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UNIT 3 POLYMERS

3.1 Introduction

Polymer – Definition:
Polymers are the substances consisting of giant or macromolecules
made by linking a large number of smaller molecules (monomers).
Polymer is a molecule formed by joining of thousands of smaller
molecular units together by chemical bonds.
A chemical process that leads to the formation of polymer is known as
polymerization.

Degree of polymerization: The number of repeat units (or) monomeric

units available in the polymer is known as degree of polymerization.

Functionality:

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Definition: The number of bonding sites (or) reactive sites or functional
groups present in the molecule.

Ex: The double bond in vinyl monomers (CH2 = CHX) can be considered as
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a site for two free valencies. When the double bond is broken, two single
bonds become available for combination.
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H 2 C=CHX → --- CH 2 – CHX ------

1. When the functionality of monomer is two bifunctional linear (or)

straight chain polymer is formed.
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Ex: (a)vinyl monomers (b)adipic acid (c)hexamethylene diamine

(d)terephthalic acid(e)ethylene glycol (f )amino acid
Example for polymer: HDPE (high density polythene)
2. When the functionality of monomer is three (tri-functional), three-
dimensional net work polymer is formed.
Ex: phenol, glycerol
Examples for polymers : Urea formaldehyde, phenol formaldehyde.

Examples for bifunctional monomers:

i)Vinyl monomers (HC 2 = P-CH) [ where P = pendant group]

a)ethylene b)propylene c)vinyl chloride d)vinyl cyanide e)vinyl
acetate
f)styrene g)acrylic acid h)methyl methacrylate

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ii)Dicarboxylic acids having general formula (HOOC – R – COOH)

a)succinic acid b)adipic acid c)terephthalic acid

iii)Amino acids with the general formula H 2 N – R-CH - COOH

a)glycine b)alanine c)valine d) - amino caproic acid

iv)Diols with the general formula HO – H 2 C – R – CH 2 - OH

a)ethylene glycol

v)Diamines with the general formula H 2 N-CH 2 -R-CH 2 -NH 2

a)hexamethylene diamine

when a trifunctional monomer is mixed in small amounts with a bifunctional

monomer, a branched chain polymer is formed.

Polymerisation:
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Ex: LDPE (LOW density polyethene)

Definition: “ The process in which the simpler molecules combine together

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to form very large molecule having high molecular weight is known as
polymerization”. The molecule is known as polymer.
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The different ways of doing polymerization are –
i)By opening a double bond
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Ex: n CH 2 = CH 2  (CH 2 – CH 2 ) n
ethane polythene

n CH 2 = CH  (CH 2 – CH)n
Cl Cl
Vinyl chloride polyvinyl chloride
ii)By opening a ring

iii)By using molecules having two functional groups

Ex: nH 2 N – (CH 2 )6 – NH 2 + n HOOC – (CH 2 ) 4 – COOH
hexamethylene diamine adipic acid

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3.2 Types of polymerization:

Polymers can be synthesized by the following polymerization processes.
I. Addition polymerization (or) chain polymerization
II. Condensation or, step or, step growth polymerization
III. Copolymerisation

I) Addition polymerization:
The addition polymerization is the process in which the liniking together of
monomer molecules by a chain reaction is observed.

Polymer synthesized by addition polymerization has the same empirical

formula as that of monomer.

No molecule is evolved during polymerisation and the polymer is an exact

multiple of the original monomeric molecule.

Where P = pendant group IT

Ex: nCH 2 = CH  (CH 2 – CH 2 )n
P
R
P -H -CH 3 -Cl -C 6 H 5
Polymer Polythene Polypropene Polyvinyl Polystyrene
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chloride
* Addition polymerization is usually induced by light, heat or, a catalyst for
opening the double bond of the monomer and creating the reactive sites.
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II) Condensation polymerization:

An intermolecular reaction involving two different bifunctional reactants

with affinity for each other and taking place through repeated condensation
reaction is known as condensation polymerization.
* Monomers having – COOH and – OH or, -COOH and –NH 2 undergo
condensation polymerization.
The reaction always accompanies the elimination of H 2 O, HCl, CH 3 OH,
NH 3 molecules.
Examples:
1)Nylon 6.6 : [polymerization involving adipic acid and hexamethylene
diamine]

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2)Terelene: (polyethylene terephthalate)

[polymerization involving ethylene glycol anol terephthalic acid]
3)Polyurethane: Polymerisation involving a diol
Ex: bisphenol A) and a diisocyanate (ex: toluene diisocyanate) to give
polyurethane.
Condensation polymerization involving trifunctional reactants give rise to a
cross – linked three-dimensional polymer.
Differences between addition and condensation polymerization:

Addition polymerization Condensation polymerisation

1)It requires the presence of a double bond 1)It requires two reactive functional groups
in the monomer to be present at both ends of the monomer.

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There should be at least two different bi-or,
poly- functional monomers having
functional groups with affinity for each
other.
2. In this reaction, no by product is formed 2) generally a by product is formed in this
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reaction.
3. Homo-chain polymer is obtained. 3) Hetero-chain polymer is obtained (either
(generally thermoplastic) thermoplastic or, thermostat)
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4. The growth of chain is at one active 4) The growth of chain occurs at minimum
centre. of two active centres.

5.Examples: 5)Examples:
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a)polymerisation of ethylene to form a)condensation polymerisation of

polythene(PE) hexamethylene diamine and adipic acid to
n CH 2 = CH 2  (CH 2 – CH 2 )n form Nylon 6.6
ethylene polythene nH 2 N – (CH 2 ) 6 – NH 2 + hexamethylene
diamine
nHOOC –(CH 2 ) 4 – COOH adipic acid

b)polymerisation of vinyl chloride to form

poly-vinyl chloride (PVC) b)condensation polymerisation of
n CH 2 = CH  (CH 2 – CH)n terephthalic acid and ethylene glycol to
give polyethylene terephthalate (terelene)
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c)polymerisation of styrene to form c)condensation polymerisation of tolerene

polystyrene. diisocyanate and diol to form polyurethane
n CH 2 = CH  (CH 2 – CH)n

styrene polystyrene

d)polymerisation of acrylonitrile (vinyl d)Nylon -6:

cyanide) to form polyacrylonitrile NH2 – (CH2)5 – COOH   - amino
(orlon). caproic acid (NH – (CH2)5 –C)n Nylon – 6
n CH2 = CH  (CH2 – CH)n
CN CN
Vinyl cyanide polyacrylonitrile
(acrylonitrile) (orlon)

e)polymerisation of methyl methacrylate to e)condensation polymerisation of

form polymethyl methacrylate (plexiglas, hexamethylene diamiinie anid sebaec acid
Lucite) to form nylon – 6, 10.
methyl methacrylate NH2 – (CH2)6 – NH2 + hexamethylene

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polymethyl methacrylate (Plexiglas, diamine HOOC – (CH2)8 – COOH 
Lucite) Sebaeic acid
(N – (CH2)6 – N – C – (CH2)8 – C)n
Nylon – 6, 10
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f)Nylon – 11:
NH2 – (CH2)10 – COOH  amino
decanoic acid
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(N – (CH2)10 – C)n
Nylon - 11
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III) Copolymerisation:

Addition polymerisation involving a mixture of two (or) more suitable or

compatible monomers gives a copolymer and the process is known as
copolymerization.
(OR)
A reaction in which a mixture of two (or) more monomers is allowed to
undergo polymerisation is known as copolymerization. The polymer is
known as copolymer.
Examples:
1)Copolymerisation of styrene and methyl methacrylate

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2)Copolymerisation of acrylo nitrile and vinyl chloride

3)Copolymerisation of styrene and 1,3 – buta diene.
mCH2 = CH + n CH2 = CH – CH = CH2 copolymerisation

Depending on the linkage, the following four types of monomers are

possible.

S.No. Copolymer Structure Description

1) Atternate -M 1 -M 2 -M 1 -M 2 -M 1 -M 2 - Monomers are
arranged in
regular alternate
fashion
2 Block A block of
-M 1 -M 1 -M 1 -M 2 -M 2 -M 2 - repeating unit of
one kind of

IT monomer is
followed by
block of another
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kind of monomer
3 Random -M 1 -M 2 -M 2 -M 1 -M 2 -M 1 - Monomers
randomly
distributed along
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the polymer
chain
4 Graft Have branched
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-M 1 -M 1 -M 1 -M 1 -M 1 - structures in
which the
monomer
segments on the
back bone and
branches differ

3.3 Chain growth mechanism : [Free radical mechanism]

The mechanism involves three steps.

I. Chain initiation II. Chain propagation III Chain termination

I. Chain Initiation: This involves two steps.

i)Decomposition of the initiator to form free radicals

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In  2R*

ii)Addition of the first vinyl monomer molecule to the free radical to form
intermediate (I)

R + CH 2 = CH  R – CH 2 – CH

I) chain initiation : Initiator added to the monomer undergoes dissociation

to form free radicals. Initiators commonly used are acetyl peroxide (CH 3 CO
– O – O – COCH 3 ), benzoyl peroxide (C 6 H 5 COO-O-COC 6 H 5 ) and azobis –
isobutyronitrile (AIBN).
In  2R*
R*+M RM* where M = Monomer

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C 6 H 5 CO –O-O-COC 6 H 5  2C 6 H 5 COO* (or) (R*)
Benzoyl peroxide free radical

R*or C 6 H 5 COO* + H 2 C = CH  R-CH 2 - *CH

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II ) Chain propagation: The intermediate (free radical) immediately reacts
with a monomer molecule to form the reactive species which is responsible
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for the growth of the polymer chain.

III) Chain termination: Termination reaction may occur due to a coupling

reaction or a disproportionation reaction.
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a) In coupling or combination reaction two reactive or, free radical polymer

chains combine together to form a dead polymer.
b) The disproportion reaction involves the transfer of a hydrogen atom from
one of the free radical polymer chain to another free radical giving rise to
one saturated and one unsaturated polymer molecules. Disproportionation
also terminates the propagation or growth of the polymer chain resulting in a
dead polymer
c) The chain can be terminated by reaction with the solvent molecules like
carbon tetrachloride.
d) Chain can be terminated by the reaction of growing polymer chain with
inhibitors like hydroquinone and trinitrobenzene.

3.4 Step – Growth polymerisation:

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It proceeds by step – wise fashion

Monomer  Dimer Trimer  oligomer  n times polymer.

Monomer in step – growth polymerisation is capable of combining with

itself or with any other species present with equal reactivity, hence it
disappears early in the reaction.

The degree of polymerisation and hence the molecular weight of the

polymer rises steadily throughout the reaction. The reactivity is governed by
the functional groups.

It can be either addition or, condensation polymerisation.

Ex -1: As a diamide, urea is capable of forming polymers. It reacts with

is formed.

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formaldehyde to form urea-formaldehyde resins. A space-network polymer

Condensation (Step-growth)Polymerisation:
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Ex-1: Phenols and formaldehyde react to form phenol-formaldehyde
resins (Bakelite and related polymers)
When phenol is treated with formaldehyde in the presence of acid or
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alkali, a high-molecular weight substance is obtained in which many
phenol rings are held together by – CH2 - groups
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The stages involved in the formation of the polymer are –

a)phenol reacts with formaldehyde to form O – or P – hydroxyl methyl
phenol.

b)Hydroxy methyl phenol reacts with another molecule of phenol to form

a compound in which two rings are joined by a – CH 2 – link. During this
reaction one water molecule is eliminated.

c)This process continues to yield a product of high molecular weight.

The final product contains many cross-links and hence has a rigid three-
dimensional structure because three positions in each phenol molecule
are susceptible to attack. Thus it is a space-network polymer.

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Ex-2: A diol reacts with a dicarboxylic acid to form an ester. But each
moiety of the simple ester still contains a group that can be react to
generate another ester linkage and hence a large molecule, which itself
can react further and so on.

If each monomer molecule contains just two functional groups, growth

can occur in only two directions. A linear polymer is obtained.
Ex: Dacron

If the reaction occurs at more than two positions in a monomer, highly

cross –linked space network polymer is obtained.
Ex: Glyptal

Carboxylic acids react with amines to yield amides, and with alcohols to
form esters.

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When an acid containing more than one-COOH group reacts with an
amine that contains more than one –NH 2 group to form polyamides.
Ex: Nylon – 6, 6.
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When an acid containing more than one-COOH group reacts with an
alcohol that contains more than one – OH group to form polyesters.
Ex: Dacron, Glyptal
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3.4 Plastics:

Plastics are the high polymers that can be molded by the application of
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heat and pressure. During molding process, there is no chemical change.

The plastics have linear structure.

Examples: Polythene, polyvinyl chloride, polystyrene, nylons, polyesters.

Thermoplastics:
Thermo plastics are the polymers that become soft on heating and
hard on cooling and the process can be repeated for a number of times.
They undergo reversible changes on heating.

Examples: Polythene (PE), polypropylene (PP), polyvinyl- chloride

(PVC), polytetrafluoroethylene (PTFE or Teflon), polystyrene (PS),
plexiglass, nylons, polyesters, PMMA, PVA, HIDS.

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(Polymethyl methacrylate)

Thermoplastics –
 are formed by addition polymerisation
 consists of linear polymer chains with negligible cross-linking
 are soft and less brittle.
 are soluble in organic solvents.
 soften on heating and hence are amenable for moulding into any shape
in the hot condition on cooling, the resin becomes hard and rigid and
retains the moulded shape.
 can be reheated and moulded into any other shape reversibly any
number of times without any change in the chemical nature.

Thermosetting polymers or, Thermosets:

Thermosets are the polymers that undergo chemical changes and cross-

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linking on heating and become permanently hard, rigid and infusible.
They will not soften on heating, Once they are set.
Examples: Phenol-formaldehyde resin, urea-formaldehyde resin, epoxy
resins (araldite), melamine, bakelite
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Thermosets (Thermosetting resins):
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 are mostly formed by condensation polymerisation.
 are mostly branched polymer chains with potential to form a 3-
dimensional structure.
 become hard and rigid on heating during moulding process.
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 are not soluble in common organic solvents.

 exhibit their characteristic properties of non-softening and non-
swelling nature, hardness and brittleness.
 cannot be softened, reformed, reshaped once they are set.
 cannot be reclaimed from wastes.

Differences between thermoplastics and thermosettings:

Thermoplastics Thermosettings
1.Formed either by addition or by 1.Formed by condensation
condensation polymerisation polymerisation reactions.
reactions
2.They have 3-dimensional, cross-
2.They have either linear or branched linked network structure.

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structures.
3.Adjascent polymer chains are held
3.Adjascent polymer chains are held together by strong covalent bonds
together by either vanderwaals called crossed-links.
forces, or by dipole-dipole forces or
by hydrogen bonds. 4.They do not soften on heating.

4.They soften on heating and stiffen 5.They are insoluble in any solvent.
on cooling
6.They cannot be remoulded and
5.Low molecular weight hence cannot be used.
thermoplastics are soluble in their
suitable solvents. 7.They cannot be reclaimed from
waste. They cannot be recycled.
6.They can be remoulded, re-shaped
and re-used. 8.They undergo chemical changes

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7.They can be reclaimed from waste
i.e., they can be recycled.
such as further polymerisation and
cross-linking during moulding
process.
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8.There is no change in chemical 9.They undergo irreversible changes
composition and structure during on the application of heat.
moulding process.
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10.They are hard, rigid and infusible.
9.They undergo reversible changes,
on the application of heat. 11.They neither dissolve nor swell in
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organic solvents.
10.They are soft and flexible.
12.They are brittle materials.
11.They swell or dissolve in organic
solvents. 13.The moulded articles can be taken
out of the moulds even when they are
12.They are tough materials still hot without any deformations.

13.The moulded articles are to be 14.Curing can be done by applying

cooled to room temperature before heat and pressure.
taking out from the moulds to avoid
deformation. 15.Examples: Phenol-formalde-hyde
resin (PF), urea-formaldehyde resin
14.Curing can be done by cooling. (UF), Melamine – formaldehyde

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resin (MF), epoxy resins, XLPE,

15.Examples: Polyethylene(PE), bakelite.
Polypropylene(PP), Poly Vinyl
Chloride(PVC), Polystyrene(PS),
POlytetrafluoroethylene (PTFE or
Teflon), Polymethyl methacrylate
(PMMA – Lucite or plexiglass)
nylons, Polyesters.

3.5 Compounding of plastics:

Definition: “The process of mechanical mixing of various additives with
polymers (without chemical reaction) to impart some special properties to
the end product is known as compounding of plastics”.

The additives get incorporated into the polymer to give a homogeneous

mixture.

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The functions of additives are
 To modify the properties of the polymer
 To introduce new properties into the fabricated articles.
 To assist polymer processing
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 To make the polymer products more pleasing and colourful.
 They should be cheap and sufficient in their functions.
 They should be stable under processing and service conditions.
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 They should not impart taste or odour.
 They should be non-toxic for food grade application of final
compound after processing.
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 They should not adversely affect the properties of polymer.

The principal additives used in compounding are

a)Fillers b)Plasticizers c)Lubricants d)Flame retarders
e)Colourants
f)Stabilisers g)Activators, accelerators and cross-linking agents
h)Nucleating agents i)Blowing agents.

3.6 Fabrication of plastics:

A variety of methods are used for fabricating plastic articles and products
depending upon the nature of the resion used and the end use of the finished
product. The methods are
1)Casting 2)Moulding 3)Extrusion 4)Blowing 5)Vacuum forming
6)Lamination 7)Surface coating

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1)Casting: Casting is the simplest technique used for fabricating products

of both thermoplastic and thermosetting resins. The molten compound
mixture is poured into lead moulds and cured at about 70oC for several hours
at atmospheric pressure to give finished products free from internal stress
and amenable for polishing.

Ex: The curing time for phenolic resions is about 50 hours.

2)Moulding: Moulding is the most widely used method for fabricating

plastic products. The different moulding methods used are –
a) Injection moulding b) compression moulding c) cold moulding
d) Transfer moulding

a)Injection moulding:
The method is mainly used for thermoplastic resins. The compounded

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mixture in the form of a powder/granules is fed into the heated cylinder
(temperature range is 90-260oC) of the injection moulding machine. The
softened plastic mass in the cylinder is injected at a controlled rate by a
screw or, piston, plunger under high pressure into a cold mould. Curing of
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the softened plastic into rigid product occurs during cooling in the mould.
The mould is opened after sufficient curing to remove the finished product.
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b)Compression moulding:
The method is useful for fabricating thermoplastic and thermosetting resins.
The required amount of a compounded mixture is placed in the mould and
the mould is closed carefully. Then the mould is subjected simultaneously
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to high temperatures (in the range 100-200oC) as well as high pressures

(100-500kg/cm2). Thermosetting resins undergo curing during heating while
thermoplastic resins undergo curing during cooling of the mould.

c)Cold moulding:
In this method, the object is formed in the mould by the application of high
pressure in the cold. Then it is taken out of the mould, heated (cured) to
remove excess solvent and to promote further condensation and hardening.

d)Transfer moulding:
The method is a modification of injection moulding suitable for use with
thermo setting plastics. They moulding composition is first plasticized by
applying minimum heat and pressure in a chamber outside of the mould and

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then it is injected into the mould where curing takes place under the
influence of heat and pressure. The method is used for more complicated
shapes and permits the use of delicate inserts.

3)Extrusion:
The method is also known as extrusion moulding. The method is used for
fabricating thermoplastics having uniform cross-section such as sheets, rods,
tubes, insultaed electric cables etc., The compounded mixture is heated to a
plastic condition and forced through a die of the required shape by a screw
conveyor. The extruded product is cooled as it emerges out of the die on a
conveyor by blowing air or spraying water.

4)Blowing:
In this method, the softened thermoplastic resin is blown by air or steam into
a closed mould, fust like industrial glass-blowing. The method is used for
making bottles, toys etc.

5)Vacuum forming:

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The method is useful for making boxes and complicated shapes from
thermoplastic resions, it has 2 steps.
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a)The thermoplastic material is made into a sheet by a process known as
calendaring by passing the compound mixture between heated rollers and
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again between cooled rollers.

b)The sheet is held firmly in a frame and heated to soften it. The soften
material is drawn into the mould by a vacuum pump and cured to form the
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finished product.

6)Lamination:
Lamination of sheets of cloth, paper or wood is carried out by impregnating
then with a solution of the resin, piled one over the other to get a desired
thickness and subjected to heat as well as pressure by pressing between
polished sheets of steel to expel the solvent and heat to cure the resin.
Usually thermosetting resins are used for lamination. The finished product
has a high tensile and impact strength.

7)Surface coating:

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Surface coating of a finished product made of metal and alloys or other

materials by polymeric resins is adopted for protective or decorative
purposes.

Ex: 1)Polyethylene is used to coat refrigerator parts, soap boxes and steering
wheels.
2)Polytetrafluoroethylene (PTFE) or, Teflon, is coated on the surface of
kitchen utensils for providing a non-sticky surface.

Surface coatings are carried out by coating the polymer powder on the hot
degreased and cleaned surface of the article.
3.8. preparation, properties, engineering applications of polyethene and
PVC:
I)Polyethylene:

Polythylene is the simplest homo polymer and a thermoplastic. The

IT
structure of polyethylene is (CH2 – CH2)n
There are two commericalgradesof polyethylene. They are
i)Low density polyethylene (LDPE)
ii)High densitypolyethylene(HDPE)
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i)Low density polyethylene (LDPE):
Preparation:
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LDPE is prepared by polymerisation of ethylene under high pressure (1500 –
50,000Psi) and high temperature (350oC) using a trace of oxygen or any
peroxide such as benzoyl peroxide as initiator.
C

Properties:
o LDPE has a linear structure with extensive branching
o It has a low degree of crystallinity (40%)
o It has a low density (0.912 – 0.935)
o It has a low melting point (110oC)
o It has lower tensile strength, stiffness and hardness
o Its chemical resistance is also poor
ii)High Density polyethylene (HDPE):
Preparation:
HDPE is prepared by coordination polymerisation of ethylene using Ziegler
natta catalyst [TiCl 4 + Al(C 2 H 5 ) 3 in hydrocarbon solvent]
Properties:
 HDPE is a linear polymer with no branching.

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 It has relatively high degree of crystallinity (90%)

 It has high density (0.96)
 It has high melting point (140oC)
 It has high tensile strength, stiffness and hardness.
 It is not attacked by chemicals.

Distinguishing properties of LDPE and HDPE

LDPE HDPE
1)Produced by chain polymerisation 1)Produced by coordination
using oxygen (or)peroxides like polymerisation using Ziegler-Natta
benzoyl peroxide. Catalyst [TiCl 4 + Al (C 2 H 5 ) 3 ]

2)Linear polymer with extensive 2)Linear polymer with practically no

branching. branching.

3)Relatively lower degree of 3)Relatively higher degree of

crystallinity (40%).

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4)Lower density (0.912 – 0.935)
crystallinity (90%)

4)Higher density (0.96)

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5)Lower melting point (110oC) 5)Higher melting point (140oC)

6)Lower tensile strength, stiffness, 6) Higher tensile strength, stiffness

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hardness and hardness.

7)Chemical resistance is low 7)Chemical resistance is high

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8) It is a white, waxy, translucent

material.

9) It does not dissolve in any solvent

at room temperature.
Applications:
1) Films and sheets: A large amount of polyethylene produced is used as
packing materials for food and textile.
2)Molded articles: It is used for the manufacture of molded articles such as
bottles, cans, buckets, toys, tubs, pipes, squeeze bottles etc.,
3) Insulating material: It is used for wire and cable coating because of its
excellent electrical insulation properties.

II) Poly vinyl chloride (PVC):

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

Properties:
1)PVC is a colourless and adourless powder.
2)It is chemically inert and non-inflammable and exhibits high resistance to
light, atmospheric oxygen, acids and alkalis.
3)It is soluble in chlorinated hydrocarbons, tetrahydrofuran (THF) and
cyclohexanone.
4)Pure resin possesses a high softening point (148oC) and a greater stiffness
and rigidity compared to polyethylene, but is brittle.
5)It is the most widely used synthetic plastic.

Applications:

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1)Rigid PVC unplasticized PVC have superior chemical resistance and high
rigidity but is brittle. It is used for making sheets, that are employed for tank
– linings, light-fittings, safety, helmets, refrigerator components, tyres, cycle
and motor cycle mudguards. It is also extruded in strip and tube form for
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use in the place of non-ferrous metals.

2)Platicized PVC is used for making continuous sheets of different

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thicknesses from 0.1mm to 8mm. It is employed for packing rain coats,
table-clothes and curtains, electrical insulation like coverings of electric
cables, injection moulding of articles like toys, tool-handles, toiled-goods,
radio-components, plastic-coated cloth, chemical containers, thermal
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insulating foam, conveyor belts etc.,

Plasticized PVC is obtained by adding plasticizers like dibutyl phthalate,

dioctyl phthalate, tricresyl phosphate etc.

II ) Polyvinyl chloride (PVC):

PVC is made by addition polymerization. It is of two types.
i)Rigid PVC : (Unplasticized PVC):
Preparation: Rigid PVC is made by heating vinyl chloride (in the form of
emulsion of it in water) in the presence of small amount of benzoyl peroxide
or H 2 O 2 as catalyst under pressure in an autoclave.
Properties:

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a)Presence of chlorine atoms on the alternate carbon atoms of PVC causes

an increase in the interchange attraction. This increases the hardness and
stiffness of polymer. Its softening point is also high (148oC)

b)The Cl-Cl dipole makes PVC a polymeric polar molecule, but because of
the immobility of the dipole at room temperature, power factor of PVC is
comparatively low.

c)PVC is colourless, odourless and non-inflammable.

d)It has superior chemical resistance but is soluble in ethyl chloride and
tetrahydrofuran (THF).
e)It has excellent oil resistance and resistance to weathering.

Applications:
a)It is used in acid recovery plants and in plants for handling hydrocarbons,

resistance to chemicals.

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many of which adversely affect the polyolefins. This is due to its very good

b)Rigid PVC has great potential importance to building industry since it has
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excellent resistance to weathering. When considered regarding initial cost,
installation and maintenance cost, it is found to be very economical. Hence,
it is used for making pipes for drainage and guttering. It is also replacing
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wood for making window frames that neither corrodes or not.

c) Rigid PVC is also used for making bottles –

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I For consumable liquids (like edible oils, fruit squashes, table wine and
vinegar).
ii)For liquids of household use (like bislery mineral water, cosmetics and
detergents).

ii)Plasticized PVC:
Preparation: plasticized PVC is obtained by adding plasticizers such as DOP
(dioctyl phthalate), dibutyl phthalate, tricresyl phosphate etc., to rigid PVC.

Properties:
Plasticized PVC is a very good insulator for direct current and low
frequency AC current.

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Applications:
a)Plasticized PVC is completely replaced rubber insulated wire for domestic
flex and is used widely industrially.

b)It is used for sheathing in cables where polyethylene is employed as

insulators.

c)Plasticized PVC is used for making leather cloth which is used in

i)Car applications in upholstery and trim,
ii)Kitchen upholstery
iii)Bathroom curtaining
iv)Ladies handbags.

Compared to leather, PVC-leather cloth has greater abrasion resistance, flex

resistance and washability. Its cost is very low.

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d)It is also used for making
i)Plastic rain wear ii)Baby pants iii)All PVC-shoes for beach wear &
iv) Garden hose.
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These applications are due to flexibility and water-proof nature of
plasticized PVC. It is also more economical and better aesthetically.
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3.9 preparation, properties and engineering applications of PS and
Teflon:
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Polystyrene (PS):
Polystyrene (PS) is an addition polymer of styrene. It is a thermoplastic and
has the following structure.

The monomer styrene is obtained by the alkylation of benzene followed by

catalytic dehydrogenation.

Preparation: Polystyrene is prepared by free radical addition polymerization

of styrene in the presence of benzoyl peroxide as catalyst.
Properties:
Polystyrene is a white, amorphous, linear thermoplastic.
It is chemically inert.

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Because of the presence of bulky phenyl groups, packing of polystyrene

chains is not efficient and hence it is amorphous polymer. Its specific
gravity (1.054) is also low.
Polystyrene can be nitrated by fuming nitric acid
 It can be sulphonated by conc. H 2 SO 4 .
 It yields water- soluble emulsion at about 100oC.
 It is highly electric insulating, highly resistant to acids.
 It has relatively low softening range (90 – 100oC) and is brittle.
 It has the unique property of transmitting light through curved
sections.
 It is readily attacked by a number of solvents.
 Its optical properties are excellent and its refractive index (1.60) is
quite high.
 Its tensile strength is about 8000Psi.

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Applications:
1) Moulded articles: A large amount of polystyrene is used for the
manufacture of household articles such as containers, jars, lids, bottles,
cabinets for TV, radio and washing machines, combs, toys, brush handles
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etc.
2) Optical objects: Because of its refractive index and clarity, it is used for
the manufacture of lenses, fluorescent light diffuser etc.,
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3) Insulating material: Because of its excellent electrical resistant properties,
it is used for wire and cable coatings.
4) It is used for the production of a variety of foamed products.
5) The sulfonated polystyrene is used as an ion-exchange resin.
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Polytetrafluoro ethylene (PTFE) : (Teflon):

Teflon is the trade name for polytetrafluoro ethylene. The linear structure of
Teflon is (CF 2 – CF 2 ) n
The monomer used is tetrafluoro ethylene which is a non-toxic gas.
The monomer is obtained by the following reactions:
CHCl 3 + 2HF  CHClF 2 + 2HCl
Chloroform Chlorodifluoro methane

Pyrolysis
2CHClF 2 CF 2 =CF 2 +2HCl

Preparation:

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Teflon is usually prepared by emulsion polymerisation of tetrafluroethylene,

under pressure in the presence of benzoyl peroxide as catalyst.

Properties:
 Teflon is essentially a linear polymer with no branching
 It is a thermoplastic
 Teflon has the following unique properties:
 High degree of crystallinity (93-98%)
 High melting point (327oC)
 High density (2.30g/cm3)
 Chemical inertness over a wide range of temperature
 Excellent electrical insulation properties.
 Non-adhesive characteristics
 Very-low coefficient of friction
 Excellent toughness and heat resistant.

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Applications: Teflon is used for
 Wire and cable insulation
 Laminates for printed circuitry
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 Coatings of frying pans.
 Non-lubricating bearings.
 Variety of seals, gaskets, packings valve and pump parts and stop-
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cocks for burettes.
 Insulators for motors, generators, coil transformers and capacitors.

Bakelite:
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Properties:
 Phenolic resins are hard, rigid and strong materials
 They have excellent heat and moisture resistance.
 They have good chemical resitance.
 They have good abrasion resistance.
 They have electrical insulation characteristics
 They are usually dark coloured.
 Lower molecular weight grades have excellent bonding strength and
adhesive properties.

Applications: Phenol formaldehyde resins are used for

 Domestic plugs and switches
 Handles for cooker and saucepans.
 Distributor heads for cars

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 Adhesives for grinding wheels and brake linings.

 Varnishes, electrical insulation and protective coatings.
 The production of ion exchange resins.
 Impregnated paper, wood and other fillers, for producing decorative
laminates and wall coverings and industrial laminates for electrical
parts including printed circuits.

Nylon:
Synthetic fiber forming polyamides are termed as ‘Nylons’.
Preparation:
 Nylon – 6 can be prepared by self-condensation of  - amino caproic
acid.
 Nylon-6 can be prepared by ring opening polymerisation of
caprolactam.
 Nylon-6 can be synthesized from cyclohexane.
The steps involved are –

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 Conversion of cyclohexane to cyclohexanone by oxidation.
 Treatment of cyclohexanone with hydroxyl amine to form an oxine.
 Conversion of cyclohexanone oxime into caprolaction by Beckmann
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rearrangement in the presence of H 2 SO 4 .

Nylon 6.10:
 Nylon 6.10 is prepared by the condensation polymerisation of
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hexamethylene diamine and sebacic acid.

Properties:
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 The structure of nylons are linear that permits side-by-side alignment.

The molecular chains are held together by hydrogen bonds. Thus
nylons have high crystallinity that imparts high strength, high melting
point, elasticity,
 toughness, abrasion resistance and retention of good mechanical
properties upto 125oC.
 They are also sterilisable.
 They have good hydrocarbon resistance since nylons are polar
polymers. Larger the number of carbon atoms, greater will be ease of
processing and hydrocarbon and moisture resistance.
Applications:
 Nylon 6.6 is primarily used for fibers that find use in making socks,
undergarments, carpets etc.,

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 Nylon 6.6 is also used in mechanical engineering for well known

applications like gears, bearings, bushes, cans etc.,
 Nylon 11 and Nylon 12 are used for making flexible tubing for
conveying petrol.
 Mouldings have application in medicine and pharmacy because of
sterilisability.
 Durable but costly hair combs.
 Nylon 6.6 is also used for facketing electrical ware to provide a tough,
abrasion resistant outer cover to protect the primary electrical
insulation.
 Nylon 6 is mainly used for making tyre cords.
 Nylon 6.10 is suitable for monofilaments that are used for bristles,
brushes etc.,
 Glass reinforced Nylon plastics are used in housings and cosings of
domestic appliances, radiator parts of car and for relay coil formers.

Nylon – 11:

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Nylon -11 can be prepared by the self-condensation of w –amino undecanoic
acid.
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Nylon 6,6:
i)Nylon 6.6 is prepared by the condensation polymerisation of
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hexamethylene diamine and adipic acid in 1:1 molor ratio without an
external strong acid.

ii)Nylon 6.6 can be prepared starting form 1,3-butadiene

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3.10 Conducting polymers:

Definition: A polymer that can conduct electricity is known as conducting
polymer.
Classification: Conducting polymers can be classified as follows.

I) Intrinsically conducting polymers:

The polymers have extensive conjugation in the backbone which is

responsible for conductance. These are of two types.

1)Conducting polymers having conjugated  - electrons in the backbone:

Such polymers contain conjugated -electrons in the back bone which
increases their conductivity to a large extent.

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Explanation: Overlapping of conjugated -electrons over the entire

backbone results in the formation of valence bands as well as conduction
bands that extends over the entire polymer molecule. The valence band and
the conduction bands are separated by a significant band gap. Thus,
electrical conduction occur only after thermal or photolytic activation of
electrons to give them sufficient energy to jump the gap and reach into the
lower levels of the conduction band.

All the three forms of polyanilines have conductivities of the order of 10-10
Scm-1. conductivity of these polymers having conjugated -electrons in the
backbone is not sufficient for their use in different applications.

2)Doped conducting polymers:

In comparison to conventional polymers, the conducting polymers having
conjugated -electrons in the backbone can be easily oxidized for reduced as

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they have low ionization potentials and high electron affinities. The
conductivities can be increased by creating positive or negative charge on
polymer backbone by oxidation or reduction. It is a referred to as doping.
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This is of two types.
a)P-doping or oxidative doping
b)n-doping or, reductive doping
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a)p-doping:
It is done by oxidation process. P-doping involves treatment of an
intrinsically conducting polymer with a lew’s acid, thereby oxidation takes
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place and positive charges on the polymer backbone are created. The
oxidation process leads to the formation of delocalized radical ion called
‘Polaron’. A second oxidation of this polaron, followed by radical
recombination yields two positive charge carriers on each chain which are
mobile. These delocalized positive charges are current carriers for
conduction.

The common p-dopants used are I 2 ,Br 2 ,ASF 5 ,PF 6 , naphthyl amine.

b)n-doping: n-doping is done by reduction process. N-doping invoves the

treatment of an intrinsically conducting polymer with a lewis base like
sodium naphthalide.

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n-doping leads to the formation of polaron and bipolaron in two steps. This
followd by recombination of radicals yields two negative charge carriers on
each chain of polyacetylene which are responsible for conduction.

II ) Extrinsically conducting polymers:

These are the polymers whose conductivities due to the presence of

externally added ingredients in them. These are of two types.

1) Conductive element filled polymer: In this type, the polymer acts as

the binder to hold the conducting element such as carbon black, metallic
fibres, metallic oxides together in the solid entity.
Minimum concentration of conductive filler which should be added so that
the polymer starts conducting is known as ‘percolation threshold’. Because
at this concentration of filler, a conducting path is formed in polymeric
material. Generally special conducting grade C-black is used as filler which

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has very high surface area, more porosity and more filamentous properties.
These polymers possess reasonably good bulk conductivity. They are
generally low in cost, light in weight, mechanically durable and strong and
are easily processable in different forms, shapes and sizes.
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2) Blended conducting polymers: These polymers are obtained by
blending a conventional polymer with a conducting polymer. These
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polymers possess better physical, chemical, electrical and mechanical
process and they can be easily processed.

Ex: upto 40% polypyrrole will have a little effect on tensile strength and
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also give a much higher impact strength than obtained with a carbon-black
filled compounds at only 10% loading.

Applications of Conducting Polymers:-

In rechargeable Light weight batteries based on perchlorate doped

Polyacetylene-lithium Systems: These are about 10 times lighter than
conventional lead storage batteries. These can produce current density up
to 50mA/cm2.
 In electrochromic displays and optical filters: ICP’s can absorb
visible light to give coloured products so can be useful for
electrochromic displays and optical filters. Thus the conducting
polymers can be used as electro chromic materials i.e., the

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materials that change colour reversibly during the

electrochemical processes of charge and discharge.
 In wiring in aircrafts and aerospace components.
 Conducting polymers are also used for making sensors for pH,
O 2 , NO x ,SO 2 ,NH 3 and glucose.
 In telecommunication systems.
 In electromagnetic screening materials.
 In electronic devices such as transistors and diodes.
 IN solar cells, drug delivery system for human body etc.,
 In photovoltaic devices.
 In non-linear optical materials.
 In molecular wires and molecular switches.
 Membranes made up of conducting polymers can show
boundary layer effects with selective permeability for ions,
gases etc., Hence they are useful for ion-exchangers and

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controlled release of drugs.
3.11 Natural rubber:
Natural rubber is found in several species of rubber trees grown in
tropical countries of these Hevea brasiliensis is the most important source
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of natural rubber and the rubber obtained from this is known as “Hevea”
rubber. Rubber is stored in the form of white fluid called ‘latex’ behind
the bark of the rubber tree.
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Natural rubber is a high polymer of isoprene (2-methyl-1,3-butadiene). It
is a hydrocarbon polymer having molecular formula (C 5 H 8 ) n .
Polyisopren eexists in two geometric isomers cis and transforms. Natural
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rubber is soft and has cis-configuration while ‘Guttapercha’ or, ‘Ballata’

has trans configuration.
Deficiencies of natural rubber:
 Natural rubber as such has no practical utility value. It is because
of many inherent deficiencies. They are –
 It is hard and brittle at low temperature and soft and sticky at high
temperature.
 It is soft and soluble in many hydrocarbon solvents and carbon
disulphide (CS 2 ).
 It has high water absorption power.
 It is a sticky substance, rather difficult to handle
 It is readily attacked by acids and alkalies.
 It has low tensile strength.

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 It has poor abrasion resistance.

 It is sensitive to oxidative degradation

Vulcanization:
Vulcanization is a process of heating the raw rubber at 100 – 140oC with
sulfur for
1 – 4 hours. The sulfur combines chemically at the double bonds of
different rubber molecules and provides cross-linking between the
chains.

The degree of vulcanization depends on the amount of sulfur used. Tyre

industry uses 3 – 5% sulfur. If the amount of sulfur is increased to 30%,
a hard and rigid rubber called “ebonite” is produced.

Advantages of vulcanization:

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 The tensile strength of vulcanized rubber is very good. It is 10 times
the tensile strength of raw rubber.
 It has excellent resilience i.e., articles made from it returns to the
original shape when the deforming load is removed.
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 It has better resistance to moisture, oxidation, abrasion.
 It has much higher resistance to wear and tear compared to raw
rubber.
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 It has broader useful temperature range (-40 to 100 C) compared to
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raw rubber’s useful temperature range (10 – 60oC).
 It is a better electrical insulator Ex: Ebonite
 It is resistant to i) Organic solvents like petrol, benzene, CCl 4 , ii) Fats
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and oils, but it swells in them.

 It has only slight tackiness.
 It has low elasticity. They property depends on the extent of
vulcanization. Ebonite has practically no elasticity.
 It is very easy to manipulate the vulcanized rubber to produce the
desired shapes.
3.12 Elastomers:
Definition: Elastomers are high polymers that undergo very long
elongation (500 – 1000%) under stress, yet regain original size fully on
released of stress.
The property of elastomers is known as elasticity. This arises due to the
coiled structure of elastomers.
Characteristics of Elastomers:
 Elastomers have linear but highly coiled structure.

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 Inter chain cohesive forces are negligible because these are

hydrocarbons.
 They have high degree of elasticity.
 They can retract rapidly.

BuNa – S : [Styrene rubber or, SBR (Styrene – butadiene rubber)

or GRS ( Government controlled styrene rubber)]

Preparation:
Buna – S is a prepared by the copolymerization of butadiene (75%) and
styrene (25%) in an emulsion system at 50oC in the presence of cumene
hydroperoxide as catalyst.
If the emulsion polymerisation is carried out at low temperatures (-18 to
5C) in the presence of redox catalyst like cumene hydroperoxide +
dextrose in the presence of iron salt, the resultant SBR is known as cold

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SBR.

Vulcanization can be done either by sulfur or sulfur monochloride

(S 2 Cl 2 ). Less sulfur and more accelerators are required for vulcanization.
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Properties:
 High abrasion resistance
 High load-bearing capacity
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 Resilience (regaining original shape after removal of applied force)
 It swells in oils and solvents.
 Low oxidation resistance, as it gets readily oxidized, especially in the
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presence of traces of ozone present in the atmosphere.

 Vulcanized and compounded cold rubber has a greater tensile strength
and greater abrasion resistance than the SBR or natural rubbers.

Applications:
SBR is used in the following applications.
1) Motor tyres 2)Shoes soles 3)Foot wear components
4) Insulation of wire and cables 5)Carpet backing
6)Gaskets 7)Adhesives 8)Tank-lining

Butyl rubber:
Preparation:
Butyl rubber is prepared by the aluminum chloride initiated cationic
copolymrisation of isobutene with small amount (1-5%) of isoprene.

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Properties:
 Under normal conditions, it is amorphous but it crystallizes on
stretching.
 It is quite resistant to oxidation due to low degree of unsaturation.
 Due to very low unsaturation, it can be vulcanized but it cannot be
hardened much.
 It can be degraded by heat or light to sticky low-molecular weight
products so stabilization is must.
 Being non-polar, it has good electrical insulation properties.
 Compared to natural rubber it possesses outstanding low permeability
to air and other gases.
 It does not crystallize on cooling and hence remains flexible down to
– 50C.
 Because of its hydrocarbon nature, butyl rubber is soluble in
hydrocarbon solvents like benzene but has excellent resistance to

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polar solvents like alcohol, acetone and ageing chemicals (ex: HCl,
HF, HNO 3 , H 2 SO 4 etc.)

Applications: It is used for

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 Insulation of high voltage wires and cables
 Inner tubes of automobile tyres.
 Conveyor belts for food and other materials.
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 Lining of tanks
 Hoses
Thiokol rubbers:
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Preparation:
Thiokol is prepared by the condensation polymerisation of sodium
polysulfide (Na 2 S x ) and ethylene dichloride (ClCH 2 CH 2 Cl).In these
elastomers, sulfur forms a part of the polymer chain.

Properties:
 They have excellent resistance to swelling and disintegration by
organic solvents and gasoline, kerosene, lubricating oils.
 Outstanding resistance to oxygen ozone, sun light.
 It undergo swelling by benzene and derivatives of benzene.
 It has lower tensile strength and modulus than natural rubber. It tends
to lose shape under continuous pressure.
 It has offensive-mercaptan-like odour, that restricts its use.

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Applications:
 Manufacture of oil hoses, chemically resistant tubing and engine
gaskets.
 Diaphragms and seals in contact with solvents.
 Printing rolls
 Containers for transporting solvents and
 Solid propellent fuels for rockets.

3.13 Fibers:

Fibers are a class of materials that are continuous filaments or discrete

elongated pieces. They are highly crystalline form of polymers.

The requisite properties for a natural or synthetic polymer molecule to

function as a fiber for use in textile are –
1)High tensile strength 2)Flexibility 3)Abrasion resistance
4)Amenability of dyeing

IT 5)Chemical stability in terms of resistance to

hydrolysis under washing conditions.
exposure to light
6)Resistance to degradation on
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Classification:

Fibers are classified into two types. They are

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1)Natural fibers 2)Artificial fibers (Synthetic fibers)

1)Natural fibers: Natural fibers include the fibers produced by plants,

animals and geological material. They are environment friendly and
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biodegradable. They are –

i)Vegetable fibers: They are cellulosic material like cotton, jute, plant
fibers are used for making textiles, ropes, mats, paper bags etc.,

ii)Wood fibers: The strength of a plant is due to the presence of wood

fiber. Wood pulp is used in making paper. Wood fibers like jute are
used for making bags.

iii)Animal fibers: They are made of protein. Pure silk, wool, hair are
animal fibers.

iv)Mineral fibers: Ex: Asbestos, Mica etc.,

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2)Synthetic fibers:

Synthetic fibers can be produced in large quantities and cheaper than

some of the natural fibers. Fiber forming synthetic polymers include
polyamides (nylon6 and nylon – 6,6), polyesters (ex.polyethylene
terephthalate, terylene or, Dacron), Polyolefins (Polyacrylo nitrile).
Polyethylene, polypropylene are also produced in the form of fibers
which are hydrophobic, chemically resistant and difficult to dye and
hence used for making ropes.

Polyester:
Synthesis of polyester is achieved by poly condensation of purified
terephthalic acid (1,4 – benzene carboxylic acid) and monoethylene
glycol.
The esterification is catalysed by the presence of mineral acid like HCl.

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Fiber reinforced plastics: (FRP):

The fiber polymers impregnated with solids / fillers to impart

mechanical strength and hardness without loosing elasticity are known as
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fiber reinforced plastics (FRP).
Various fillers are known to impart characteristic property to the plastic
material.
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Ex – 1: Fillers like carborundum, quartz and mica are added to impart
hardness and strength.
2)Barium salt fillers are impervious to X-rays.
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3)Asbestos fillers added to plastic provide heat and corrosion resistant.

Nature of polymers used for FRP: Both thermoplastics and thermoset

plastics are used such as polyethylene, polypropylene, Nylon-6,
polyester, melamine.

Applications:
 For making door handless, battery cases, exhaust fans engine cooling
fans etc., in automobiles using the base polymers like polyethene,
polypropylene, nylon – 6.
 For making nose cones, pistol grips and riffle bullets in defense
industries using the base polymers nylon-6 and polystyrene.

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 For making shuttle and textiles using nylon-6 as base polymer in

textile industries.
 For making the consumer goods like doors, windows, tables, chairs,
almyrahs, cameras, housings etc., using polypropylene and
acrylobutadiene styrene blended plastics.
 For making computer tape, insulators, wires and cable insulation,
switch, gear parts exhaust fans as electrical appliances using the base
polymers like polypropylene nylon and styrene acrylonitrite
copolymer.
 For making the items like water meters and chemical pump housings,
tubings, seat coverings etc., using the base polymers like
polypropylene,m PVC and nylon – 6.

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