Unit 4

POLYMERS
What we are going to learn or discuss in this chapter:
1. Introduction to polymers
2. Synthesis of polymers
3. Classification of polymers
4. Application of polymers
1. Introduction to polymers
▪ Polymers are macromolecules made up of repeating units called monomers.
▪ The repeating units in the polymer chain called monomers”.
▪ poly’ meaning many and ‘meros’ meaning part.
▪ A polymer comprised of more than 100 monomers; structures with lower numbers of monomers are
known as oligomers(low degree of polymerization)
▪ Polymers or oligomers may be linear, slightly branched, or highly interconnected
▪ The branched structure develops a large three-dimensional network.
▪ The size of a polymer molecule may be defined either by its mass or by the number of repeat units in
the molecule.
▪ Polymerization: The process in which large number of small molecules (monomers) linking
together to form a large molecule (polymer) in presence of temperature, pressure and catalyst.
▪ Degree of Polymerization: “The number of repeating units of monomers present or combined
together in polymer.
❖ It is calculated as the ratio of molecular weight of a polymer and molecular weight of the repeat
unit
❖ Affect physical properties of polymers.
• Some common examples of polymers are:
✓ Polyethylene,
✓ wood (cellulose)
✓ Rubber
✓ protein, Enzymes, DNA etc. as biopolymers
• Example of monomers are:
✓ Glucose(𝐶6 𝐻12 𝑂6 ) a monomer for cellulose (wood)
✓ Ethylene a monomer for Polyethylene
✓ Amino acid (N𝐻2 CH(R)(COOH)) a monomer for protein
List where 20 amino acids are grouped according to the
characteristics of the side chains in protein
• Aliphatic - alanine, glycine, isoleucine, leucine, proline,
valine
• Aromatic - phenylalanine, tryptophan, tyrosine
• Acidic - aspartic acid, glutamic acid
• Basic - arginine histidine, lysine
• Hydroxylic - serine, threonine
• Sulphur-containing - cysteine, methionine
• Amidic (containing amide group) - asparagine, glutamine
• 2. Synthesis of polymers
• The reaction involved in synthesis of polymers is called
polymerization that links various monomers together.
• The essential feature of a monomer is to have two or more
functional groups (polyfunctionality).
• Monomers have the capacity to form chemical bonds to at
least two other monomer molecules.
• Bifunctional monomers can form only linear, chainlike
polymers. Monomers with higher functionality yield cross-
linked, network polymeric products.
• There are two types of polymerization i.e.
A. Addition (chain growth) polymerization and
B. Condensation (step growth) polymerization.
A. Addition polymerization(Chain growth)
• The word chain indicates elongation of carbon skeleton to form a polymer
• It involves unsaturated monomers
❖ For example, the addition polymerization of many ethylene molecules yields
polyethylene and that of styrene molecules gives polystyrene.
• Addition polymerization is undergone by monomers having C = C linkage.
• e.g. ethylene, vinyl chloride, propylene, butadiene, styrene etc.
• The rate of reaction is very high.
• Addition polymerization requires radical initiators or Lewis acid/base as
catalyst.
• Polymers include polyethylene, polyvinyl chloride, acrylics, polystyrene, and
polyoxymethylene (acetal) are made by addition polymerization.
There are 4 types of addition polymerization reaction:
i. Radical polymerization in which the initiating species (Z*) is a radical while the site of
reactivity (*) is a carbon radical.(the most important step)
ii. Anionic polymerization in which the initiating species (Z*) is a nucleophile while the
site of reactivity (*) is a carbanion.
iii. Cationic polymerization in which the initiating species (Z*) is an acid while the site of
reactivity (*) is a carbocation.
iv. Coordination catalytic polymerization in which the initiating species
• THE POLYMERIZATION REACTION INVOLVES THREE STEPS :
a) Initiation. b) Propagation or branching and c) Termination .
a) Chain Initiation Step:
• started by means of a reactive initiator molecule.
• The initiator molecules can be a free radical, a cation or anion.
• The reactive centers react easily with other monomers without eliminating the active center.
b)Chain propagation step:
• Period for monomers to be added to the growing chain, with the free radical,
cation or anion transferring to the chain end.
c)Chain termination step:
• The polymerization is stopped since chain reactions do not continue
indefinitely.
• The radical, cation, or anion is “neutralized” stopping the chain
propagation
• If a polymer is given, you can identify the monomer unit that is
repeated in it
• If the mass of the polymer is known, the number of the
monomer molecules is determined by dividing the molar mass
of the polymer by the molar mass of the monomer
B. If the PVC had a molar mass of 1.33 × 105 g/mol, how
many monomer units (n) are there?
Question (Exercise 4.1)
Show the steps followed in the polymerization of styrene to
polystyrene. Describe each step.
(a) Initiation:
• (b) Propagation:
© Termination

B. CONDENSATION (step growth )POLYMERIZATION

• Involves the combination of monomer molecules, with the release or elimination of
one molecule of a simple by-product such as H2O, HCl, salt or alcohol etc.
• products are normally referred as condensate.
• The monomers involved two or more functional groups such as -OH, - COOH, - NH2 etc.
• Unlike addition / chain polymerizations, polymer loses simple molecules at every
combination, as a result does not have exact multiple number of monomer units.
Examples:
• dibasic acids with diamines to give polyamides
• dibasic acids with diols to form polyesters
• Proteins, starch and cellulose are examples of natural
condensation polymers.
• Polyester (Polyethylene terephthalate or Dacron) and the
polyamide Nylon 66 represented below, are two examples of
synthetic condensation polymers
Thus,
a. Condensation polymerization is undergone by the monomers
which possess functional groups.
b. Generally monomers are like acids, amines, alcohols, phenols,
carbonyl compounds etc.
c. This type of polymerization occurs stepwise, hence the rate of
polymerization is comparatively slow, it depends on kind of
catalyst the temperature and the time of reaction
Example:
▪ Dacron is a copolymer and is formed when equimolar
amounts of 1, 4-benzene dicarboxylic acid (terephthalic
acid) and 1, 2-ethanediol (ethylene glycol) react.
▪ Dacron is a strong and impact resistant.
▪ It is colorless and has high transparency.
▪ It is mainly used for synthetic fibbers.
▪ Mixing with various amounts of cotton it gives fabrics that
are durable, easily dyed and crease-resistant.
▪ It is also used for making bottles and packaging materials.
• Nylon 66 (the numbers indicate there are six carbon atoms
each in hexamethylene diamine and adipic acid)
• Uses of nylon include:
✓ making parachutes, ropes, clothes, stockings, hair combs,
and rugs.
✓ They are also used to reinforce automobiles tires.

• Exercise 4.2(page 223) is your home work

2. CLASSIFICATION OF POLYMERS
I. Based on source of origin
Thus
• The polymers obtained from nature (plants and animals) are called natural
polymers. These polymers are very essential for life.
• They are as under.
(a) Starch: It is polymer of glucose and it is food reserve of plant.
(b) Cellulose: It also a polymer of glucose. It is a chief structural material of the plant
both starch and cellulose are made by plants from glucose produced during
photosynthesis.
(c) Proteins: These are polymers of alpha-amino acids, they have generally 20 to
1000 alpha amino acid joined together in a highly organized arrangement.
• These are building blocks of animal body and constitute an essential part of our
food.
(d) Nucleic acids: These are polymers of various nucleotides.
• Generally macromolecules such as polysaccharides (e.g., starches, cellulose, gums,
etc.), proteins (e.g., enzymes), fibbers (e.g., wool, silk, cotton), polyisoprenes (e.g.,
natural rubber), and nucleic acids (e.g., RNA, DNA) are biopolymers.
• Note: Semi-synthetic polymers: Rayon and other cellulose
derivatives like cellulose nitrate, cellulose acetate etc., are
semi-synthetic polymers.
• These are thermoplastic polymers. Viscose rayon in the
form of a thin transparent film is known as cellophane.
Cellophane is softened with glycerol. Unlike plastic sheets
it absorbs water.
• Rayon: Rayon is a manmade material which consists of
purified cellulose in the form of long fibres.
II. Based on Structure
• Linear polymers are well packed and therefore have high
densities, high tensil (pulling) strength and high melting points.
Some common example of linear polymers are polyethylene
nylon, polyester, PVC, PAN etc.
• branched chain polymers are irregularly packed and therefore,
they have low tensile strength and melting points than linear
polymers. Some common examples are low density polythene,
glycogen, starch etc. (Amylopectin).
• Cross-linked polymers are hard, rigid and brittle because of
network structure (as of figure) e.g., Bakelite, melamine
formaldehyde resin etc.
III. based upon molecular forces:
1. Elastomers: The polymers that have elastic character like rubber (a material
that can return to its original shape after stretching.
In elastomers the polymers chains are held together by weak intermolecular
forces. Because of the presence of weak forces, the polymers can be easily
stretched by applying small stress and regains their original shape when the stress
is removed. The most important example of elastomers is natural rubber.
2. Fibers: These are the polymers which have strong intermolecular forces
between the chain. These forces are either hydrogen bonds or dipole-dipole
interaction. Because of strong forces, the chains are closely packed giving them
high tensil strength and less elasticity. Therefore, these polymers have sharp
melting points. These polymers are long, thin and thread like and can be woven in
fabric. Therefore, these are used for making fibers. Example : Nylon 66, Dacron,
silk etc.
3. Thermoplastics: These are the polymers which can be easily softened
repeatedly when heated and hardened when cooled with little change in
their properties. The intermolecular forces in these polymers are
intermediate between those of elastomers and fibers. There is no cross
linking between the chain.
The softening occurs as the polymer chain move more and more freely
because of absence of cross link. When heated, they melt and form a fluid
which can be moulded into any desired shapes and then cooled to get the
desired product. Example: Polythene, polystyrene, PVC, Teflon etc.
4. Thermosetting polymers: These are the polymers which undergo
permanent change on heating. They become hard and infusible on heating.
They are generally prepared from low molecular mass semifluid substances.
When heated they get highly cross linked to form hard infusible and
insoluble products. The cross links hold the molecule in place so that heating
does not allow them to move freely. Therefore a thermosetting plastic is
cross linked and is permanently rigid. Example : Bakelite, melamine
formaldehyde etc.
• On the basis of nature of monomer. Polymer are of two
type
(i) Homo polymers and (ii) Copolymers
▪ A polymer formed from one type of monomers is called
homo polymer. For example, polythene is a homo polymer
of monomer ethene.

▪ Copolymers: A polymer formed from two or more different

monomers is called copolymer or mixed polymer. For
example, nylon-66 is a polymer of two types of monomers:
hexamethylenediamine and adipic acid.
▪ The composition of the copolymer depends on the proportion of the
monomers and their reactivity. It may be noted that some monomers do not
polymerize at all but copolymerize. For example, maleic anhydride does not
polymerize as such. However, it copolymerizes with styrene in a highly
symmetrical manner to form styrene maleic anhydride copolymer.
• It may be noted that many types of copolymers can be
obtained depending upon the distribution of monomer units
in the chain.
• Two monomers can combine in either regular fashion
(although this is rare) or random fashion. For example, if
monomer A is copolymerized with monomer B, the resultant
product may have a random distribution of the two units
throughout the chain or it might have alternating
distribution.
• (– A – B – A – B – A – B – A – B –) Alternating copolymer
• (– A – A – A – B – A – B – B – A – B –) Random copolymer
• Two other types of copolymers that can be prepared under
certain conditions are called block copolymers and graft
copolymers.
(a) Block copolymers are those in which different blocks of
identical monomer units alternate with each other as
(– A – A – A – A – B – B – B – B – A – A – A – A – B – B – B – B –)n
These are prepared by initiating the polymerization of one
monomer as if growing a homo polymer and then adding an
excess of second monomer to the active reaction mixture.
(b) Graft polymers are those in which homo polymer branches
of one monomer units are grafted on the homo polymer chains
of another monomer units as:

These are prepared by radiation of gamma-rays on a

completed homo polymer chain in the presence of the second
monomer.
• Exercise 4.3 and Review Exercise of this chapter are your home work