ENGINERING CHEMISTRY

(CHEM-136)
DR. SUBHADRA RAJPOOT
 MODULE-5 POLYMER
•Polymers
•Classification of polymers
•Types of polymerization
•Molecular Mass of Polymer
•Properties of some
Important Polymer
• POLYMER: Polymers are defined as high
molecular mass macromolecules which consist
of repeating structural units derived from the
appropriate monomers.
• Monomer : The unit molecules that combine
with each other to form a polymer is called a
monomer
 CHARACTERISTICS OF IDEAL
POLYMER
• Should be inert and compatible with the
environment.
• Should be non-toxic.
• Should be easily administered.
• Should be easy and inexpensive to fabricate.
• Should have good mechanical strength.
 Classification of Polymers
There are several ways of classification of polymers.
 Thermoplastic polymers

• They are those polymers which can be

softened on heating and hardened on cooling
room temperature.
• They may be linear or branched chain
polymers.
• these polymer can be recycled many times.
Ex , Polythene, polyesterne, PVC.
 Thermosetting polymers
• This polymer is hard and infusible on heating.
• These are not soft on heating under pressure and
they are not remoluded.
• These polymers are cross linked or heavily
branched molecules
• These polymers we cannot reused or recycle .

• Ex. Some common examples are bakelite, urea-

formaldelyde resins, etc.
 POLYMERISATION
The process by which monomers are converted into polymers is called polymerization
Degree of Polymerization – Number of monomer or repeating unit(n) in the polymer chain is called degree of polymerization (DP)
Degree of polymerization (DP) is used to calculate the average molecular weight of polymer.
 Types of Polymerization Reactions
There are two general methods of polymerization:
(i) Addition polymerizations or chain growth polymerization
(ii) Condensation polymerization or step growth polymerization
 Addition polymerization
1.Molecules of the same monomer or different
monomers simply add together to form a
polymer.
2.The monomers used are mainly the
unsaturated compounds.
3.Addition polymerization generally follows 03
mechanism on the basis of reactive intermediate
such as free radical, a carbocation or a
carbanion.
(a)Free radical polymerization
(b)Cationic polymerization
(c)Anionic polymerization
 Addition polymerization
4.Addition polymerization is a three step
process:
(i) Chain initiating step
(ii) Chain propagating step
(iii) Chain terminating step.
 (a) Free radical addition
polymerization 
• The monomers used are generally mono-
substituted alkenes.
• The most commonly used catalysts are
benzoyl peroxide, hydrogen peroxide or t-
butyl peroxide etc.
Step I- Chain initiation step: In this step,
peroxide undergoes homolytic fission, e.g.,
benzoyl peroxide on heating produces phenyl
initiator free radical.
Step II Chain propagation step :The new free
radical adds to another molecules of
monomer to form a larger free radical.
Step III Chain termination step :There are 02
ways of chain termination:
(a) Coupling reaction
(b) disproportionation reaction
(b) Cationic polymerization
•  It involves formation of carbocation which are
generated by Lewis acids (like BF3, AICI3, SnCI4,
etc.) and protonic acids such as H2SO4, HF, etc.
• Higher the stability of carbocation
intermediate, more is the reactivity of
monomers towards cationic addition
polymerization. It involves the following steps:
(b) Cationic polymerization
Step I. Initiation Step
(b) Cationic polymerization
 (c)Anionic polymerization
•  It involves formation of a carbanion, Steps
involved in this process are
Step I Initiation Strong bases act as initiator.
(c)Anionic polymerization
 Condensation Polymerization
1. Such polymerization involves a repetitive
condensation reaction between two bi-
functional monomers.
2. It occurs in a stepwise manner with
elimination of some smaller molecules like
H2O, NH3, HCI, ROH, etc., therefore it is also
named as step Growth Polymerization.
3. For example: Dacron is obtained by the
condensation polymerization of ethylene
glycol and terephthalic acid.
 Molecular Mass of Polymers
The growth of the polymer chain depends upon the
availability of the monomers in the reaction. Thus,
the polymer sample contains chain of varying
lengths and hence, its molecular mass is always
expressed as an average molecular mass. It is of 02
type-
a) Number-Average Molecular Mass Mn
b) Mass /Weight Average Molecular Mass Mw
a) Number-Average Molecular
Mass (Mn)
• If N1 molecules have molecular mass M1 each,
N2 molecules have molecular mass M2 each,
N3 molecules have molecular mass M3 each and
so on,
Mn = Σ Ni Mi / Σ Ni
• It is determined by osmotic pressure method.
 b) Mass /Weight Average Molecular
Mass (Mw)
• If N1 molecules have molecular mass M 1 each,
N2 molecules have molecular mass M 2 each,
N3 molecules have molecular mass M 3 each and so
on,
Mw = Σ Ni Mi2 /Σ Ni Mi
• It is determined by light scattering and
ultracentrifugation method.
 Polydispersity Index (PDI)
• It is the ratio of the mass average molecular mass
to the number average molecular mass
• PDI = Mw / Mn
• For natural polymers, PDI is usually equal to one
which means that they are monodisperse. In other
words, such polymers are more homogeneous. On
the contrary, synthetic polymers generally have PDI
> 1 which means that they are less homogeneous.
 Preparation of some important polymers
1. Polyethene
The polythene is of two types:
(i) Low density polyethene (LDPE):
• It is obtained by polymerization of ethene at
350 to 750 K and 1000 to 2000 atm pressure.
• It is chemically inert and tough but flexible and a
poor conductor of electricity.
• It is used in the insulation of electricity carrying
wires and manufacture of squeeze bottles, toys
and flexible pipes.
 Preparation of some important polymers
(ii) High density polyethene (HDPE):
• It is obtained by the addition polymerisation of
ethene at 330 to 350 K at atmospheric pressure.
• It is tough and hard with high tensile strength.
• It is used in the manufacture of plastic
containers, house wares, pipes
 Nylon 6,6 
It is manufactured by condensation polymerisation of
adipic acid and hexamethylenediamine.

Properties
•These are used in manufactured of carpets, textile Fibres, bristles
and brushes.
•Being tough nylon is used a substitute for metals in bearings and
gears.
 Polyesters

Polymers have ester linkage are called polyesters and are

prepared by condensation polymerisation of diacids and
diols.

Properties
•The fibre of terylene is highly crease-resistant.
•It is also not damaged by pests like moths or mildew.
Uses
•It is used in manufacture of wash and wear fabrics.
Phenol-Formaldehyde Resin (Bakelite).

  These are made by the reaction

of phenol and formaldehyde in basic medium. The
reaction involves of formation of methylene bridges
in ortho, para or ortho as well as para position as
shown in the following reactions.
 Properties

• This is used for making combs, fountain pen

barrels, gramophone records, electrical goods,
formica table tops and
many other products.
• Sulphonated bakelites are used as ion-
exchange resins for softening of hard water.
 SUMMARY
• Polymer: A substance with giant molecules having high molecular
mass.
• Polymerisation: The process in which large number of small
molecules combine to form a giant molecule or a macromolecule.
The small molecules are called monomers.
• Homopolymer: A polymer formed by combination of only one type
of monomers.
• Copolymer: A polymer formed by combination of two or more
different types of monomers.
• Addition Polymers: The polymers formed by combination of large
number of monomers without the elimination of any smaller
molecules.
• Cross-linked Polymers: Monomers cross-link to form a network.
These are hard and rigid.
• Condensation Polymers: During formation of such polymers,
elimination of smaller molecules such as H2O, NH3, etc., takes place.
• Poly vinylchloride: It is formed by the polymerisation of viny1chloride (CH2 =
CH -Cl).
• Elastomers: In this type of polymers, the polymeric chains are held by weak
intermolecular forces. For example, rubber.
• Fibres: These are thread like polymers having hydrogen bonds as
intermolecular forces between different polymeric chains. For examples,
cotton, nylon-66.
• Thermoplastics: These are the polymers that soften on heating and can be.
moulded into any shape. Intermolecular forces in them are intermediate
between fibres and elastomers.
• Thermosetting Polymers: These polymers are very hard, infusible and have
extensive .cross links. For example, bakelite.
• Plastic: A polymer which is readily deformable and can be moulded into any
shape.
• Vulcanisation: Heating of natural rubber with sulphur to make it strong.
• Resilency Property: The property of returning to the original shape after
distortion within elastic limit.
• Plasticizer: A substance that when added to a thermoplastic improves its
workability.