Polymers

Types of Polymerization, thermoplastics &

thermosetting polymers, preparation,
properties and applications of Teflon, PVC,
Nylon, Bakelite & Urea-Formaldehyde.
Elastomers: Natural rubber, Vulcanization of
rubber & Synthetic rubber
 Why polymers are so important and
so pervasive?
• As we look around----
• Enzymes, skin, hair, nucleic acids, etc…..
• Milk, potatoes, green vegetables, meat, etc…
• Food packaging materials…..
• Clothes- cotton, wool, polyester, nylon, etc…
• Artificial organs, joints, blood bags, etc…
• Woods and other plant derived materials…
• Plastic pipes, electronic devices, mobile, computer,
etc…..
• The list seems endless…………..
 Introduction
• The word ‘polymer’ is coined from two Greek words:
poly means many and mer means unit or part.
• The term polymer is defined as very large molecules
having high molecular mass (103-107u).
• These are also referred to as macromolecules, which
are formed by joining of repeating structural units on a
large scale.
• The repeating structural units are derived from some
simple and reactive molecules known as monomers
and are linked to each other by covalent bonds.
• The process of formation of polymers from respective
monomers is called polymerization.
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• Examples:-
• The transformation of ethene to polythene and
interaction of hexamethylene diamine and adipic acid
leading to the formation of Nylon 6, 6 are examples of
two different types of polymerization reactions.
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• The number of repeating units in the chain so formed is
called the degree of polymerization.
• Polymers with a high degree of polymerization are called
“high polymers” and those with low degree of
polymerization are called “oligopolymers”. High polymers
have very high molecular weights and hence are called
“macromolecules.”
• The number of reactive site present in a molecule is known
as its functionality. For a substance to act as a monomer it
must have two reactive sites.
• For example, Ethylene is a bifunctional molecule, because
when double bond is broken, two single bonds become
available for combination.
 Classification of Polymers
• On the Basis of chemical composition:
• Organic polymers: Polyethylene, polyvinyl alcohol, starch,
cellulose, etc.
• Hetero-organic polymers: Polysiloxanes, polytitoxanes,
proteins, etc.
• Inorganic Polymers: Borazole, polyphosphoric acid, hydrogen
borides, etc.
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• On the basis of chemical structure:
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• On the Basic of chain structure /arrangement:
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• On the Basic of Physical State:

• On the Basis of Polarity:

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• On the Basis of Tacticity or Configuration:
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• On the Basis of Intermolecular Force of Attraction:

(a) Elastomers: The polymers which are capable of being

stretched rapidly at least 150% of their original length
without breaking and return to their original shape on
release of stress are known as elastomers.
(b) Fibers: They are thin, long threadlike materials which have
great tensile strength in the direction of fibres. they
posses strong intermolecular forces.
(c) Plastics: Plastics are the substance which are sufficiently
viscous to retain their own shapes, especially when cold.
This property is termed plasticity.
 Thermoplastic:
• Thermoplastic , soften on heating and become plastic so that it can be converted to any
shape by moulding.
• On cooling, they become hard and rigid. On re-heating, they soften again and the
material can be remoulded to any desired shape.
• Thus, their softness and hardness are temporary phenomena which are attainable by
heating or cooling.
• The plstics that are formed by addition polymerization are thermoplastic and have linear
long chain polymeric structure without any cross-linking.
• In thermoplastic, the chemical structure or the molecular weight are not changed during
the heating or moulding operations.
• Only the secondary bonds between the individual molecular chains are broken on
heating which results in their softening and flow properties.
• On cooling, these secondary bonds are re-established as a result of which they become
hard again.
• Obviously, thermoplastics are weaker, softer and less brittle as compared to
thermosetting.
• The molecular weights of thermoplastic are smaller than those of thermosetting. Also
their inter-molecular forces are weaker than in thermosetting plastics. That is why
thermoplastics swell or dissolve in some solvents.
• Examples : Polyethylene, polystyrene, polyvinyls, (such as nylons), acrylics and
cellulose derivatives.
 Thermosetting
• Thermosetting are those which set upon heating and cannot be reformed
when once they are set.
• In general, those plastics which are formed by condensation are
thermosetting.
• The thermosetting have three dimensional network structure and have very
high molecular weights.
• These have predominant covalent cross links between the long chain
molecules which are responsible for the three dimensional network
structure.
• When these materials are moulded, additional cross linking are formed
between the long chains leading to further increase in molecular weight.
• When cross linking are formed, the thermosetting acquire some of their
characteristic properties such as hardness, toughness, non-swelling and
non-softening properties, brittleness, etc.
• The strength of these bonds are retained even on heating and hence they
cannot be softened or remoulded or reclaimed when once they are cured
as can be done in the case of thermoplastic.
• Examples : Phenol formaldehyde resins (Bakelite), urea and melamine
formaldehydes resins, alkyds, polyesters resins, silicones, etc.
Types of Polymerization or Mechanism of
Polymerization
• Addition Polymerization:
• Addition polymerization is a typical chain reaction. The
three type of mechanism for addition polymerization are
given:-
(a) Free Radical Addition Polymerization
(b) Cationic Addition Polymerization
(c) Anionic Addition Polymerization
• All the three mechanism completes in following three
steps:-
(i) Initiation
(ii) Propagation
(iii) Termination
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• Free Radical Addition Polymerization:
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• Free Radical Addition Polymerization:
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 3. Co-ordination polymerization
It usually involve a transition-metal catalyst. here the active species is a
coordination complex, which initiates the polymerization by adding to the
monomers’s carbon-carbon double bonds. the most important catalyst for co-
ordination polymerization is ziegler–natta catalyst discovered to the effective for
alkene/alkyne polymerization.

polymerization of
dienes
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Teflon (Polytetrafluoro ethylene)
Teflon (Polytetraflouro ethylene)
Teflon (Polytetrafluoro ethylene)
PVC (Polyvinyl chloride)
PVC (Polyvinyl chloride)
 Nylon
Nylon is a generic term for synthetic polyamides capable of forming fibres.

Polyamides are a group of polymers which contain the amide (—CONH—)

linkage in the main polymer chain. Polymers of this type are the synthetic
linear aliphatic polyamides which are capable of fibre formation.

Amino acid polymers are designated by a single number, as Nylon : 6 for poly
(w-amino-caproic acid) or polycaprolactum.

Nylons from diamines and dibasic acids are designated by two numbers, the
first representing the diamine, and second representing acid as Nylon 6 : 6
for the polymer of hexamethylene diamine and adipic acid and Nylon 6 : 10
for that of hexamethylene diamine and sebacic acid.
 Nylon 6:6

It is known as Nylon 6:6, because both the monomer (i.e. hexamethylene

diamine and adipic acid) contain six, six carbon atom.
Nylon 6:6
 Bakelite (Phenol-formaldehyde)
• Bakelite was the earliest thermosetting resin named after the
Belgian American chemist, Bakeland, who patented it in 1909.
• It was prepared by condensation of phenol and formaldehyde.
• The reaction is catalyzed by alkali and acids.
• The nature of the product depends mainly on the nature of
the catalyst and the proportion of the reaction (i.e. phenol
formaldehyde ratio).
• The formation of phenol formaldehyde resins involves the
following steps:
Bakelite (Phenol-formaldehyde)
Bakelite (Phenol-formaldehyde)
Bakelite (Phenol-formaldehyde)
Bakelite (Phenol-formaldehyde)
 Urea-Formaldehyde
• It is a important amino resins.
• Amino resins or amino plastics are prepared by the reactions of
formaldehyde with nitrogen compounds such as urea, melamine
and other amino compounds. Because of their attractive light
colours, these resins have great commercial importance.
• It is prepared by the reaction of urea and formaldehyde in neutral
or acidic conditions. The first products formed during the formation
of resin are monomethylol and dimethyol urea.
 Urea-Formaldehyde
• Now dimethylol urea undergoes condensation polymerization and formed
cross linked polymer.
Urea-Formaldehyde