Learning objectives

 Know that an addition polymer is formed by joining up many small molecules

called monomers.

 Understand how to draw the repeat unit of an addition polymer, including

poly(ethene),
poly(propene), poly(chloroethene) and poly(tetrafluoroethene).

 Know that condensation polymerisation, in which a dicarboxylic acid reacts with a

diol, produces a polyester and water.

 Identify the repeat units and / or linkages in addition polymers and in condensation polymers.

 Understand how to write the structural and displayed formula of condensation

polymers, showing the repeat unit.

 Describe the environmental challenges caused by plastics.

Polymers are everywhere, ranging from naturally occurring polymers, for example
proteins (polypeptides) and sugar (polysaccharides), which you probably have met
before, to synthetic polymers used for like plastic bags and clothing. Polymers are
large molecules consisting of many repeating units. This chapter looks at two
different ways that polymers can be made: addition polymerisation for polymers
such as poly(ethene) and PVC, and condensation polymerisation for polymers
such as polyester.
A polymer is any substance containing very large molecules, formed when lots of
small molecules join together.

For example, look what happens when ethene molecules join:

These crates are made from

poly(ethene)

Polymers are large molecules

built up from many small units
called monomers.
• Polythene is a plastic that was discovered by accident. Through the careful examination
of this substance, when it was accidentally discovered, the plastics industry was born.
• Polythene is now produced in millions of tonnes worldwide every year.
• It is made by heating ethene to a relatively high temperature under a high pressure in
the presence of a catalyst.
• The reaction that took place is:
• In a chemical equation for this process, we show that a large number of ethene
molecules are adding together by using the letter n to indicate very large
numbers of monomer molecules.
• The polymer formed, in the chemical equation, is shown as a repeat unit which
repeats n times to form the polymer chain.
• When small molecules like ethene join together to form long chains of atoms,
called polymers, the process is called polymerisation.
• The small molecules, like ethene, which join together in this way are called
monomers.
• A polymer chain, a very large molecule or a macromolecule, often consists of
many thousands of monomer units and in any piece of plastic there will
be many millions of polymer chains.
• Some polymers are homopolymers containing just
one monomer.
Examples: Poly(ethene), poly(propene), and poly(chloroethene)
• Other polymers are copolymers, made of two or
more
different types of monomers.
Examples: Nylon and Proteins.
Polythene is a synthetic polymer. Synthetic means it is made in a factory. Other synthetic
polymers include nylon, Terylene, lycra, chewing gum, and plastics such as polystyrene and
perspex. Hair gels and shower gels contain water-soluble polymers.

Terylene Fabric Lycra Fabric Coloured Perspex Acrylic Sheets

For billions of years, nature has been busy making natural polymers. Look at these examples:

Starch is a polymer made by plants. Your skin, hair, nails, bones and muscles are mostly
The starch molecules are built from polymers, made of macromolecules called proteins. Your
molecules of glucose, a sugar. body builds these up from
amino acids.
• The polymer in your hair and nails, and in wool and silk, and animal horns and claws, is
called keratin.
• The polymer in your skin and bones is called collagen.
• So – you contain polymers, you eat polymers, you wear polymers, and you use polymers.
Polymers play a big part in your life!

Wood: over 75% cellulose.

This wood may end up as paper.
All polymers, natural and synthetic, consist of macromolecules,
formed by small molecules joined together. But these
macromolecules are not all made in the same way.

There are two types of reaction: addition polymerisation and

condensation polymerisation.
Another look at the polymerisation of ethene. The reaction can be shown in a short form
like this:

Where n stands for a large number. It could be

many thousands. The catalyst for the reaction is
usually a mixture of titanium and aluminium
compounds.

It’s an addition reaction

The reaction above takes place because
the double bonds in ethene break,
In addition polymerisation, double allowing the molecules to add on to each
bonds in molecules break and the
molecules add on to each other. other. So this is called addition
polymerisation.
SOURCES OF MONOMERS
The alkene fragments from the catalytic cracking of
petroleum fractions produce the starting materials.
Alkenes such as ethene contain a C=C double bond.
These molecules can take part in addition reactions
where the double bond is broken and other atoms attach
to the carbon atoms.
The double bond in ethene enables many molecules of
ethene to join each other to form a large molecule
(polyethene).

ETHENE
(an alkene)
• during (addition) polymerisation, alkenes undergo an addition reaction
• all the atoms in the original alkenes are used to form the polymer
• long hydrocarbon chains are formed

• the diagram shows… the original monomer and

the repeating unit in the polymer

the number of
repeating units is
n represents a ethene poly(ethene) the same as the
large number number of original
MONOMER POLYMER molecules
From monomer to polymer
From monomer to polymer
• Write down the formulae for the number of monomer units you want, but change each double
bond to a single bond.
• Draw single bonds between the monomer units
• Put ‘continuation bonds’ at either end of the chain to show that the chain carries on in the
same
way.
From monomer to polymer
Making other polymers by addition
propene  poly(propene) common name: PP or polypropylene

the monomer, Poly(propene) is more rigid

propene than poly(ethene), tough
and durable.

It is used for making crates,

ropes and fibres in some
carpets

A repeat unit of
poly(propene)

How to write
an equation
chloroethene  Poly(chloroethene) common name: PVC

the monomer, PVC is also useful e.g. for

chloroethene window frames (because it is
stiff, and doesn’t bend easily)

and insulation on wires

(because it does not catch
fire easily, and is easy to add
a colour to)

a repeat unit of poly(chloroethene)

How to write an
equation for the
reaction:
 OTHER POLYMERISATION REACTIONS

ETHENE POLY(ETHENE)

PROPENE POLY(PROPENE)

CHLOROETHENE POLY(CHLOROETHENE)
POLYVINYLCHLORIDE PVC

TETRAFLUOROETHENE POLY(TETRAFLUOROETHENE)
PTFE “Teflon”
Identifying the monomer
If you know the structure of the addition polymer, you can work out what the monomer
was. Like this:
• Identify the repeating unit. (It has two carbon atoms side by side, in the main chain.) You
could draw brackets around it.
• Then draw the unit, but put a double bond between the two carbon atoms. Get rid of the
continuation bonds.
• That is the monomer.

So this is the monomer

that was used. It is the
This shows part of a molecule of alkene propene. Note
poly(propene). The unit within the C=C double bond.
brackets is the repeating unit.
Identifying the monomer
Given a repeat unit for a polymer, you should be able to draw the monomer from
which it was formed:

1. remove the connecting bonds (and any brackets)

2. change the bond between the two carbon atoms of the chain into a double bond

Practice: Draw the monomers that

formed these two polymers:

PTFE poly(styrene)
the monomer, Poly(ethene) is a really useful
ethene plastic. It is easy to shape,
strong, and transparent.
e.g.
plastic bags, drinks
bottles,
dustbins,
clingfilm
BUT it melts easily and catches
fire easily !
a repeat unit of poly(ethene)

How to write an
equation for the
reaction:
Some addition polymers
Main Features (or Summary)
• All polymers are long-chain molecules made by joining together a large number of
monomer molecules .
• Addition polymerisation involves monomer molecules that contain a C=C double bond.
• Addition polymers are homopolymers, made from a single monomer.
Question
The structure of compound A is shown below

Draw one repeat unit of the addition polymer formed from compound
A.

Answer:
Question
Addition polymers are made from alkenes.

Complete the Fig. below to show one repeat unit of the addition polymer formed from but-2-
ene.
Question
Propene forms a polymer named poly(propene).

Draw the displayed formula of a section of poly(propene) showing three repeat

units.
A condensation polymer is one that is formed when a condensation reaction takes place
between the monomers to join them together in the polymer chain.
A condensation reaction is one in which two molecules react together to form a new, larger
molecule with the elimination of a small molecule (usually water).
Condensation polymerisation usually involves two different monomers, each with a different
functional group. These groups react with each other, joining monomers together to form the
polymer.
In condensation polymerisation, no double bonds break. Instead:
• two different monomers join.
• each has two functional groups that take part in the reaction.
• the monomers join at their functional groups, by getting rid of or eliminating small
molecules.

We will consider two types of condensation

polymers: polyamides and polyesters.
A polyamide is a polymer where the monomer units are joined together by amide (peptide)
links. e.g. nylon and proteins.
The two types of monomer that form a polyamide are carboxylic acids and amines.
An amine is a compound with –NH2 functional group. The carboxylic acid reacts with an
amine to form an amide. The –CONH– group is called an amide linkage.
Brief History
Nylons were developed in the 1930s by a research team
headed by an American chemist, Wallace H. Carothers,
working for DuPont (an American company).
Knowledge of silk and wool gave clues as to how protein
molecules are built. Wallace Carothers imitated the linkage in
proteins and produced the first synthetic fibre, ‘nylon’.

Wallace Carothers
Nylon is a solid when first formed, but it can then be
melted and forced through small holes.
The long filaments cool, and the fibres produced are
stretched to align the polymer molecules and then dried.
The fibres can be woven into fabric to make shirts, ties,
sheets, etc., or turned into ropes or racquet strings.
However, nylon is not just made into fibres. It has proved
to be a very versatile material and can be moulded into
strong plastic items such as gearwheels.
Nylon fibre is formed by forcing
molten plastic through hundreds of
tiny holes
Nylon is a copolymer of two different monomers, a diamine and a dicarboxylic acid. Each
monomer consists of a chain of carbon atoms (which are shown as blocks). At both ends of
the monomers are functional groups.
An amine group (-NH2) reacts with a carboxylic acid group (-COOH) to make a link between the
two molecules.
Each time a link is made, a molecule (usually water) is lost.

diamine
dicarboxylic acid
dicarboxylic acid diamine
Making Nylon (the reaction)
So nitrogen atom at one end of the
diamine has joined to the carbon
atom at one end of the dicarboxylic
acid, by eliminating a molecule of
water.

The reaction continues at the other

ends of the monomers. In this way,
thousands of molecules join, giving a
macromolecule of nylon.
Making Nylon (the reaction)
Making Nylon (the reaction)

Nylon is formed from carboxylic groups reacting with amine groups. The section between the dashed lines is the
repeat unit.
Generally, polyamides have the structure:

Looking at this structure, it is easy to see that the repeat unit of this polyamide
is:
Making Nylon in the Lab
Nylon, a polyamide
A. Identify the repeat unit
B. Draw the structures of the monomers
A polyester is a polymer where the monomer units are joined together by ester links. e.g. PET
(Polyethylene terephthalate)
The two types of monomer that form a polyester are dicarboxylic acids and diols. An ester
linkage is formed (with water being lost each time).
The reaction
This shows the reaction between the two monomer molecules:

The reaction continues at the other ends of the

monomers. In this way thousands of molecules join.
The reaction

So the group where the monomers have joined is called an ester linkage.
Generally, polyesters have the structure:
The reaction

The ester linkage that joins the monomer units in the man-made polyester can be broken down
by acid or alkaline hydrolysis. So it not good news if spots of alkali fall on your shirts or
sweater!
 Molecules A and B can form condensation polymers.

Draw the part of the structure of the synthetic polymer that would form when two molecules of
A
and two molecules of B combine. Show all of the bonds in the linkages.
Polymer X is a condensation polymer.
Part of the structure of polymer X is shown.

A. How many molecules of water are produced when this part of polymer X is formed from its
monomers?
B. What type of condensation polymer is X?
 Addition polymerisation Condensation polymerisation
Usually many molecules of a single Molecules of two monomers usually used
monomer
Monomers used
Monomer is unsaturated, usually contains Monomers contain reactive functional
a C=C double bond groups at ends of each molecule

Nature of reaction An addition reaction – monomers join Condensation reaction with loss of a
together by opening the C=C double small molecule (usually water) each time
bond a monomer joins the chain

Only a single product – the polymer Two products – the polymer plus water (or
some other small molecule)
Nature of product Non-biodegradable Can be biodegradable (nylon takes 40-
50 years)
Resistant to acids PET can be hydrolysed back to
monomers by acids or alkalis
Natural Polymers
Proteins
Proteins are natural polyamides. They are condensation polymers formed from amino acid
monomers.
Amino acids contain carbon, hydrogen, oxygen, and nitrogen, and some contain sulfur.
The general structure of an amino acid molecule is shown below.

Note the COOH and NH2 functional

groups.

An amino acid is a carboxylic acid with an

amino (NH2) group. R stands for the rest of
the molecule.
Proteins
There are 20 different amino acids and they each possess two functional
groups. One is the carboxylic acid group, –COOH. The other is the amine
group, –NH2.
The difference between the 20 amino acids used to make proteins lies in the
different side
chains (R-).

COOH bonds drawn vertically, to help you see how the amino acids
join The simplest amino acid is glycine, where R = -H
Proteins
Amino acids are the building blocks of proteins. Similar to nylon, proteins (including enzymes)
are polyamides as they contain the –CONH– group, which is called the amide or, in the case of
proteins, the peptide link.
Proteins are formed by condensation polymerisation.

When proteins are made, an amide link (peptide

link) is formed by the reaction of the amine group
of one amino acid with the carboxylic acid group
of the next amino acid.

This is an example of a condensation reaction.

Water is eliminated.
Proteins
How amino acids join up to make proteins
This shows four different amino acids combining:

The section of the amino acid

within the protein chain is called
the amino acid residue.

There is no regular repeat unit in

proteins because the amino acid
residues are not in any regular
order.
Proteins

Proteins are large and complex. The

chains are often coiled. The genes in the
cells of plants and animals control which
amino acids join up, and in what order.
Proteins
Protein chains formed by the reaction of many amino acid molecules have the general structure
shown below.

• Further reaction with many more amino acids takes place at each end of
each molecule to produce the final protein.
• For a molecule to be a protein, there must be at least 100 amino
acids involved.
• Proteins make up some 15% of our body weight and, along with fats
and carbohydrates (such as starch and glucose), they are among
the main constituents of food.
Proteins

The structure of a protein – human insulin (the different coloured circles represent
different amino acids in this protein)
Comparing proteins and synthetic polyamides
• In a protein, there are many types of amino acids
monomers which have been polymerised. In nylon
there are two types of monomers which have been
polymerised.
• In a protein, the order of the amino acid residues is
irregular. There is no repeat unit. In nylon there is a
regular order of repeat units.
• In a protein, the amide linkages are in the same
direction. In nylon the order alternates.

amide linkage(s) in protein amide linkage(s) in nylon

Protein Hydrolysis
Hydrolysis is a common form of a chemical reaction where water is mostly used to break down
the chemical bonds that exists between a particular substance. Hydrolysis is derived from a
Greek word hydro meaning water and lysis which translates to the word break or to
unbind.
Proteins can be hydrolysed (broken down) to amino acids by heating in concentrated
hydrochloric acid. This is the reverse of the condensation process that formed them
(proteins).
Protein Hydrolysis

The mixture of amino acids can then be separated by

chromatography. Amino acids are colourless substances, so a
locating agent is used. The locating agent reacts with amino acids to
produce coloured spots.
The importance of proteins in your food
When your body digests food, it breaks the proteins back down
to amino acids. These then join up again to make proteins your
body needs.
For example all these substances in your body are proteins:
• the enzymes that act as catalysts for reactions in your body
cells
• the collagen in your skin, bones, and teeth
• the keratin that forms your hair
• haemoglobin, the red substance in blood, that carries oxygen
• hormones, the chemicals that dictate how you grow
and develop.
Assignment
Read on, and prepare notes on the following macromolecules in food.
 Carbohydrates
 Fats and oils
Include all chemical reactions, as well as, the name(s) of the bonds formed.
Synthetic polymers are usually called plastics. (Plastic means can be moulded into shape
without breaking, and this is true of all synthetic polymers while they are being made.)

The properties of plastics

Most plastics have these properties:
• They do not usually conduct electricity or heat.
• They are unreactive. Most are not affected by air, water, acids, or other chemicals. This means they are usually
safe for storing things in, including food.
• They are usually light to carry – much lighter than wood, or stone, or glass, or most metals.
• They don’t break when you drop them. You have to hammer most rigid plastics quite hard, to get them to
break.
• They are strong. This is because their long molecules are attracted to each other. Most plastics are hard to tear
or pull apart.
• They do not catch fire easily. But when you heat them, some soften and melt, and some char (go black as if
burned).
By choosing monomers and reaction conditions carefully, you can make plastics with exactly
the properties you want.
For example, look at how you can change the properties of polythene:

At about 50°C, 3 or 4 atmospheres At about 200°C, 2000

pressure, and using a catalyst, you atmospheres pressure, and with a
get long chains like these. They are little oxygen present, the chains So by choosing the right conditions,
packed close together so the will branch. Now they can’t you can change the density of the
polythene is quite dense. pack closely, so the polythene is polythene, and make it ‘heavy’ or
far less dense. ‘light’ to suit your needs.
There were only a few plastics around before the 1950s. Since
then, dozens of new ones have been developed, and more are on
the way.
Now it is hard to imagine life without them. They are used
everywhere.
One big reason for their success is their unreactivity. But this
is also a problem. They do not break down or rot away. They
are non-biodegradable, meaning they cannot be broken down
by bacteria in the environment.

Most of the plastics thrown out in the last 50 years are still around
– and may still be here 50 years from now. A mountain of waste
plastic is growing.
Polythene: the biggest problem
It is the most-used plastic in the world, thanks to its use in plastic bags and food packaging.
Around 5 trillion polythene bags are made every year. (That’s 5 million million.) Most are used
only once or twice, then thrown away.
In recent years, there has been increasing awareness of the need to adapt our use of these
materials in the following ways:
• To reduce the level of plastic packaging wherever possible
• To avoid the use of ‘single-use plastic’ (and the subsequent littering with it)
• To reuse and recycle wherever possible.

The alternatives to dumping plastic waste are certainly more economical and more
satisfactory but also create their problems.
 Incineration schemes have been developed to use the heat generated from burning waste
for heating purposes.
 However, problems with the combustion process (which can result in the production of toxic gases) mean
that
especially high temperatures have to be employed during the incineration process, driving energy costs up.
 Incineration of PVC, for instance can release acidic fumes of hydrogen chloride.
 Burning (incinerating):
• Incinerators are expensive to build
• Toxic fumes can be released
• Energy from burning is useful e.g. for home/factory heating

Sorting and recycling plastics:

• very labour intensive to collect and sort
• plastics must be washed before sorting into different types
• not all types of plastic can be recycled
The cost of recycled plastic can be higher than new plastic !
 Disposal in landfill sites suffer from the problem that most plastics are not
biodegradable.
 As a result, plastic waste fills available space
 Research is being carried out to produce plastics that are biodegradable or photodegradable.
(However, degradation products can leach into groundwater)

Landfill is a poor solution:

• the plastics never rot away
• more and more space is needed, and land
is valuable
• wildlife may be harmed by eating plastics
or getting entangled
 Accumulation in oceans.
 Thousands of seabirds and sea turtles, seals and
other marine mammals are killed each
year after ingesting plastic or getting
entangled in it (Center for biological diversity)
 Increased awareness of this problem has been part
of the background to drive to reduce the
level of ‘single-use plastics’ in our shopping and
packaging.