Lecture 2

Chemical Grouping of Polymers

• The two types of polymerizations lead to the formation of
‘addition polymers’ and ‘condensation polymers’

• The type of functional groups and number of functional

groups in the monomer determines the chemical
groupings polymers would have and be

• At the end of this section you should be

– Familiar with basic groupings of polymers based on their
chemistry
– Able to identify monomers as monofunctional or bifunctional,
and so on
– To differentiate between homopolymers, copolymers and
terpolymers
– able to give alternating names of addition and condensation
polymers, as chaingrowth and step-growth
• Addition Polymers
– Addition polymerization is common among
unsaturated monomers,
• It is also referred to as chain-growth polymerization.
– Common monomers are the unsaturated olefin
compounds.
• They form vinyl polymers.

• Condensation Polymers
– Formation involves the linking of monomers with
loss of smaller units like H2O, CO2, NH3molecules.
– It is also referred to as step-growth
polymerization.
– The monomers involved are usually saturated.
• Examples: Polyamides and polyesters
Grouping based on functional group(s) and
number of types of monomers that form the
polymer.

• Linear polymers with simpler structures and

formed from a monomer with a single functional
group are refreed to as homopolymers.
– Examples include natural rubber [poly isoprene],
polythene and polypropene.

• Polymers are referred to as bifunctional when two

functional groups are on each monomer that forms
it
– e.g. vinyl halides [with halogen alpha to double bond],
acrylonitriles [with nitrile and double bond], 1,3-
butadienes [with two double bonds], isoprene [2-
methyl-1,3-butadiene], phenyl ethene [styrene].
Activity
Identify each of the following bifunctional Monomers, also
identify the functional group on each

Formula Name
1

5
Grouping Based on Number and Types of monomers

• Polymers formed from only two types of monomers are

called copolymers.
• Copolymers can further be classified based on the pattern
of arrangements( linkages of the two types of monomers)
in the structure of each polymer
– Linear alternating copolymer: There is frequent and regular
alternation between the two monomers. Eg. X-Y-X-Y-X-Y- X-Y-

– Statistical copolymers (random copolymer): The two monomers

are randomly distributed depending on each monomer’s
reactivity. E.g. Y-Y- X-Y-X-X-X-X-X-Y-Y-Y X-Y-X-Y-

– Blocks: Sequence is observed in the copolymer with substantial

blocks of each monomer type. i.e. -Y-Y-Y-X-X-X-X-X-Y-Y-Y-X-X-X-
X-X-Y-Y-Y-

– Grafted copolymer: blocks of the monomers are grafted on

backbone of the other as branches. e.g.
Grouping Based on Number and Types of
Monomers

• More complex polymers formed from

not less than three different
monomers are terpolymers
– Note:
• Complexity in the structure of polymers
formed increases with increase in number of
monomers involved, and also with increase
in number of functional groups in each
monomer.
 Activity

1. What are trifunctional polymers?

– Give examples
2. Identify the monomer(s) in
– polypropene
– polytetrafluoroethene
 Cross-linked polymers

• Allylic positions on polymers with double bonds are

very reactive.

• Their reactions lead to formation of bridges

between molecules. This is called cross-linking.

• Crosslinkings afford polymers to be:

– Crystallizable and strong (since molecules lie close
together)
– Of high melting point.
• The crystallite region can be destroyed when polymer
molecules are heated.
 Grouping based on stereochemistry

• Polymers can be grouped as based on

their stereochemistry” For example
using poly-2-methyl
propene(CH3)2C=CH2
– When all the methyl groups alternate
uniformly, it is the syndiotactic form.
– If all the methyl groups are on one side of
the structure, it is the isotactic form.
– For the non-uniform alternation of the
methyl groups, it is the atactic form..
 Polymerisation

• At the end of this section you should

be able to
– Understand/ explain the two basic
patterns of polymerizations as addition
and condensation polymerizations
– Know the alternative names for addition
and condensation polymerizations
– Understand that modifications are
involved in polymerization reactions to
suite the desired polymer products
 Polymerisation
• Synthetic polymers today find application in nearly every
industry and area of life.
– Polymers are widely used as adhesives and lubricants, as well as
structural components for products ranging from children's toys
to aircraft.
– They have been employed in a variety of biomedical applications
ranging from implantable medical devices to controlled drug
delivery
– Polymers such as poly (methyl methacrylate) find application as
photoresist materials used in semiconductor manufacturing and
dielectrics for use in high-performance microprocessors.
– Polymers have also been employed as flexible substrates in the
development of organic light-emitting diodes for electronic
displays.
– All these applications are possible through the two basic patterns
of polymerizations: addition and condensation polymerizations.
Addition (free radical) Polymerization
• In addition polymerization reactions
the monomers are unsaturated [with
double or triple bonds].

• During the course of the reaction,

– At the double bond(or triple bond) the
pi electrons are released to form new C-
C bonds with two other molecules of
the monomer
Addition (free radical) Polymerization
• E.g. in ethylene, the double bond initially with pi
and sigma bonds, is broken so that the two
electrons in the pi are now utilized in forming new
C-C single bonds with two other ethylene
molecules, leaving only the sigma bond of the
initial double bond in place.
• This is repeated on every unsaturated bond;
hence all appear as single bond in the polymer
product, like a chain.

– Addition chain-growth polymerization gives

rise to direct integral multiple of the
monomer units with same percentage
composition of elements in the total
monomers which make it up
Mechanisms in Addition Polymerization
Reactions

• Radical addition chain-growth

polymerization occurs through 3 steps
– Initiation – a reactive is molecule is
formed;
• molecule which can be radical, cationic or
anionic
– Propagation stage - the growth of the
chain continues.
– Termination stage- the chain stops
growing and the reaction is terminated
 Example: - Polymerization of ethylene
• Free radical addition
– Conditions
• Temperature – about 200C
• Pressure – about 1500 - 2000 atmospheres
• Initiator – a small amount of oxygen as an impurity
 Polymerization of ethylene

• Carbon-carbon pi-bonds are

prone to electrophilic attack
• The pi-bond breaks and
simultaneously forms a new
sigma bond between the
electrophile and a carbon
atom of the original pi-bond.
• The other carbon of the pi-
bond becomes a cation - and
is activated which further
reacts with another alkene
monomer.
• The polymer continues to add
monomers very rapidly until
all of the alkene is consumed.
• Both cations and radicals are
electron deficient and can
both initiate addition
Synthetic rubber
 Copolymer
• Styrene-butadiene rubber (SBR) - which is
a copolymer of butadiene and styrene
 Condensation Polymerization
• A chemical reaction where two reactants combine to form a
polymer with the expulsion of a small molecule is called
condensation polymerisation.
– This type of reaction does not need a double bond in the
reacting molecules (like in addition polymerisation), but
requires two different functional groups on two different
molecules.

• Polyesters
– A dicarboxylic acid, such as terephthalic acid, and a
diol, such as ethylene glycol, can react with each other
at both ends to exclude a molecule of water for each
link formed in the polymer chain - producing a
polyester
• Polycarbonates
– The diol often used for this reaction is Bisphenol
A, produced from the reaction of phenol and
acetone.
– The phenols are better leaving groups that aliphatic
alcohols - and so are more reactive in
transesterification reactions.
– A polycarbonate has similar properties to
polystyrene or perspex (PMMA), but the
polycarbonate is stronger and more rigid and has
higher impact resistance - ideal as a polymer for
safety use - such as in motorcycle crash helmets.
Polycarbonate is produced as follows:
 Polysaccharides

• This class of polymer, like the polyesters, contain

oxygen atoms in the polymer backbone. The
polysaccharides are naturally occuring polymers
with the monomers joined by acteal links. A
hemiacetal group from one monomer condenses
with an alcohlol group from another, eliminating
water. The polymers forms are often called sugars
or carbohydrates. The polymers have a wide
variety of biological functions and are derived from
simple sugars such as glucose. eg. starch is a
polysaccharide of glucose (hemiacetal at C-1
condensing with hydroxyl group at C-4):
 Polyamides

• Another important condensation reaction is that

between a carboxylic acid and an amine to
produce an amide. Amide polymers are
produced by reacting diamines with dicarboxylic
acids - producing polyamides or nylon.

• In 1935, Wallace Carothers, working for Du Pont

on high molecular weight compounds, produced
a compound known as Nylon-6,6 - prepared
from adipic acid and hexamethylenediamine:
 Polypeptides

• A polyamide link is similar to that

found in polypeptides and proteins,
which are natural polymers derived
from amino acids.
• In these natural polymers the
monomer units are linked by amide
groups, formed by the condensation of
one amino group of one a-amino acid
with the carboxylic group of another:
• Synthetic polyamides were developed as alternatives to
the textiles wool and silk. Silk is a polymer of the amino
acids glycine and alanine, whereas wool is more
complex, having disulphide (sulphur-sulphur) bonds to
link the polymer chains together. The sulphur is present
due to the amino acid cysteine:
 Polyurethanes

• These polymers have a similar

structure to the polyamides, which
have the urethane (carbamate)
group as part of the polymer
backbone.