UNIT IV POLYMER CHEMISTRY

Introduction to polymers, functionality of monomers, chain

growth and step growth polymerization, coordination
polymerization, with specific examples and mechanisms of
polymer formation, Poly Dispersity Index (PDI) & it’s significance
Plastics – Thermo and Thermosetting plastics, Preparation,
properties and applications of – PVC, Teflon, Bakelite, Nylon-6,6,
carbon fibres.
Elastomers–Buna-S, Buna-N–preparation, properties and
applications.
Conducting polymers – polyacetylene, polyaniline, – mechanism of
conduction and applications.
Bio-Degradable polymers - Poly Glycolic Acid (PGA), Poly Lactic
Acid (PLA).
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POLYMERS –Introduction - Precisely
• The word polymer is derived from two Greek words “Poly”
and “Mers”. In Greek, “Poly” means many and “Mers” means
parts or Units.
• A polymer is a large molecule which was formed by the
combination of small molecules.
• The individual small molecule from which the polymer was
formed are known as “monomers” and the phenomenon
combination of monomers to form giant molecule (polymer)
is called polymerization.
• Ex. H H
H H
Polymerisation
n C C * C C *

H H
H H n
ETHENE
polythene
(Monomer)
(polymer)

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POLYMERS - Introduction

monomers

Polymer

The word, polymer, implies that polymers are constructed from

pieces (monomers) that can be easily connected into long chains
(polymer). When you look at the above shapes, your mind should
see that they could easily fit together.

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POLYMERS - Introduction
• The number of repeating units or the monomers present in the
polymer chain is called “degree of polymerization (DP)”.
• Molecular weight of polymer = Molecular weight of monomer X
degree of polymerization.
• The polymers with high degree of polymerization are called high
polymers. They have high molecular weight (104 - 106), hence,
they are also called macro molecules.
• The polymer with low degree of polymerization are called oligo
polymers or oligomers.
• Polymers are generally known as plastics. The term ‘plastic’
derived from the Latin word ‘Plastiko’ means fit for molding.
• All the plastics are polymers, but all the polymers are not
necessarily plastics.
• Performance, reliability and cost make the polymeric materials
useful for a wide variety of applications.
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Functionality of a monomer
✓The number of bonding sites (or) reactive sites (or) functional
groups present in the molecule.
✓Example: The double bond in ethene monomers (CH2 = CH2) can
be considered as a site for two free valences. When the double
bond is broken, two single bonds become available for
combination.

✓For a monomer, minimum two reactive sites are necessary to

polymerise. Such monomers are known as bifunctional
monomers.
✓Bifunctional polymers are usually straight / linear polymers. The
monomer units are held by covalent bonds while different chains
are held by weak van der Waals forces. 5
Functionality of a monomer
✓When the functionality of monomer is three (tri-functional),
three dimensional net work polymer is formed.
✓Examples for tri-functional polymers: Urea-formaldehyde, phenol
formaldehyde
✓Mixtures of bifunctional and trifunctional polymers are branched
polymers as well as cross-linked polymers.
✓Example for bi-functional monomers
Vinyl monomers (HC2 = 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
Dicarboxylic acids having general formula (HOOC – R – COOH)
a)succinic acid b)adipic acid c) terephthalic acid
Amino acids with the general formula H2N – R-CH - COOH
a) glycine b)alanine c) valine d) - amino caproic acid 6
POLYMERS – Classification – Based on their origin
• Natural polymers: The polymers which are
available/made naturally. Ex. DNA, proteins,
carbohydrates
• Synthetic polymers: The polymers which made by
human being. Ex. Nylons, Poly-ethylene, Poly-styrene
• Semisynthetic polymers: Polymers which are derived
from natural polymers by chemical modification.
Example: Cellulose acetate, Cellulose nitrate (gun
cotton).
POLYMERS – Classification - Molecular Structure of polymer
• Physical properties of polymers depend not only on their
molecular weight/shape, but also on the difference in the chain
structure
Polymer
Structures

Linear
Network

Branched

Cross-linked
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Linear Polymers
• These are polymers in which monomeric units are linked
together to form linear chain
• Linear – a chain with two ends
• These linear polymers are well packed and have high
magnitude of intermolecular forces of attraction and therefore
have high densities, high tensile (pulling) strength and high
melting points.
• Some common example of linear polymers are high density
polyethylene nylon, polyester, etc.

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Branched Polymers
✓Monomers are joined to form long chains with side chains or
branches of different lengths.
✓Irregularly packed and therefore, they have low tensile strength,
low density, boiling point and melting points than linear
polymers.
✓These branches are usually a result of side-reactions during the
polymerization of the main chain
✓Some common examples are low density polythene, glycogen,
starch etc.

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Polymer chains can branch :
Cross-linked Polymers
• A cross-link is a bond that links one polymer chain to another
(Covalent or Ionic bonds).
• Monomers unit are cross-linked together to form a three-
dimensional network polymers.
• Materials often behave very differently from linear polymers
• Many “rubbery” polymers are cross-linked to modify their
mechanical properties; in that case it is often called vulcanization
• Generally, amorphous polymers are weak, and cross-linking adds
strength: vulcanized rubber is polyisoprene with sulphur cross-links

Polymer chain

Polymer chain 11
 Network Polymers
✓Polymers that are “trifunctional” instead of bifunctional.
✓There are three points on the monomer that can react.
✓This leads to three-dimensional connectivity of the polymer
backbone.
✓Highly cross-linked polymers can also be classified as network
polymers.
✓Examples: epoxies, phenol-formaldehyde polymers.

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Classification based on Tacticity
Tacticity – stereoregularity or spatial arrangement of chain
i. Isotactic – All R groups on same side of chain

Isotactic polypropylene
ii. Syndiotactic – R groups alternate sides

Syndiotactic polypropylene
iii. Atactic – R groups random

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Classification of polymers based on Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
Bulky groups on Bulky groups on
same side of chain opposite sides of chain

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Classification based on Thermal Properties
Thermoplastics Thermosetting plastics
They soften on heating They do not soften on heating; On
prolonged heating they burn
They consist of long chain which They have three-dimensional network
are linear polymers joined by strong covalent bonds
They are formed by addition They are formed by condensation
polymerization polymerization
They are soft, weak and less brittle They are hard, strong and more brittle

They can be reclaimed from They can not be reclaimed from

wastes wastes
They are usually soluble in organic They are insoluble in organic solvents
solvents since they have strong cross linking

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Classification based on Monomers or Nomenclature of Polymers
1. Homopolymer: a polymer made up of only one type of monomer
-A–A–A–A–A–

2. Heteropolymer (or) copolymer:

A polymer made up of two or more monomers
-A–B–A–B–A–

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Nomenclature of Polymers
• Copolymers are further divided into

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 Classification based on polymerization or mode of synthesis
Addition polymers/polymerisation: The addition polymers are formed by
the repeated addition of monomer molecules possessing double or triple
bonds. In these polymers, the molecular formula of the repeating unit is
the same as that of the monomer.

Condensation polymers/Polymerisation: These are formed by repeated

condensation reaction between two different bi-functional or tri-
functional monomeric units. In these polymerization reactions, the
elimination of small molecules such as water, alcohol, hydrogen chloride.

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Differences between Addition and Condensation Polymers
Addition Polymers Condensation Polymers
Monomers with unsaturation Bi or Trifunctional monomers
involved in the polymerization. involved in polymerization.
Repeated addition of monomers Repeated reactions of active
without any expulsion of functional groups in monomers with
byproducts forms addition expulsion of simple byproducts such
polymers. as water, alcohol, HCl, etc., forms
Condensation polymers.
The molecular formula of The molecular formula of monomer is
monomer is the Empirical formula not the Empirical formula of
of Addition Polymer i.e, there is Condensation Polymer i.e, there is
no molecular mass change decrease in the molecular mass of
the polymer
Formed by chain growth Formed by step growth
polymerization polymerization
Ex. Polythene, PVC, Teflon, Ex. Bakelite, Urea formaldehyde
Polystyrene etc., resins, Terylene, Nylon 6,6 etc.,19
Questions

1. What is polymerization? (6 marks)

2. What is the functionality of a monomer? (3 marks)
3. What is the number of functionality in adipic acid and hexa-methylene diamine
(1 mark)
4. Classify the polymers based on their molecular structure (Linear, branched,
cross-linked and network) (6 marks)
5. What is homo polymer and give one example? (1 mark)
6. What is hetero/co –polymer and give one example? (1 mark)
7. Classify the polymers based on their synthesis strategy/types of polymerization?
(addition and condensation polymerization) (6 marks)

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