UNIT IV- Polymers

Polymer: Polymer is a macromolecule, built up by the linking together of a

large number of smaller molecules called monomer (or) A polymer is a gaint /
macro molecule formed by the repeated union of several simple molecules
(monomers). The repeated units in a polymer chain are linked through strong
covalent bonds. Average molecular weight of a commercial polymer is
normally in the range of 103- 107.
Eg: Polyethylene, polystyrene, Teflon etc,

Monomer: The repeating unit of polymer is called monomer (or) These are
simple molecules having 2 or more bonding sites through which each can link
to the other monomer to form a polymer chain. Monomers are often called as
“building blocks” of a polymer.
Polymerization:
The fundamental chemical process by which the monomers (low molecular
weight) are converted into polymers ( high molecular weight) is called the
polymerization reaction. All polymerization reactions need suitable initiators.
Eg: nCH2 = CH2 Polymerization [--- CH2---CH2---] n
Ethylene Initiator Polyethylene
(Monomer) (Polymer)
Functionality:
The total number of functional groups or bonding sites present in a monomer
molecule is called the functionality of the monomer. Depending on the number
of bonding sites, the monomer is called bifunctional, trifunctional or
polyfunctional. A simple molecule should have atleast bifunctionality, which is
the basic requirement to qualify as a monomer and to undergo polymerization.
Functionality of some commercial monomers:

S. Monomer Functional Group Reactive Functionality

No Centres
1 Vinyl Compounds Two reactive centres at the double Two
bonds
2 Ethylene glycol Two alcoholic OH groups Two
3 Adipic Acid Two –COOH groups Two
4 Hexamethylene Two –NH2 groups Two
diamine
5 Phenol Three active centres at ortho & Three
para positions
Degree of polymerisation: The total number of repeating units in a polymer
chain is called degree of polymerisation (DP).

Eg: If 100 molecules of ethylene polymerise, the DP = 100.

nCH2 = CH2 [--- CH2---CH2---]n
Ethylene Polyethylene
Where ‘n’ is the degree of polymerization
Tacticity: The arrangement of functional groups on carbon back-bone of the
polymer is called tacticity of the polymer. Depending on the tacticity, there are
3 different polymers.

1. Isotactic polymers: Those polymers in which the functional groups are

arranged on the same side are called isotactic polymers.
2. Atactic polymers: When there is irregular arrangement of functional
groups on the backbone of the polymer chain, these polymers are called
atactic polymers
3. Syndiotactic polymers: The polymers with alternate arrangement of
functional groups are called syndiotactic polymers.

Classification of the polymers:

(a). Based on their origin:

Polymer

Natural polymers Synthetic polymers

(their origin is (produced by synthesis)
nature)
Elements organic Inorganic polymers Organic
polymers polymers
ex:poly
Inorganic Organic ex:Silicones sulphurnitride
polymers polymers
ex:Asbestors ex:silk,wool,
cotton etc.s Plastics Rubber
Rubber
ex: BUNA-S Fibres
ex:BUNA-S
Butyl ex:Polyester ,
Butylrubber
rubber Nylon

Thermoplastics Thermoset plastics

ex:Polyethylene ex:Bakelite
Polystyrene Male mine

b). Based on nature of polymerisation:

 POLYMERS

Homo polymers(made of Co-polymers(two or more

identical monomers) than two different monomers)
ex:[-m1-m1-m1-m1-m1] ex:[-m1-m2-m1-m2-m1-m2 ]

Straight chain Branched homo Cross linked

homopolymers polymers (the homo polymers Straight Branche
(the monomeric (the monomeric chain d co Cross linked
monomeric units are units have 3-D copolym polymer co polymers
units are linear branched network ers s

regular straight irregular alternate straight

chain copolymer straight chain chain copolymer
copolymer

Types of polymerisation:- The mechanism of polymerization takes place by

2 ways:

1. Chain/ Addition polymerization

2. Step/ Condensation polymerization

Mechanism of polymerisation:

Mechanism of polymerisation

Chain Step polymerisation

polymerisation(addition
(condensation polymerisation)
polymerisation)

Free radical Coordination

Ionic polymerisation
polymerisation polymerisation

cationic anionic
polymerisation polymerisation

1. Chain/ Addition polymerisation: A chain polymerisation is a reaction in

which rapid self addition of several bifunctional monomers to each other takes
place by chain reaction without the elimination of any by-product. It yields a
polymer product which is the exact multiple of monomers. Thus the mechanism
is also called addition polymerisation. The compounds containing double bonds
undergo chain polymerisation.
Eg: Vinyl compounds.
Addition
n [CH2 = CH ] Polymerization [--- CH2---CH---] n

y y
Vinyl Compound Vinyl polymer

Where y= H (Ethylene), CH3, (Propylene), Cl (Vinyl chloride), C6H5

(Styrene), CN (Acrylonitrile).

Characteristics:

 Monomer contains double bond which makes it bifunctional.

 The polymerisation takes place by self-addition of monomers through a
chain reaction.
 No by-products like H2O, CH3OH are produced.
 The polymer has the same chemical composition as that of monomer.
 The mol.wt. is not the sum of mol. Wt. of the monomers.
 The mechanism is carried out in three steps, i.e. initiation, propagation
and termination.
 Initiator is required to start the polymerisation; initiators may be heat,
light, pressure, catalyst etc.
 The mechanism is rapid.
 Linear polymers are formed
 The conversion of bond to bond takes place during the polymerisation,
liberating 20 Kcal/mole of energy ex: alkenes, vinyl, allyl
compounds and dienes.

Chain polymerisation mechanism is of 3 different types:

1) Free radical chain polymerisation
2) Ionic chain polymerisation
3) Coordination polymerisation.
1). Free radical chain polymerisation: The complete mechanism involves 3
steps. (a) Initiation (b) Propagation (c) Termination
 a).Initiation: The polymerization is initiated by free radicals generated from
initiators such as peroxides. A free radical is an atomic or molecular species
having an odd or unpaired electron. They are highly active species (unstable).
An initiator on heating undergoes homolytic cleavage and generates free-
radicals. It adds to the monomer to produce a new free- radical.

∆ ●
R R 2R
Initiator Free Radical
● ●
R + CH2 = CH R- CH2- CH
(Free Radical)

y y

Vinyl Monomer New Free Radical

Eg: Benzoyl peroxide, hydrogen peroxide are good initiators for free radical
chain polymerisation.

b).Propagation: In this step, the new free radical attacks another monomer
molecule to produce yet another new free radical. Many repetitions of this step
leads to polymer chain growth and continues until termination occurs.
● ●
R- CH2- CH + CH2 = CH R-CH2-CH-CH2-CH

y y y y

(Growing
Polymer)

●
R-CH2 -CH-CH2–CH + n CH2═CH R-CH2-CH-(CH2-CH)n-CH2-CH

y y y y y y
(Living Polymer )
c). Termination: Termination of the growing polymer chain is carried by
coupling and disproportionation, resulting the dead polymer. In coupling, the
collision of two growing chains causes the union of the two chains at their free
radical site producing a dead polymer.

-CH2-CH-(CH2-CH)-CH2-CH + CH-CH2 (-CH-CH2-)n CH-CH2-R

 y y y y y y

R-CH2-CH- (-CH2-CH)-CH2-CH-CH-CH2 -(-CH-CH2)n-CH-CH2-R

y y y y y y
Dead Polymer

In disproportionation, H from the growing chain is transferred to the other

growing chain. This results in the formation of two polymer molecules one
saturated and other unsaturated.

● ●
R-CH2-CH-(CH2-CH)-CH2-CH + CH-CH2 (-CH-CH2-)n CH-CH2-R

y y y y y y

R-CH2-CH-(CH2-CH)-CH=CH + CH2-CH2 (-CH-CH2-)n CH-CH2-R

y y y y y y

Dead Polymer Dead Polymer

2. Step polymerisation or condensation polymerisation: It takes place by

condensation reactions of the functional groups of the monomers (by the loss of
small groups like H2O, HCl, CH3OH) hence known as Step polymerisation or
condensation polymerisation.

Characteristics:
 Monomers contain functional groups like –OH , -COOH, -nh2, - RCOOR,
Halides etc.
 it is bifunctional or trifunctional.( i.e.Monomers must be dibasic
acids ,diols,diamines or tiols etc.)
 The polymerisation takes place by slow stepwise condensation reaction of
functional groups of the monomer.
 It is accompanied by the elimination of biproducts like H2O ,CH3OH etc.
 The mol.wt. is not the sum of mol. Wt. of the monomers.
 I t is not a three step mechanism of initiation, propogation and termination.
 The reactions are catalysed by catalysts.
 The reactions are not exothermic.
1 Ex: The polymerisation of diacid with diol produces polyester.
2 Ex: The polymerisation of a diamine with diacid gives Nylon (a polyamide)
PLASTICS: Plastics are the organic materials of high molecular weight, which
can be mouled into any desired form, when subjected to heat and pressure in the
presence of a catalyst.

Unique properties of plastics are:

 Lightness in weight
 Good thermal and electrical insulation.
 Corrosion resistance
 Easy workability
 Adhesiveness
 Low fabrication cost
 Chemical inertness
 Low thermal expansion coefficient
 High refractive index
 Good shock-absorption capacity
 High resistance to abrasion
 Impermeable to water
 Good strength and toughness
 Absorbent of vibrations and sound.
DIFFERENCE BETWEEN THERMO SET AND THERMOPLASTICS.

THERMOPLASTICS. THERMO SET PLASTICS

1. These are processed by 1. These are proceeded by
addition polymerization. condensation Polymerization.
2. Softens on heating and retaining the 2. These are infusible and insoluble
same chain on cooling. mass on heating i.e., heat resistance.
3. They are along chain linear 3. They are branched or cross-linked
polymers without any branched or Polymer.
cross linked chain.
4. On repeated heating and cooling, 4. Some sort of chemical changes
there is no change in chemical nature. occur on heating.
5. These plastics undergo purely 5. These Plastics undergo physical
physical process. as well as chemical process.
6. By heating the plastics, they 6. These plastics cannot be
can be preceded. proceeded by heating.
Preparation, properties and applications of some thermoplastic and thermo
set resins:

1. PVC:
Poly Vinyl Chloride is obtained by heating a water emulsion of vinyl chloride in
presence of a small amount of benzoyl peroxide or hydrogen peroxide in an
auto clave under pressure.
Vinyl chloride, so needed is generally prepared by treating acetylene at 1 to 1.5
atmospheres with hydrogen chloride at 600C to 800C in the presence of metal
chloride as catalyst.

CH≡CH + HCl → CH2═CH- Cl

Acetylene Vinyl chloride
Properties:
 It occurs as a colourless rigid material.
 It is having high density and low softening point.
 It is resistant to light, atmospheric oxygen, inorganic acids and
alkalis.
 It is most widely used synthetic plastic.
Uses:
 It is mainly used as cable insulation, leather cloth, packing and
toys.
 It is used for manufacturing of film, sheet and floor covering.
 PVC pipes are used for carrying corrosive chemicals in
petrochemical factories.
Teflon
Teflon is obtained by the chain polymerization of tetra fluoro ethylene in
presence of benzoyl peroxide as an initiator.

Properties: Due to the presence of highly electronegative fluorine atoms, Teflon

has got-
1. High melting point.
2. Exceptionally high chemical resistance and abrasion resistance.
3. High density.
 4. High strength and hardness so that, can be machined to drilling and
punching.
5. Very good electrical insulator.

Engineering applications
It is used as insulating material for non lubricating bearings, stop cocks
It is used as Teflon tape for packing of glasswares.

Fibres: The polymers which can be drawn in the form of ling filaments with
high tensile strength, high rigidity or stiffness and irreversible deformation are
called fibres.
These fibres posses high crystallizability and high melting points.
Fibres can be classified into: 1. Natural fibres (Cotton, Wool, Silk etc.)
2. Synthetic fibres (Polyester, Nylon etc,)

Preparation, Properties and Engineering Applications of Synthetic Fibres:

1. Polyamide/ nylon:
Preparation: Nylon is a polyamide resin, produced by copolymerisation of
diamine with diacid. Depending on the number of carbon atoms in diamine and
diacid , there are different types of nylons like nylon6:6, nylon 6:10. Where the
first number indicates the carbon atoms in diamine and the second number
indicates the number of carbon atoms in diacid.
Nylon-6, 6: It is prepared by polymerizing Hexamethylene diamine and
Adipic acid in 1:1 ratio.

Properties:

Nylons possess high strength, hardness and high melting point. The high
melting point of the nylons is due to the hydrogen bonding between the
hydrogen atom of amide group (-NH) and oxygen the C=O group.
Nylons possess high crystallinity, abrasion resistance and good mechanical
properties.
Nylons are insoluble in common solvents and dissolve only in phenols and
formic acid. They possess high temperature; absorb little moisture of ‘drip –
dry ‘nature.
Nylons possess good chemical resistance and are good electrical insulators.
Nylons possess good resistance to environmental conditions

Engineering Applications:

The major application is in the Textile industry

Because of high thermal and abrasion resistance nylins are used in mechanical
engineering applications like gears , bearings , machine parts where greater
friction is there
Flexible tubing for conveying petrol etc are made from nylons.
are used in auto mobile industry and telecommunication industry for making
radiator parts and coil Nylons formers respectively.