Dr. Muhammad Irfan, PhD & Post Doc.

Assistant Professor

Department of Chemical & Energy Engineering

The Structure and Properties of Polymers

What is a polymer?

• A long molecule made

up from lots of small
molecules called
• monomers.
The Structure and Properties of
Polymers

monomer
polymer
 All the same monomer
Homopolymers
• Monomers all same
type (A)
• A+A+A+A→
• -A-A-A-A-
• eg poly(ethene)
polychloroethene PVC
Different monomers – to form
Copolymers
• Monomers of two
different types A + B
• A+B+A+B
• → -A-B-A-B-
• eg polyamides
• polyesters
 Copolymerisation
• When more than one monomer is used.
• An irregular chain structure will result eg
propene/ethene/propene/propene/ethene
• Why might polymers designers want to design
a polymer in this way?
• (Hint) Intermolecular bonds!
 The Structure of Polymers (plastics)
• Polymers are created by the chemical bonding
of many identical units. These polymers are
specifically made of small units bonded into
long chains. Carbon makes up the backbone of
the molecule and hydrogen atoms are bonded
along the carbon backbone.
The Structure of Polymers (plastics)
• Polymers that contain primarily carbon and hydrogen are
classified as organic polymers. Polypropylene and
polystyrene are examples of these.
Even though the basic makeup of many polymers is
carbon and hydrogen, other elements can also be
involved. Oxygen, chlorine, fluorine, nitrogen, silicon,
phosphorous and sulfur are other elements that are found
in the molecular makeup of polymers.
• Polyvinyl chloride (PVC) contains chlorine.
• Nylon contains nitrogen. Teflon contains fluorine.
• Polyester and polycarbonates contain oxygen.
 The Structure of Polymers (plastics)
• There are also some polymers that, instead of
having a carbon backbone, have a silicon or
phosphorous backbone and these are
considered inorganic polymers.
 Natural Polymers
• Wool, cotton, linen, hair, skin, nails, rubber,
and flesh are all naturally occurring polymers
• Most naturally polymers are made of protein
or cellulose
 Synthetic Polymers
• Commonly referred to as plastics – pliable,
able to be moulded
• The bonding process.
– When thermoplastic polymers are heated they become
flexible. There are no cross-links and the molecules can slide
over each other.
– Thermosetting polymers do not soften when heated because
molecules are crosslinked together and remain rigid.
 Thermoplastics (80%)

• No cross links between chains.

• Weak attractive forces between chains broken by
warming.
• Change shape - can be remoulded.
• Weak forces reform in new shape when cold.
 Thermoplastics
• Those which soften on heating and then harden again on cooling

These are called thermoplastic polymers because they keep their plastic
properties
• These polymer molecules consist of long chains which have only weak
bonds between the chains
• The bonds between the chains are so weak that they can be broken when
the plastic is heated
• The chains can then move around to form a different shape
• The weak bonds reform when it is cooled and the
• thermoplastic material keeps its new shape
 Thermosets

• Extensive cross-linking formed by covalent bonds.

• Bonds prevent chains moving relative to each
other.
• What will the properties of this type of plastic be
like?
 Thermosetting
• Those which never soften once they have been moulded
These are called thermosetting polymers because once set
into a shape, that shape cannot be altered
• These polymer molecules consist of long chains which have
many strong chemical bonds between the chains
• The bonds between the chains are so strong that they cannot
be broken when the plastic is heated
• This means that the thermosetting material always keeps its
shape
 Addition Polymerisation
• When ethene is subjected to high pressure it changes from a
gas to a liquid
• Liquid ethene (still under high pressure) is heated in the
presence of a catalyst (O2), an addition reaction takes place.
• For addition polymerisation to occur, the monomer must have
a double C bond.
• This bond breaks to allow the long chains to form.
• Modifying ethene, substituting different functional groups for
hydrogen atoms produces other monomers that can be
polymerised to make polymers with different properties.
 Addition polymerisation
• Monomers contain C=C bonds
• Double bond opens to (link) bond to next
monomer molecule
• Chain forms when same basic unit is repeated
over and over.
• Modern polymers also developed based on
alkynes R-C C - R’
 Addition Polymerisation
• A carbon – carbon double bond is needed in the
monomer
• A monomer is the small molecule that makes up
the polymer

H H
H H high pressure/trace O2
n C C C C
catalyst
H H H H n
ethene
poly(ethene)
 Addition Polymerisation
• The polymer is the only product
• Involves the opening out of a double bond
• The conditions of the reaction can alter the
properties of the polymer
• Reaction proceeds by a free radical
mechanism
• Oxygen often used as the initiator
 Addition polymerisation
H
H H H H H
C C C C C C
H
H H
 Addition polymerisation
• Conditions are high pressure and an oxygen
initiator (to provide the initial free radical).
• Monomer = phenylethene
• Polymer = poly(phenylethene)
 Prediction the repeating unit
• This is easy, basically open out the
double bond.

H Cl H H H H
C C C C C C
H H H Cl H Cl
chloroethene poly(chloroethene) aka
polyvinylchloride (pvc)
Linear polymers with side branches
• Linear polymers are those in which the main
backbone is unbranched.
• The way in which side branches are arranged
on linear polymers (polypropylene) can affect
the properties of the polymer.
Linear polymers with side branches
• Isotactic • Atactic
– Same side of the linear – Irregular points on both sides
polymer of the linear polymer
– Greater effect of – Chains of molecules cannot
dispersion forces therefore get close together, therefore
high density, rigid and low density.
tough and a high softening – Soft, waxy – little use
temp.
 Poly(propene)
• This varying degree of randomness will affect
the strength and melting point of the polymer.
• The less random, the stronger the polymer
and the higher the melting point
• This is because in a more ordered polymer
they chains can get closer together and hence
the van der Waal’s forces will be greater.
 Linear polymers with cross links
• Cross links are covalent bonds that can form
between polymer chains.
• If the number of crosslinks is small an elastomer
(vulcanised rubber) will result.
• If the number of crosslinks is large a hard
inflexible thermosetting polymer will be
produced.
 Linear polymers with cross links
• To make a thermosetting polymer, the linear
chains are produced first
• The cross linking is brought about either by
heat or by adding a chemical to react between
the lateral functional groups linking the chains
together.
• Araldite is a good example of a two part glue –
the 2nd method of producing a thermosetting
polymer.
 Condensation Polymers
• Condensation polymerisation uses monomers
that have two functional groups per molecule.
• These are said to be difunctional.
• Polymerisation occurs when these monomers
react ‘head-to-tail’ to form a new bond that will
eventually join the monomers together
• A small molecule (often water) is eliminated
 Condensation Polymers

• Suitable functional groups

• -NH2 amine -OH alcohol

O O
• -C carboxyl -C acid chloride
OH Cl
 Condensation Polymers
• Involves 2 monomers that have different functional
groups.
• They also involve the elimination of water or another
small molecule.
• Hence the term condensation polymer.
• Monomer A + Monomer B → Polymer + small
molecule (normally water).
• Common condensation polymers include polyesters
(the ester linkage) and polyamides (the amide linkage
as in proteins).
• May be natural (protein, starch, cotton, wool, silk) or
synthetic (viscose, nylon, polyester)
 Polyesters
• The OCR example here is terylene, a polymer of
benzene-1,4-dicarboxylic acid and ethane-1,2-diol.
• The ester linkage is formed between the monomers

O
C
O
the ester linkage
 Polyesters
• The structures of other polyesters
O O
n HO C C OH + n HO CH2 CH2 OH
heat with
an acid
catalyst

O O
C C O CH2 CH2 O

poly(ethan-1,2-diyl benzene-1,4-dicarboxylate)
 Polyamides

• These involve the linkage of two monomers through

the amide linkage as in proteins (e.g. silk)

O
C N
H
the amide linkage
 Nylon 6,6 a polyamide

H H O O
N (CH2)6 N C (CH2)4 C
H H HO OH
1,6-diaminohexane hexanedioic acid

O O
N (CH2)6 N C (CH2)4 C
H H
part of a nylon polymer chain
 Kevlar a polyamide

O O
H2N NH2 C (CH2)4 C
HO OH

O O
N N C (CH2)4 C
H H

part of the kevlar polymer chain

 Uses of polyamides
• The main use of polyesters and polyamides is as
fibres in clothing.
• Most clothing now has a degree of manufactured
fibres woven into the natural material (such as
cotton).
• This gives the material more desirable
characteristics, such as stretchiness, and better
washability.
• Don’t forget that proteins are also polyamides, you
must know how the linkage works with natural
polymers such as proteins.
 Addition Polymers
• PVC, Teflon, Polystyrene
 Addition Polymers
• Ethene can be polymerised to produce both
low and high density polyethene
(commonly known as polyethylene)
• LDPE produced with high temp and high pressure – long
side chains – low density (plastic bags)
– Soft, flexible and translucent with a waxy surface that repels
water.
• HDPE produced with lower temp and pressure – very few
short branches – dispersion forces more effective – high
density (plastic bottles)
– Rigid, stronger and more opaque than LDPE
– Slightly flexible, waxy surface that repels water
 Addition Polymers
• Rubber is an addition polymer that occurs
naturally
• The monomer in natural rubber is isoprene.
It polymerises to form long chains.
• Molecular formula (C5H8)n
• Rubber still contains double bonds which
can be attacked by oxygen and can perish
(unlike polythene)
 Addition Polymers
• Rubber –
– not elastic – long chains straighten out when stretched
and remain this way
– Susceptible to temperature changes – brittle when cold
and sticky when hot.
– Vulcanisation improved durability and elasticity of
rubber.
• The linear chains are cross linked using heat and sulfur
 Condensation Polymers
• Nylon
– Can be extruded when molten to form fibres or
sheets of strong, durable and elastic material
– Its invention had a great impact on the textile and
clothing industries.
 Condensation Polymers
• Nylon 6 : 6
– Nylon is a linear chain containing up to 100
repeated units.
– The name nylon 6 : 6 refers to the existence of
6 carbon atoms on each of the units
 Condensation Polymers
• PET plastic Polyethene terephthalate.
– Soft drink bottles
– An example of a polyester
– Note the removal of H2O (condensation polymer)
 Polymer Selection
• Due to their versatility, polymers can be
produced for almost any imagined purpose.
• A huge range of polymers exist today and are
used for many different applications.
• Their versatility has made them one of them
one of the most useful classes of substances
that we rely on in today’s society.
• This versatility can be attributed to the many
different ways that they can be modified
 Recycling
 Most plastics are
produced from crude
oil, coal or gas.
 Many of them are not
biodegradable and
have become a visible
part of our
environmental litter.