CHAPTER 13

INTRODUCTION TO POLYMER

At

the end of this lecture,

students should be able to:

Determine types of polymer

Determine physical properties of
polymer
Determine types of polymerization

Introduction
Polymer

is a macromolecule
comprised of repeating structural
units joined by covalent bonds.
Greek word: poly=many, mer= parts

The

repeating unit is a group of

atoms covalently bonded together
in a specific spatial arrangement.
Monomer: the building block or structural
unit of the polymer.

Types of Polymers
Polymer
Inorganic
Natural
clays (bricks,
cement, pottery)

sands (glass)

Organic

Synthetic

Natural

fibres

polysaccharides
(starch, cellulose)

proteins
(collagen, lignins)

polyisoprene
(rubbers)

Classification Based on Source

Synthetic
adhesiv
es
fibres
coating
s
plastics
rubber
s
resins

Types of Polymers
Polymers are usually divided into two
groups according to their physical or
chemical hardening processes:.
Thermoplastic:

solid materials are

produced by simply cooling a polymer melt
(physical process).
e.g. polystyrene, polyethylene
Thermoset: produced by crosslinking
reaction (chemical process) between
polymer molecules.
e.g. epoxies, phenol resins
Classification Based on Physical

Types of Polymers
Thermoplasti
cs

Thermosets

High molar mass molecules

Low molar mass molecules

No crosslinking

Crosslinked

Soften upon heating

Decompose chemically
upon heating

Can be remelted

Cannot remelt

Recyclable

Non recyclable

Classification Based on Physical

Types of Polymers

There are three different types based on the structure

of the polymers.
Linear polymers on Structure

Branched chain polymers

Cross linked or Network polymers

Classification Based on the Structure of the

Types of Polymers
POLYMER
PVC
PS

NAME
Poly(vinyl chloride)
Poly(styrene)

SBR

Styrene-butadiene-rubber

PET

Poly(ethylene terephthalate)

PVAc

Poly(vinyl acetate)

PVA

Poly(vinyl alcohol)

PAN

Poly(acrylonitrile)

SAN

Styrene-acrylonitrile copolymer

ABS

Acrylonitrile-butadiene-styrene
terpolymer

Classification of Polymers
Polymers

can be classified as:

Addition polymers
Condensation polymers
However, some polymers are neither
condensation nor addition polymers.

Therefore,

polymers are classified based on

the polymerisation mechanism:
Chain reaction
Step reaction

Classification of Polymers
Homopolymers

- consist of chains
with identical bonding linkages to
each monomer unit.
This usually implies that the polymer
is made from all identical monomer
molecules.
These may be represented as : -[A-A-AA-A-A]-

Classification of Polymers
Copolymers

- consist of chains with

two or more linkages usually implying
two or more different types of
monomer units.
These may be represented as : -[A-B-AB-A-B]-

Mode of Polymerisation
Addition

polymerisation:

sequential addition of one bifunctional/

polyfunctional monomer to growing polymer
chains without the elimination of any
part of the monomer molecule.

Pn + M Pn+1

Addition Polymerisation

A simple representation is -[A-A-A-A-

Addition Polymerisation

A simple representation is -[A-A-A-A-

Mode of Polymerisation
Condensation

polymerisation:

polymers formed from bifunctional

monomers with the elimination of a small
molecule species (w). The reaction can
occur between any two growing polymer
molecules.

Pm + Pn Pm+n + w

Condensation Polymerisation

A simple representation is -[A-B-A-B-

Condensation Polymerisation

A simple representation is -[A-B-A-B-

Types of Polymerization
Reactions
Chain

reaction:

polymerisation process by repeated

addition of monomer molecules to
growing polymer chain without the
elimination of low molar mass molecules.
CH2=CHR

Y*

CH2=CHR

Y-CH2-CHR

Y-CH2-CHR-CH2-CHR etc.
where Y* is an initiator

Chain Polymerisation
There are four types of
intermediates for chain polymerisation
(based on the type of initiator):

Carbon free radical (initiator: free radicals)

Carbocation ion (initiator: cations)
Carbanion (initiator: anions)
Carbene (initiator: coordination compounds)

Free Radical Mechanism

Very

fast process (fraction of a

second).
Requires initiation to start the
process, then propagation to grow
the polymer chain.
Termination is the last process to
end the polymerisation process.

Free Radical Mechanism

uv

Cl2 2 Cl
Propagation: Cl + CH4 HCl + CH3
CH3 + Cl2 CH3Cl + Cl
Termination (3 types)
(i) dimerisation:
CH3 + CH3 CH3-CH3
(ii) disproportionation:
CH3-CH2CH2 + CH3(CH2)2CH2
CH3CHCH2 + CH3(CH2)2CH3
(iii) chain transfer: a chain transfer agent
deposits a hydrogen with one electron on the
radical of a growing polymer chain and this
process initiate another polymerisation process.
Initiation:

Molecular Weight Control

In

polymerisation process, the aim is

to control the molecular weight.
The following variables influence the
molecular weight:
Temperature: the higher (optimum) the
temperature, the shorter the time required
to polymerisation.
Solvent: when a polymer molecule
precipitates out of a solution, it will not
polymerize anymore; therefore the correct
solvent is important.

Molecular Weight Control

Concentration of initiator: For addition
polymerisation, higher concentration of
initiator will result in lower molecular
weight polymer.
Concentration of monomer:
Type of initiator: the initiator forms
radicals by decomposition reaction which
has a half life which is dependent on
temperature and type of initiator.

Cationic Polymerisation
Three

groups of monomers can be

polymerised cationically:
Olefin derivatives CH2=CHR with
electron-rich substituents R
Monomers CH2=Z with double bonds
containing heteroatoms or heterogroups Z
Rings with heteroatoms

Cationic Polymerisation
Monomer

Application

Isobutylene

CH2=C(CH3)2

Elastomer, adhesives

Vinylethers

CH2=CHOR

Adhesives, textile
aids, platicizers

Formaldehyde

CH2=O

Engineering plastics

Ethyleneimine

Cyclo-(NHCH2CH2)

Paper additive,
flocculant

Tetrahydrofuran

Cyclo-(O(CH2)4)

Soft segment for

polyurethanes

Cationic Polymerisation
Initiators: Bronsted acids (perchloric acid,
trichloroacetic acid, trifluoromethanesulfonic acid,
etc.); Lewis acids (AlCl3, TiCl4, etc.)
Coinitiators:
perchlorate)

water, carbenium salts (acetyl

The

growing polymer chain is positively

charged which stabilise itself by addition of
nucleophilic species.

Very

few monomers are polymerised

cationically on an industrial scale.

Cationic Polymerisation

Anionic Polymerisation
Anionic

polymerisation are initiated by

bases or Lewis bases such as alkali
metals, alkoxides, amines, phosphines,
Grignard compounds and sodium
naphthalene.
The type and proportion of the initiating
species strongly affect the polymerisation
rates and the tacticity of the polymers
(tacticity: refers to how the pendant groups are
arranged in a polymeric strand isotactic,
sindiotactic, atactic)
Tacticity (from Greek 'taktikos': of or relating to arrangement or
order) is the relative stereochemistry of adjacent chiral centers
within a macromolecule

Tacticity of the polymers

Anionic Polymerisation

Anionic Polymerisation
Narrow

molar mass distribution

Employed

for the production of

thermoplastics especially block
copolymers (syrene-butadiene-styrene type)

Physical Properties
The

physical properties of polymer

material are largely determined by:

Molecular weight
Strength of intermolecular forces
Regularity of the polymer structure
Flexibility of the polymer molecule

The

physical properties include

melting point, glass transition
temperature, solubility, melt
viscosity, tensile strength.

Physical Properties
Melting

point:

a temperature range in which the viscosity of the

polymer changes from a solid to a liquid (the
polymer must be thermoplastic)
Glass

transition temperature (Tg):

a point where there is a change in polymer

molecule chain motion which has drastic effects on
strength.
Crystalline

melt temperature (Tm):

the crystalline domains of a polymer melt become

amorphous.

Physical Properties
Tensile

strength:

measures how difficult it is to break a substance

when stress is applied to pull it apart.
Tensile strength generally increases with molecular
weight.

THE END