid by this method.

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 UNIT-4

INDUSTRIAL POLYMERS

Preparation of fiber forming polymers, elastomeric material.Thermoplastics: Polyethylene, Polypropylene,

polystyrene, Polyacrylonitrile, Poly Vinyl Chloride, Poly tetrafluoro ethylene, nylon and polyester.
Thermosetting Plastics: Phenol formaldehyde and epoxide resin. Elastomers: Natural rubber and synthetic rubber
- Buna - N, Buna-S and neoprene. Conducting Polymers: Elementary ideas, examples: poly Sulphur nitriles, poly
phenylene, poly pyrrole and poly acetylene

Preparation of fiber forming polymers, elastomeric material.

4.Fiber forming polymers

o These are polymeric materials from which man-made fibers are formed.
o Nylon is a typical example of fiber-forming polymers. They exhibit high tensilestrength, highrigidity or
stiffness and undergo irreversible deformation.
o The molecules in these materials should have a very high DP.
o They should be packed very close to each other in a highly held together by strong interchain cohesion forces
which resist deformation and do not allow any relative movement between the chains.
o The material should have a very high Crystallizable.
o This property can be increased by regularity, polar groups in the repeat units and stiffing units such as
aromatic and cyclic rings in the chain backbone.

Elastomeric materials:

Elastomeric are popularly known as rubbers. Balloons, shoe soles, tyres, surgeons gloves, garden hoses, are
examples of articles made of elastomerics.

Natural rubber is the most classical example made of elastomeric.

These are several synthetic elastomeric include polybutadienes, styrene-butadiene (SBR)and acrylonitrile
copolymers, polyisoprene, polychloroprene, ethylene-propylene copolymer, isoprene isobutylene copolymer
silicone rubbers.

4.1THERMOPLASTICS

These polymers are linear,long chain polymers, which can be softened on heating and cooling reversibly.This is
called thermoplastics’.,their hardness is a temporary property, subject to change with rise or fall of
temperature.Eg:polythene,polypropylene (PP), polyvinyl chloride (PVC), PTFE.,etc.

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 4.1.1POLYETHYLENE

Polyethylene is made by addition or radical polymerization of ethylene (olefin) monomers.

Preparation:

Types of Polyethylene (PE):

Low-density polyethylene (LDPE)

High-density polyethylene (HDPE)

PROPERTIES:
o Higher tensile strength compared to other forms of polyethylene
o Low cost polymer with good processability
o Good low temperature resistance
o Temperature resistance up to 80°C continuously and 95°C for shorter times.
o Low cost polymer with good processability
o High impact strength at low temperature, good weatherability
o Excellent electrical insulating properties
o Very low water absorption
o FDA compliant
o Transparent in thin film form

USES:
It is used in the field of pipe fittings, wire cables, fuel tanks, packaging…

DISADVANTAGES:

• Susceptible to stress cracking

• Lower stiffness than polypropylene
• High mould shrinkage
• Poor UV- and low heat resistance
• High-frequency welding and joining impossible

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4.1.2 Polypropylene:

Preparation:

Properties:

▪ Resistant to heat distortion

▪ Excellent electrical properties
▪ Chemically inert
▪ Inexpensive and poor resistance capacity

Uses:

It is used in TV cabinets. luggage’s, packing films, sterilized bottles.

4.1.3 polystyrene

Preparation:

Properties:

Good dimensional stability even at low temperature

Good toughness
High elongation, high resistance to stress cracking.
Lower hardness and rigidity than by alcohols, ketones, ethers etc.

Uses:

Mainly used for the manufacture of motor tyres.

Floor tiles, gaskets,foot-wear components
Tank linings, insulation for high voltage wire and cables.

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4.1.4 polyacrylonitrile

Preparation

It is also called as polyvinyl cyanide.it is produced from acrylonitrile by the radical polymerization technique
using peroxide initiators.

Acrylonitrile can be obtained by from acetaldehyde and hydrogen cyanide.

Properties:

• PAN is soluble in DMF, Dimethyl sulphoxide, adiponitrile,

• Resistance to heat up to around 200c and exhibits very good mechanical properties.

Uses:

o It is used to produce PAN fibers.

o The copolymer of acrylonitrile with butadiene is a material of great industrial importance.

4.1.5 polyvinyl chloride (PVC)

Preparation: it is obtained by heating a water emulsion of vinyl chloride in presence of a small amount of benzoyl
peroxide or hydrogen peroxide in an autoclave under pressure.

Properties:

✓ PVC is colorless, odorless, non-inflammable chemically inert powder, but soluble in chlorinated
hydrocarbons, such as ethyl chloride
✓ PVCis most synthetic plastics
✓ Greater stiffness and rigidity
✓ Uses:
• Making sheets
• Tyres, cycle, motorcycle mudguards
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 • Rain coats, table cloths, curtains, electrical cables

4.1.6, Polytetrafluoroethylene (TEFLON)

Preparation:

It is obtained by polymerization of water-emulsion of tetrafluoroethylene, under pressure in presence of benzoyl

peroxide as catalyst.

Properties:

High density, waxy touch, very low coefficient of friction,

good electrical and mechanical properties.
Extreme toughness, high softening point, very viscous, opaque mass.

Uses:

As insulating material and for making gaskets,

packings, pump parts, tank linings, chemical carrying pipes, asbestos fibers and clothes.
Non lubricating bearings and non-sticking stop cocks.

4.1.7 NYLON

Preparation:

Nylon 6 6 is obtained bt the polymerization of Adipic acid with hexamethylene diamine.

Properties:

They are light, horny and high melting

They are insoluble in common solvents
They have good strength, absorb little moisture and trip dry in nature.
Very flexible

Uses:

It is used for fibers, making socks,

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 ladies’ shoes,
under garments, dresses, carpets.

4.1. Polyester

Preparation:

Polyester resins are condensation products of dicarboxylic acid with dihydroxy alcohols. For example, terene is
formed by condensation of ethylene glycol (a diol)and terephthalic acid(a saturated diacid).

Properties:

Polyester is used to good forming material and is converted into commercial fibers.
High stretch -resistance
High crease and wrinke-resistance
High resistant to mineral and organic acids, but is less resistant to alkalis.

Uses:

It is mostly used for making synthetic fibers, like terylene, Dacron

For blending with wool to provide better crease and wrinkle resistance
As glass reinforcing material in safety helmets, aircrafts battery boxes, etc.

4.2 Thermosetting Plastics:

Thermosetting polymers(thermosets):Thermosets are those polymers, which during moulding (by heating)get
hardened and once they have solidified i.e., they are permanent polymers.Such polymers during moulding acquire
three-dimensional cross-linked structure,with strong covalent bonds.

Thus,a thermosetting polymer once moulded cannot be reprocessed.

Eg: polystyrene (terylene), Bakelite, epoxy resin, melamine, urea formaldehyde etc.

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4.2.1 Phenol formaldehyde resin

Phenol formaldehyde resins are formed by the condensation between phenol and formaldehyde.

The polycondensation reaction can be catalyzed either by acids and bases.

Uses:

The Bakelite resins are usually compounded with fillers such as asbestos powder or sawdust and used for
moulding electrical items, telephone instruments.
The resols are used for making laminates, paper, fabric or asbestos cloth are impregnated with the resols.
Many layers of the impregnated material are pressed together in a hydraulic press and heated to around 500
C.
To form a single sheet of a greater thickness.

4.2.2 Epoxide resins:

the epoxy polymers are basically polyethers.one type of epoxy polymer is prepared from epichlorohydrin and
bisphenol-A.

The reaction is carried out with excess of epichlorohydrin

The epoxy resins obtained through these reactions will be either highly viscous liquids or solids with high melting
points.

The epoxy resins can be further cured with substances such as amines,polysulfides and polyamides.

Preparation:

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 .

Properties:

• Chemical resistant material

• Good adhesion
• Excellent structural adhesives.

Uses:

▪ It is used in industrial floorings, foams, potting materials for electrical insulations.,

▪ One constituent in many of the fiber-reinforced plastics (FRP)is a poxy polymer.

4.3 ELASTOMERS:

➢ Elastomer are high polymers, which have elastic properties in excess of 300%.
➢ An elastomer(rubber)is any vulcanisable man-made rubber-like polymer. when vulcanized into the
rubbery products exhibiting good strength and elongation, polymers used as elastomers.
➢ An elastomer molecule is not straight chained Eg: polyethene, nylon etc., but in the case of coil, it can
be stretched like a spring.

4.3.1 BUNA-S:

It is probably the most important type of synthetic rubber, which is produced by copolymerization of
butadiene and styrene.

Preparation:

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 Properties:

o It possesses high abrasion-resistance

o High load bearing capacity and resilence.it gets oxidized in presence of ozone present in the
atmosphere
o It swells in oils and solvents.
o It can be vulcanized in the same way as natural rubber by Sulphur or Sulphurmonochloride.

Uses:

o Mainly used in the manufacture of motor tyres.

o Floor tiles, shoe soles, foot wear components, wire and
o cable insulations carpet backing adhesions, tank linings etc.…

4.3.2 BUNA-N:

Is made by copolymerization of isobutene with small amounts (usually 1 to 5%) of isoprene.

Preparation:

Properties:

➢ Low permeability to air and other gases

➢ Excellent resistant to heat, abrasion, ageing, chemicals, polar solvents
➢ It is soluble in benzene.
➢ Good electrical insulating properties.

Uses:

➢ For making cycle, automobile tubes, automobile parts, hoses,

➢ conveyor belts for food and other materials,
➢ tank linings, insulation for high voltage wires and cables.
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4.3.3NEOPRENE:

POLYCHLOPRENE IS OTHERWISE CALLED AS NEOPRENE.

Chloroprene is manufactured by the addition of hydrogen chloride to vinyl acetylene.

Vinyl acetylene is produced by the dimerization of acetylene.

The polychloroprene is synthesized by the emulsion technique.

It can be readily vulcanized with the help of zinc oxide or magnesium oxide.

Properties:

The vulcanized products are having excellent tensile strength.

Higher oil resistance

Uses:

➢ Coating to wires and cables

➢ Shoe soles
➢ Solid tyres
➢ Gloves and industrial hoses.

4.4 Conducting polymers:

Polymers which can conduct electricity are called conducting polymers. Ordinary polymers obtained by usual
methods are nearly insulators. However, some specific polymers may act as conductors.

Classification: Conducting polymers may be classified as

1.Intrinsically conducting polymers: These types of polymers have a solid backbone made up of extensive conjugated
system, which is responsible for conductance. They may be of two types: (i) Conducting polymers having conjugated
π-electrons in the backbone: These polymers essentially contain a conjugated π-electron backbone responsible for
electrical charge. Under the influence of electrical field conjugated π -electrons of the polymer get excited, which
can then be transported through the solid polymer. Further, overlapping of orbitals of conjugated π -electrons over
the entire backbone results in the formation of valence bands as well as conduction bands, which extend over the
complete polymer molecule. The presence of conjugated π -electrons in polymers increases itsconductivity, e.g.,
pyrrole.

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 1. (ii) Doped conducting polymers: The conducting polymers obtained by exposing the polymer to a charged
transfer agent in either gas phase or in solution are called doped conducting polymers. Doping is the process
by which conductivity of the polymers may be increased by creating negative or positive charge on the
polymer backbone by oxidation or reduction. Doping may be of two types:p-Doping and n-Doping

2. Extrinsically conducting polymers: Those conducting polymers which owe their conductivity due to the
presence of externally added ingredients in them are called extrinsically conducting polymers. They are of
two types: (I) Conductive element filled polymers: In this type, polymer acts as a binder to hold the
conducting elements together in solid entity. The minimum concentration of the conductive filler, which is
added to let the polymer start conducting is called the percolation threshold. Important characteristics of these
polymers are: (a) They possess good bulk conductivity. (b) They are cheaper. (c) They are light in weight.
(d) They are mechanically durable and strong. (e) They are easily processable in different forms, shapes and
sizes

3. (ii) Blended conducting polymers: These types of polymers are obtained by blending a conventional polymer
with a conducting polymer either physically or chemically. Such polymers can be easily processed and
possess better physical, chemical and mechanical properties .

Applications of conducting polymers:

Conducting polymers are widely used: 1. In rechargeable batteries. 2. In making analytical sensors for pH, O2,SO2,
NH3, glucose, etc. 3. In the preparation of ion exchangers. 4. In controlled release of drugs. 5. In optical filters. 6. In
photo voltaic devices. 7. In telecommunication systems. 8. In micro-electronic devices. 9. In bio-medical
applications.

Examples:

Poly phenylene:

This polymer is composed entirely of aromatic rings forming the chain backbone.

The starting material is Para dibromo benzene

This compound when treated with activated copper powder at high temperature, yields Para phenylene as follows.

The polymer can be prepared by the cationic polymerization of benzene with aluminum trichloride and cupric
chloride.
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This polymer is very brittle and insoluble caused by the presence of aromatic ring chains linked together through p-
positions.

It can derive from the presence of resonance stabilized conjugated double bonds in the aromatic rings.

Polyaniline: it is aromatic conjugatedpolymer, synthesized by electrochemical oxidation of aniline using ammonium

peroxodisulphate or potassium iodate as oxidizing agent.

Polyaniline has a unique structure consisting of an alternating arrangements of benzene rings and nitrogen atoms.

The nitrogen atoms exist either as an amine or imine.

Depending on the relative concentration of nitrogen, polyaniline exists in three different oxidation state.

Polypyrrole:

Polypyrrole is a type of organic polymer formed from by polymerization of pyrrole is an insulator but ii is oxidized
derivatives are good conductors. The conductivity of the materials depends on the conditions and reagents used in
the oxidation, conductivities range from 2 to 100 S/cm.

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Polyacetylene (PA)
Polyacetylene is the simplest molecular framework possessing conjugated polymer.

It is also known as aniline black.it is produced from bulk powder, cast films and fibers.

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