INTRODUCTION TO POLYMER

CHEMISTRY
Dr. Prem Felix Siril

January 12, 2011 Introduction to Polymers 1

What are polymers, monomers and
polymerizations?

Polymers are macromolecules built up by the

linking together of large numbers of much
smaller molecules.

January 12, 2011 Introduction to Polymers 2

What are polymers, monomers and
polymerizations?

The small molecules which combine with each

other to form polymer molecules are termed
monomers.

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January 12, 2011 Introduction to Polymers 4
Polymer Structure

The condensation system

The condensation takes place between two

polyfunctional molecules to produce one
larger polyfunctional molecule with the
possible elimination of a small molecule
such as water. The reaction continues until
one of the reagents is used up.

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Polymer Structure

The condensation system

Adipoyl chloride Hexamethylene diamine

Nylone 6/6

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The Addition system

What are addition polymers?

Addition polymers are those formed from

monomers without the loss of a small
molecule.

Y Y

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Polymer Structure

The addition system

The major addition polymers are those formed

by polymerization of monomers containing
carbon-carbon double bond; such monomers
are called vinyl monomers or substituted
ethylenes.

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The addition system

Usually in this type of

polymerization, vinyl
monomers react with
themselves to form polymers

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The chain growth-step growth system
Chain polymerization

The characteristic of chain polymer is that

polymer growth takes place by monomer
reacting only with the reactive centers.
Monomer does not react with monomer and
the different-sized species such as dimer,
trimer, and n-mer do not react with each
other. Polymerization ceases when the
active centre destroyed by termination
reaction(s).
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Chain polymerization – anionic polymerization of
styrene

But, the following is NOT possible

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The chain growth-step growth system
Step polymerization

In step polymerization each polymer formed

can react further with monomer or other
polymers. Each dimer, trimer, etc. is just as
reactive as monomer. By this mechanism,
the size of the polymer molecules increases
slowly.

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Step polymerization – the production of poly
(ethylene terephthalate) (PET)

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Step polymerization – the production of poly
(ethylene terephthalate) (PET)
Next steps:

Or……..

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The chain growth-step growth system
The relationship between Mwt and conversion
Chain polymerization Step polymerisation

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Distinguishing features of chain- and step-
polymerization mechanisms

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Important….

Poly(propylene oxide)

It is structurally classified as condensation polymer

Both structure and mechanism are

usually needed in order to clearly
clarify a polymer
Ether functional group

However, the ring-opening polymerizations of cyclic monomers

usually proceed by the chain polymerization mechanism…

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Nomenclature of polymers
Nomenclature based on source
D Most simple and frequently used
D It is applicable to polymers synthesized from
a single monomer as in addition and ring-
opening polymerizations.
D How to name:
simple monomers: add monomer name to
the prefix poly without space or hyphen.

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Nomenclature of polymers
Nomenclature based on source
simple monomers
Ethylene & Polyethylene

Acetaldehyde & Polyacetaldehyde

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Nomenclature of polymers
Nomenclature based on source
Monomers have multiword name or abnormally
long name: parenthesis are placed around its
name following the prefix poly

3-methyl-1-pentene & Poly (3-methyl-1-pentene)

Propylene oxide & Poly(propylene oxide)

Clorotriflouroethylene & Poly(clorotriflouroethylene)

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Nomenclature of polymers
Nomenclature based on source
Note: condensation polymers synthesized from
single reactants are named in a similar
manner.

6-aminocaproic acid & Poly(6-aminocaproic acid)

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 Homopolymer vs. copolymer

What are homopolymers?

Homopolymers are polymers composed of only one
repeating unit in their molecules.

What are copolymers?

Copolymers are polymers composed of two different
repeating units in their molecules.
Such as

Acrylonitirle
Be careful !!! Styrene

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 Homopolymer vs. copolymer
Types of copolymer systems

Random copolymer -AABABBBABBAAAA-

Alternating copolymer -ABABABABABABAB-

Block copolymer -AAA-BBBBBB-AAAA-BB-

Graft copolymer

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Classification of polymers depending
on their structure
Linear polymers

What if polymerization conditions are changed or

different monomer is used, e.g. ethylene vs.
butadiene?

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 Classification of polymers depending
on their structure
Branched polymers

What is the effect of branching on polymer

Crystallinity
properties?

Is it branched polymer?!!!

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 Classification of polymers depending
on their structure
Crosslinked polymers do not dissolve but can be swelled
Cross-linked polymers
by liquids.
Light
Usingcrosslinking
appropriate monomers
improves elasticity properties
Chemical reactions
⇒ polymer is used as rubber
High degree of crosslinking gives high rigidity and
thermal stability (high melting point).
Polymer molecules are connected together at points
BOTH CROSSLINKED POLYMERS CANNOT
other than their ends
BE RECYLED
OR REPOROCESSED
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 Cross-linked polymers
Examples
Show the polymer formed by the reaction of the following monomers.
Is the resulting polymer linear or branched/cross-linked?
Solution

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 Cross-linked polymers
Examples
Show the polymer formed by the reaction of the following monomers.
Is the resulting polymer linear or branched/cross-linked?
Solution

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Thermosets vs. Thermoplastics
What are thermoset polymers?
Polymers that will not flow when heated. Thermosets
have cross-linked structure. Examples are phenolic
and epoxy resins.
What are thermoplastic polymers?
Polymers that soften, without chemical change, and take
new shapes by the application of heat and pressure
and harden when cooled. Thermoplastics have linear
and branched structures. Examples are PP, PVC and
Nylon

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Classification of polymers – polymer structure

Plastics

Thermosets Thermoplastics

Highly Lightly
Amorphous Crystalline
cross-linked cross-linked

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