POLYMERS

INFORMATION AND ACTIVITY BOOK

for post 16 chemistry courses

 Acknowledgments

This book could not have been produced without the active assistance and
encouragement of the Education Liaison Group and other ICI staff on Teesside. We are
much indebted to them all. Dr Philip A Staniland (lCI plc Wilton) lent us many source
materials. However, there is also a legion of industrialists in this and other
companies who have read, commented on and helped with sections in this book and we
have also had the benefit of earlier published work, much of which is listed in the final
appendix.

We wish to thank Dr G R Crooks CSt Mary's Sixth Form College, Middlesbrough) and
Dr A W Lewis (Bede Sixth Form College, Billingham) who contributed some of the
student activities.

Finally, we are grateful to the British Plastics Federation, The Institute of Materials,
British Plastics Training Association and the Polymer and Rubber Association for
their active support of the Polymer Industry Education Centre at the University of York.

We have been unable to trace copyright holders for a number of sources, and would
appreciate any information that would enable us to do so.
Editors

Dr. Francesca Garforth

Alan Stancliffe

Polymer Industry Education Centre

Department of Chemistry
University of York
Heslington
York
Y015DD

© Jointly held by ICI and the University of York Science Education Group

Published 1994
ISBN: 1 85342 7012

The copyright holders waive the copyright on the material which follows to the extent
that teachers may reproduce this material for use with their pupils in the establishment
for which the material was purchased, but for all other purposes permission to reproduce
any of this material in any form must be obtained from ICI or the University of York
Science Education Group. The material may not be duplicated for lending, hire or
sale.

SAFETY
Teachers are asked to pay special attention to the safety notes in section 8 concerning
the activities in the previous sections.
 CONTENTS

Sectionl Polymers
1.1 Natural and synthetic polymers
1.2 Classification of synthetic polymers
1.3 Combining monomers
1.4 Nomenclature of polymers
1.5 Structure and properties
1.5.1 Bonding
1.5.2 Structure of synthetic polymers
1.5.3 Chain length
1.5.4 Isomerism
1.5.5 Solid structure
1.5.6 Physical states and transitions
1.6 Chemistry of polymerisation
1.6.1 Addition polymerisation
1.6.2 Condensation (Stepwise) polymerisation
1.6.3 Contrasting addition and condensation polymerisation
1.6.4 Other polymerisation reactions
1.7 Summary of polymer classification
1.8 Additives
1.9 Formulation of plastics
1.10 Processing of plastics
1.11 Examples of polymers
Al Activities

Section 2 Thermoplastics
2.1 Polycarbonates
2.2 Poly(chloroethene)
2.3 Poly(ethene)
2.4 Poly(methyl-2-methylpropenoate)
2.5 Poly(phenylethene)
2.6 Poly(propene)
2.7 Poly(tetrafluoroethene)
A2 Activities
Section 3 Thermosetting plastics
3.1 Methanal plastics
3.1.1 Phenol-methanal plastics
3.1.2 Carbamide-methanal plastics
3.1.3 Melamine-methanal plastics
3.2 Polyurethanes
A3 Activities

Section 4 Elastomers
4.1 Natural rubbers
4.1.1 Molecular structure and isomerism
4.1.2 Molecular structure and physical properties
4.1.3 Vulcanisation
4.2 Synthetic rubbers
4.2.1 Poly(buta-1,3-diene)
4.2.2 Styrene-butadiene co-polymer (SBR)
4.2.3 Polysulphide rubber
4.2.4 Nitrile rubbers (NBR)
4.2.5 Polychloroprene (Neoprene) (CR)
4.3 Silicone polymers
4.3.1 Silicone fluids
4.3.2 Silicone resins
4.3.3 Silicone rubbers
4.4 Table Applications of Specialists Rubbers
A4 Activities

Section 5 Fibres
5.1 Fibres based on cellulose
5.1.1 Viscose rayon
5.1.2 Cellulose triethanoate (Tricel)
5.2 Polyamides (Nylons)
5.3 Polyesters
5.3.1 Terylene
5.3.2 Unsaturated polyester resins
5.4 Polyaramids
5.5 Poly(propenonitrile) (Polyacrylonitrile)
5.6 Processing synthetic fibres
A5 Activities

Section 6 Composites Materials

6.1 Reinforcing fibres
6.2 Matrix materials
6.3 The interface
6.4 Classes of composite material
6.5 The properties and applications of composite materials
A6 Activities
Section 7 Degradable polymers
7.1 Biopol: an example of a Biopolymer
7.2 Degradable synthetic polymers
7.2.1 Photodegradable low density poly(ethene)
7.2.2 Poly(ethenol): an example of a water soluble polymer
7.2.3 Synthetic biodegradable polymers
7.3 Disposal and recycling of polymers
A7 Activities

SectionS Teachers' Notes

Practical hints and answers to suggested activities

Appendices
Appendix 1 Polymers in Domestic Products
Appendix 2 Polymers: names, densities, Tg, Tm
Appendix 3 Suppliers of plastazote foam
Appendix 4 List of sources
 FOREWORD

Over the last forty years plastics have come to have considerable influence
over the way we live. Because of their versatility and convenience, they are
used in products of all kinds, many of which we now depend upon daily.
Until recently most synthetic polymers have been used as substitutes for
natural materials. Plastics have replaced wood and metals; synthetic fibres
have been used instead of cotton and wool; synthetic rubbers have helped
meet a demand which natural rubber alone could not meet. Now, scientists
and engineers are designing synthetic materials to meet requirements for
which natural products have never been used.

The products of the polymer industry pervade almost every activity we

engage in. Over 65 million tonnes of plastics are manufactured each year
from more than 30 polymer types, which in turn are made into an extensive
number of polymers. Everything from clothing and house insulation to
human heart valves are made from these. We need only take a look around
a kitchen or a car to realise how we have become dependent on plastics.

The introduction of many new polymers is unlikely. However, the

development of new processes using existing monomers will result in the
production of many new speciality polymers. Industrial chemists now
know enough about the physical and chemical properties of a wide range of
synthetic polymers to enable them to modify them for new applications or to
meet new demands for better performance.

One major area of continued development in the next few years will be
'smart' materials and structures. These are designed to respond to their
environment by initiating changes to their properties (e.g. photochromatic
glasses that change colour in response to light).

However, with the increase in consumption has come concern that there
must be effective management of waste from our homes and from industry.
Durability, the very thing which makes plastics so useful, creates a problem
for disposal, contributing to litter, landfill overflow and ocean pollution.
Recycling, incineration and the development of degradable plastics are seen
as possible solutions to this problem.

Polymer science is little more than 60 years old yet the increasing
multinational nature of the plastics industry will ensure that the rate of
technological advancement and pace of global competition will increase.

1
 ABOUT THIS BOOK

The polymers described in detail in this book are grouped according to one
of several possible classifications for example on the basis of physical
properties related to use. In Sections 2-6 each polymer has a separate sub-
section. Material can be extracted to suit a preferred teaching programme.
For example, poly(propenonitrile) is in Section 5 (fibres) but it could be
introduced with thermoplastics, synthetic polymers or addition polymers.

Section 1 is designed to introduce students (particularly those who have only

just completed GCSE Double Science) to some basic terminology, chemistry
and structure of polymer science. Much of this material will be covered in
any A-level chemistry course but not all students using this book will be
working towards this examination. For those undertaking Technology A-
levels, vocational courses or other post-I6 examinations, it is hoped that this
section will provide much of the information required for understanding
the basis of polymer chemistry and the plastics industry and will, with the
detailed information on individual polymers, be a useful resource for
project work. This detail includes the reaction conditions for the large scale
manufacture of the monomer(s) and polymer together with some of the
processes used to convert the polymer to a useful plastic or fibre.
References are given to raw materials, energy costs and overall economics.
Section 7 is devoted to environmental aspects, including recycling.

Activities are to be found at the end of each section. Many of these are
laboratory-based but some are written exercises only. Instructions for
experiments are set out in detail for the student but the preparation of
special reagents and availability of unusual equipment are the
responsibility of the teacher or technician.

Teachers' Notes (Section 8) give information concerning the purchase and

preparation of unusual chemicals and extra information on safety aspects.
Teachers are encouraged to read this section carefully before embarking on
any of the practical activities. These notes also outline some answers to the
questions students are asked in both the practical and written activities.

Written activities are based on material in the preceding section(s) and in

many instances, questions have references to these: the activities are
particularly suitable for homework.

2
 SECTION 1
Polymers
1.1 Natural and synthetic polymers

A polymer is just a very big molecule with a high relative molecular mass.
Polymers ("poly" meaning many, and "mers" meaning parts) are built up
from many smaller molecules known as monomers, each joined together by
the same type of chemical bond. The process of building up polymer chains
from repeated monomers is known as polymerisation and this can be done
in nature or synthetically.

The most familiar natural polymers are cotton, wool and silk (used to make
clothes), cellulose (used in paper making) and our hair and nails. Natural
polymers are created by the action of enzymes which occur in living
systems and act as very efficient protein-based catalysts. Enzymes can
speed up reactions by factors of up to 1010 (i.e. a reaction which only takes 1
second with the enzyme would take 300 years without it).

Early plastics (polymers) such as casein, cellulose ethanoate and cellulose

nitrate were semi-synthetic since the naturally occuring base material was
chemically modified.

The first true synthetic polymers were the phenol-methanal resins,

originally known as Bakelite after the Belgian, Dr Leo Baekeland, who
carried out much of the development work. Modern plastics are almost
totally synthetic polymers and are derived mainly from hydrocarbons
obtained from crude oil.

Polymers can be broadly classified as follows:

POLYMERS

I
NATURAL SEMI-SYNTHETIC .SYNTHETIC

I I
Thermoplastics Thermosetting Elastomers
Plastics

3
 Examples of natural polymers Examples of semi-synthetic polymers

amber - fossilized pine resin casein - based on skimmed

(artificial horn) milk
cellulose - from wood and cotton
cotton- from the seed covering of cotton
plants cellophane
Gutta Percha . from bark of Malayan
Palaquium
hair & horn- from animals
trees
celluloid
rayon
visooserayon
} based on
cellulose

Iatex- resin from rubber trees

lacquer. resin of Chinese lacquer tree vulcanized rubber -latex + sulphur
shellac- secretions from tropical insects (ebonite)

silk . secretion of silkworm larvae

tortoiseshell- from hawksbill turtle

Examples of natural and semi-synthetic polymers

1.2 Classification of synthetic polymers

The main categories of synthetic polymers are:

Thermoplastics
Thermosetting plastics (Thermosets)
Synthetic elastomers
Fibres
Composites

Classification can be carried out in several ways:

• according to the type of chemical reaction involved in polymerisation
(the chemical structure of the polymer)
• the physical properties of the product
• the principal uses of the product.

In this booklet polymers are shown in four categories broadly based on

physical properties and a fifth which is based on uses. These categories are
not mutually exclusive; for example poly(propene), a thermoplastic, is also
used as a fibre and polyurethane, a thermoset, is also an elastomer. A
summary of some different methods of classification is given at the end of
this chapter.

4
The table below shows the categorisation of the polymers and groups of
polymers which are treated in detail in this booklet.

ThermopIastics Thermosets Elastomers Fibres Composites

poly(ethene) methanal plastics poly(buta-l,3- Kevlar carbon

diene) fibre
poly(propene) poly(methyl-2- polyamides
methylpropenoate) polysulphide fibre glass
poly( chloroethene) polyesters
rubber
polyurethanes
poly(phenyl- poly(propenoni trile)
polyurethanes
ethene)
poly(pheny I
poly(tetrafl uoro-
ethene)-
ethene)
buta-l,3-diene
polycarbonates co-polymer

Some synthetic polymers

1.3 Combining monomers

The two main chemical processes used to produce synthetic polymers are
addition polymerisation and condensation polymerisation These are
outlined in detail later (section 1.6).

If all the monomers of a particular polymer are the same, and we represent
them by the letter A, a polymer formed is known as an A-A polymer or
homopolymer.
-A-A-A-A-A-A-A-A-A-A-A-
Polythene and PVC are examples of A-A polymers.

If two different monomers (A and B) are used, we can get an A-B polymer.
-A-B-A-B-A-B-A-B-A-B-A-
Nylon 6,6 and polyesters are examples of A-B polymers.

Such polymers are essentially linear and are usually described as long
chain molecules, since the monomers repeat many times and join together
like the links of a chain.

Writing out the long chain of a polymer molecule is very time consuming so
a shorthand version is often adopted where
-A- or -A-B-
represent the repeat unit(s) and n a very large number.

-fAt, or

5
The repeat unit for poly(propene) is shown here as an example:-

Linear polymers can have repeat units from 5 to 10000 units.

Not all polymers are linear. There are monomers which are tri-functional
and poly-functional. In these cases the polymer chains become branched or
interconnected to form three-dimensional networks. For example, propane-
1,2,3-triol is tri-functional and when used with the usual monomers
(ethane-1,2-diol and benzene-l,4-dicarboxylic acid) in the manufacture of
Terylene, produces a cross-linked product as shown below.

I
-G-T-E-T-E-T-G-T-E-T-
I
T
I
-T-G-T-E-T-G-T-G-T-
I I
T T
I I

where T = benzene-1,4-dicarboxylic acid

E = ethane-1,2-diol
G = propane-1,2,3-triol

It would be difficult to represent these types of polymer in terms of their

repeat units so they are usually represented in a form similar to that shown
above.

1.4 Nomenclature of polymers

As with all organic compounds each polymer has a systematic name which
relates directly to its chemical formula or to the formula of its monomer(s).
For example, the polymer from ethene is named poly(ethene) and the
polymer from propene is poly(propene).
Many polymers were developed before chemical nomenclature was
systematised and so have a common (or trivial) chemical name. Some
polymers also have non-chemical names which mayor may not relate to
their chemical formula. For example poly(ethene) is commonly known as
polyethylene (ethylene being the common name for ethene) and as polythene
(an abbreviation of polyethylene).

There are many exceptions to the poly( ) format. In particular brackets are
not used after poly - where the name refers to a group of polymers rather
than a specific compound, e.g. polycarbonates, polyamides, polyurethanes.

Whenever a manufacturer patents a polymer, a trade name is allocated to

it. Thus one polymer may be sold under a number of trade names. A list of
systematic and trade names, together with the name of the corresponding
manufacturer, are given for some polymers in Appendix 2.

6
1 .5 Structure and properties

1.5.1 Bonding
For a particular application, the type of plastic chosen will depend on its
strength, rigidity, toughness, stability towards radiation and chemical
attack and the temperature range it can operate in without softening or
decomposing. However, the temperature and pressure needed to make the
plastics into a usable product is also important.

All these properties relate to, and depend upon, the bonds within the
polymer molecule and the forces between the molecules, the intermolecular
forces. The atoms in the polymer molecules are held together by covalent
bonds. Covalent bonds are strong with short interatomic distances and
relatively constant angles between successive bonds. They govern the
thermal and photochemical stability of polymers. The strength of these
bonds also influences how a polymer decomposes when heated or irradiated
(degraded). For example in sulphur-vulcanised rubber there are -8-8- and -
C-C- bonds. It is at the weaker -8-8- bonds that decomposition takes place.

Intermolecular forces, although much weaker than covalent bonds, still

hold the molecules together in the solid and liquid phases. Intermolecular
attraction results from permanent or induced dipoles in adjacent
molecules. The distribution of electrons in bonds between atoms of different
elements (e.g. C = 0) results in a permanent dipole because of the
displacement of electrons towards the more electronegative element.
Induced dipoles arise from the repulsion of electrons in one atom by the
presence of the electrons in an adjacent atom; this is a temporary effect
which alters as the atoms move relative to each other. Induced dipoles
provide the weak attractive forces between those polymer molecules which
consist mainly of long hydrocarbon chains.

Intermolecular forces affect most of the physical properties of polymers.

Melting, dissolving, vaporising, absorption, deformation and flow
characteristics all involve disruption of intermolecular forces to allow
molecules to move past one another or away from each other. In polymers
this will be associated with the movements of individual segments of long
chain molecules.

The strongest intermolecular forces are hydrogen bonds, for example

between the amine and carbonyl groups of adjacent molecules and this
dictates to a large extent the high melting points of the polyamides.

1.5.2 Structure of synthetic polymers

Thermoplastics are polymers without chemical cross-links between the
chains. In this sense they resemble a tangle of fibres. There are
intermolecular forces between the chains but these are fairly weak and
easily broken by warming the material. The chains can then move relative
to one another. During this state the plastic can be moulded into particular
shapes. When cool the intermolecular forces reform between different
atoms and the material retains the new moulded shape.

7
 A representation of polymer chains of a thermoplastic. There is no cross-linking.

Thermoplastic materials can be heated and remoulded many times,

although chemical degradation may eventually limit the number of
moulding cycles possible. One advantage in commercial processing is that
any waste material or incorrectly formed component can be reground and
used again in the moulding cycle.

With thermosetting plastics the polymer chains react with one another
during the moulding process forming irreversible strong covalent bonds as
cross links, so creating a vast three dimensional network.

Sometimes
depicted as .,
A representation of polymer chains of a thermosetting plastic. There is considerable
cross-linking.

Once formed, this network cannot easily be broken down and further
heating results in charring and decomposition of the material. Melting
does not occur. Thermosetting plastics can only be heated and moulded
once, following which they become very rigid and have a high resistance to
heat. Thus, waste material cannot be re-used.

Elastomers are a specific type of thermosetting plastics. Their name reflects

the fact that they have elastic or rubber-like qualities (rubber is itself an
elastomer). Elastomer plastics are specially modified to produce limited
cross linking of molecules which in turn gives them the elastic properties of
rubber, allowing them to stretch or deform under pressure but to recover
when released (just like stretching elastic bands).

A representation of polymer chains in an elastomer. There is limited cross-linking which

gives elasticity.

8
1.5.3 Chain length

The tensile strength of polymers is related to molecular chain length,

because
• longer chains become more tangled together
• longer chains have more points of contact with neighbouring chains
and therefore there are more intermolecular forces to hold the chains
together.

As a result of the entanglement and the consequent number of

opportunities for the action of intermolecular forces between long polymer
molecules, when one molecule attempts to move, it pulls the other
molecules with it. If we imagine that we could pull one of the molecular
chains of a polymer, the other chains would also move with it as a result of
the intermolecular forces involved. This is illustrated below.

End result
Pull ••

Tangled chains Pulling one chain tends to pull

the others with it as a result of the
intermolecular forces between chains

A critical length must be reached before tensile strength increases and this
will be different for each polymer. Hydrocarbon polymers such as
poly(ethene) need an average of at least 100 repeat units for any increase in
strength whereas nylon may only need 40. This is because in nylon,
molecules are held together by relatively strong hydrogen bonds whereas
poly(ethene) molecules are only attracted through weak induced dipoles.

1.5.4 Isomerism

The possibility for isomerism in these very large molecules is immense but
only two types are considered here. During polymerisation some
monomers can join the growing chain in different ways depending on the
reaction conditions and on the nature of the catalyst used. The
arrangement of monomers within the polymer molecule will affect the
physical properties, and consequently the potential uses of the polymer.

a) Branched chains
Molecules with branched chains cannot pack together as closely as those
with linear chains. This leads to fewer intermolecular forces between
branched molecules than in their linear isomers. The resultant solids will
be amorphous rather than crystalline and the density and softening
temperatures will be lower.

9
b) Steric structure
When a polymer is derived from an unsymmetrical alkene, for example
propene, CHa - CH = CH2 or from a substituted alkene, such as
chloroethene, CH2 = CHCI, the substituent groups can be oriented in three
different ways with respect to the carbon chain. For example, the three
stereoisomers of poly(propene) are illustrated below. Also see Table 1.7.

isotactic

•
0
0
Gi3

syndiotactic

atactic

different stereoisomers of poly(propene)

Because of the regular arrangement of CHa- groups, isotactic molecules can

pack together closely and form a crystalline polymer whereas the irregular
atactic molecules cannot.
These structural differences are reflected in their physical properties which
are discussed below.

10
1.5.5 Solid structure

Amorphous materials have little order or symmetry to their structures.

Crystalline materials are those in which the molecular structures have
order. In polymer chemistry the term crystalline is used to describe areas
in a polymeric material where the chains are closely packed in an ordered
manner. It does not refer to the regular flat sided solids known as crystals,
such as those of copper sulphate and sodium chloride.

As a general rule polymers are regarded as amorphous materials but in

practice most synthetic polymers contain a mixture of amorphous and
crystalline material. The percentage of crystallinity in a polymer
determines its properties. The more crystalline the polymer, the stronger
and less flexible it becomes.

Movement of closely packed chains is hindered by the influence of stronger

intermolecular forces than those which occur where the chains are further
apart (1.6.4). Anyone polymer chain may be involved in both crystalline and
amorphous regions along its length. This is illustrated in the diagram
below:

amorphous
region

crystalline
region

Crystallinity is affected by whether the molecules of a polymer are linear or

branched and whether the linear chain is itself isotactic or atactic.

Polymers with a low crystallinity content are often glassy and transparent,
and, if rigid, may be brittle. Polymers with crystalline regions are usually
translucent or opaque and generally have higher softening points than the
corresponding amorphous polymer.

11
A summary of physical properties related to structure is shown below:

Physical Linear Branched Cross-linked

property Isotactic Atactic
crystallini ty high low low
transparency high higher, higher lower
density higher lower lower higher
softening higher lower lower decomposes
temperature
(Tg)
flexibility lower higher higher rigid

Example poly(propene) poly(propene) low density phenol-

poly(ethene) methanal
(LDPE) resins

1.5.6 Physical states and transitions

Normally when substances made of small molecules are heated, they melt
to a free flowing liquid and, if heating continues, eventually boil. With
polymers it is more complicated.

At sufficiently low temperatures all polymers are rigid and glassy in

nature. The amorphous regions as well as crystalline regions are "frozen"
so that easy movement of chains is not possible. When the polymers are
heated, and provided they do not decompose first, the polymer chains will
reach a temperature at which they can move relative to one another. This
occurs because the molecules gain enough energy to permit the covalent
bonds to rotate freely with respect to each other. The temperature at which
this happens is known as the glass transition temperature, Tg. When the
polymer is warmer than this it becomes flexible and shows the typical
plastic properties. of polymers which allows them to be moulded.

If heating continues beyond this, the melting temperature, Tm, is reached.

The crystalline areas break down and the polymer becomes a viscous fluid.
At this temperature, enough heat is being supplied to overcome the
intermolecular forces between adjacent molecules and allow the molecules
to move with respect to each other.

The three "states of matter" for thermoplastic polymers could be broadly

defined as:

heat(TJ heat (T ,J
rigid and glassy flexible and plastic
solid solid
cool cool

12
Most polymers produced today are designed with Tg and Tm values that
give the properties needed for the article to be made readily from the
polymer and to have the right properties when in use.

1 .6 Chemistry of polymerlsatlon

There are two principal types of polymerisation reaction. These are:

• addition polymerisation
• condensation polymerisation
1.6.1 Addition polymerisation

This involves small molecules with at least one double bond between carbon
atoms. The monomers add to each other to build up a polymer chain,
usually of high relative molecular mass. The empirical formula of the
polymer is the same as that of the monomer.

Most monomers used to make addition polymers are alkenes or substituted

alkenes, so the simplest example is the polymerisation of ethene.

During polymerisation one of the bonds between carbon atoms breaks

enabling each carbon to bond with an adjacent molecule. The process
contin ues from each end un til a long chain molecule of poly(ethene) is
formed containing from 4 000 to 14 000 monomer units.

H H H H H H
\ / \ / \ /
c=c + c=c + c=c
/ \ / \ / \
H H H H H H
monomer monomer monomer

H H H H H H
I I I I I I
-c-c-c-c-c-c-
I I I I I I
H H H H H H
part of a poly(ethene) chain

Long chain molecules resulting from addition polymerisation are generally

linear and the intermolecular forces between chains are weak. Materials
containing such molecules are thermoplastic. Some examples of addition
polymers are shown in the following table.

13
 Monomer FormuIaof Name of polymer Common
monomer name

ethene a-f2=~2 poly(ethene) polythene

chloroethene ~2=CHCI poly{chloroethene) PVC
phenylethene a-i 2= CH(CsHs) poly{phenylethene) polystyrene
tetrafluoroethene a=2=a=2 poly( tetrafluoroethene) Teflon, PTFE
propene ~3a-t=~2 poly(propene) polypropylene
buta-1,3-diene ~2=~-~=a-i2 poly(buta-1,3-diene) rubber

Addition Polymers

a) Co-polymerisation
In the examples shown only one type of monomer is used in each case
and the process is known as homopolymerisation. In order to produce
polymers with specific properties two or more monomers may be
polymerised (in appropriate proportions) simultaneously. Such
processes are exam pIes of co-polymerisation and the resulting products
are copolymers.

An example is a copolymer of propene with ethene which has a lower

Tg than poly{propene) itself. A section of the copolymer chain may be
represented as:

Other exam pIes will be found in the text.

b) Mechanism of addition polymerisation

Addition polymerisation is a radical process and takes place in three
stages:
• Initiation
• Propagation
• Termination

Initiation requires radicals. These are usually provided by an initiator

such as an organic peroxide (e.g. dibenzoyl peroxide) because the 0-0
bond energy in these compounds is low enough (+150 kJ mol«) for the
bond to be broken by heat or exposure to light. The bond breaks
homolytic ally resulting in the formation of two radicals.

R-O-O-R ~ R-O· + ·O-R

Dibenzoyl peroxide decomposes to form radicals which themselves

decompose rapidly:

14
 CsHs- C- 0- 0- C- CsHs 2CsHs-C-0·
II II II
o 0 o
CsHs-C-O· CsHs· + CO2
II
o
It is the phenyl radical which initiates the chain reaction.

Because of the presence of an unpaired electron a radical is an

extremely reactive species, and takes part rapidly in the next stage.

Propagation. A radical now reacts with one of the monomer molecules

by pairing its electron with one of the electrons in the double bond to give
a new radical:

CsHsn~:~2

The double bond in the alkene has been replaced by a single bond.

This new radical reacts with another alkene molecule and the chain
continues to grow:

CsHs- Q-i2- 0i2

. + 0i2= 0i2 csHs - 0i2- 0i2- 0i2-
.
0i2

Alternatively, radicals may react by taking a hydrogen atom from one of

the carbon atoms in the same chain, thus:
.
CsHs-(CH2)n- CH2- CH2- CH2- CH2- CH2

.
CsHs-(CH2)n- CH- 0-12- CH2- CH2- CH3

The new radical then reacts with molecules of ethene, forming a side
chain.

Propagation is very rapid. At anyone time the reaction mixture will

contain only growing chains and unreacted monomers until the growth
is brought to an end by termination.

Termination occurs when two radicals combine. Because the

concentration of radicals in the mixture is very low it is more likely that
a radical will collide with a molecule of monomer, thus building long
chains.

Termination can also occur by an alternative reaction:

15
 CsHs-(CH2)x- Q-i = Q-i2 + CH3-(CH2)y - CsHs

and two smaller polymers are formed.

1.6.2 Condensation (Stepwise) polY11U!risation

Condensation polymerisation takes place between molecules containing two

functional groups with the elimination of small molecules such as water or
hydrogen chloride.

A simple illustration of the process is given below:

monomer 1 monomer2 monomer1 monomer2

-A-B-A-B-

condensation polymer

In the early stages of reaction, the products contain only two or three
monomers joined together, but these fragments continue to react, until
chain lengths of up to hundreds of monomer units are produced. This can
take several hours or even days.

a) Polyesters

Esterification is a condensation reaction. During esterification a

molecule of water is eliminated between the carboxyl group of an
organic acid and the hydroxyl group of an alcohol:

R'-C~O-R R'-C-O-R + H20

II II
o o
acid alcohol ester

Monomers of polyesters are usually dibasic acids and diols( dihydric

alcohols) which react initially to form 'dimers', for example:

16
 ethana-t.z-dlol benzene-1,4-dicarboxylic acic

!
o 0
II-{}-II
HO(CH2)20- C~ C- OH

a dimer
(a "condensed" molecule)

The dimer still has two reactive ends which continue to react in the
same way with more alcohol and acid molecules until a long chain has
built up. Terylene is an example of a polyester.

b) Polyamides
The formation of acid amides from acid chlorides and primary amines
also involves a condensation reaction. In this case hydrogen chloride is
eliminated:

o H o H
II I II I
R-C-CI + H-N-R' R-C-N-R' + HCI

acid chloride primary amine acid amide

The monomers of a polyamide are usually the chloride of a dibasic

carboxylic acid (or the dibasic acid itself) and a di-amine.

t.B-diarnlnohexane decanedioyl chloride

!
H 0 0
I II 1\
H2N(CH2)6-N- C- (CH2)s-C- CI + HCI

The amide contains an amino and an acid chloride group and reacts in
the same way with more monomers to build up a very long polymer
chain:

17
 nylon 6,10

Sometimes (as for nylon 6) a single monomer containing both

functional groups is used.

The amide linkage -CO-NH- in polyamides is the same as that found in

animal fibres, such as wool and silk, and in all other proteins, where it
is usually called the peptide link.

c) Structure of condensation polymers

Bifunctional monomers yield linear polymer molecules (see
polyamides and polyesters above) and these give thermoplastic
materials. Polyfunctional monomers give rise to branched or cross-
linked three-dimensional structures; the product is thermosetting.
Once these are formed they cannot be remoulded. Examples will be
found in the text and include phenol-methanal and melamine-
methanal plastics.

1.6.3 Contrasting addition and condensation polymerisation

Condensation polymerisation is sometimes called stepwise polymerisation

because the product is built up gradually over a period of time.

Addition polymerisation, on the other hand, results from a chain reaction

and long chains are formed very rapidly.

Addition polymerisation Condensation polymerisation

The reaction mixture contains only At any stage of the process all the
monomer, high mass polymer, and a molecular substances are present in a
tiny number of growing chains. distribution which can be calculated.

Monomer is used up relatively early in Concentration of monomer decreases

the reaction. steadily as the reaction proceeds.
High weight polymer is formed at once Molecular mass of the polymer rises
with little change to its molecular mass steadily throughout the reaction.
throughou t the reaction.
Polymerisation is complete in a short Long reaction times are necessary to
time. achieve high molecular masses.
Polymerisation may take hours or even
days to complete.

18
1.6.4 Other polymerisation reactions

Some groups of polymers considered in this book do not fall neatly into the
two main categories. In particular the chemistry of the manufacture of
thermosetting plastics (phenol-methanal, phenol-amides and the
polyurethanes), often quoted as examples of condensation polymerisation, is
not as simple as the processes described in 1.6.1 and 1.6.2.

The table below shows how some polymers are produced.

Polymerisation Products
method Notes

high density poly(ethene)

poly(propene) Monomer dissolved in
Solution poly(phenylethene) suitable solvent.
copolymers

low density poly(ethene)

poly(phenylethene) Monomer is the reaction
Bulk polyesters, polyamides fluid.
polyurethanes

poly(phenylethene)
poly(chloroethene), poly- Monomer emulsified in
Emulsion (buta-1,3-diene) water. Surfactant used.
poly(tetrafl uoroethene)
phenylethenelbuta -1,3-
diene rubber

poly(ethene) Solid catalyst particles

poly(propene) fluidised by gaseous
Fluid catalyst bed
monomer. Very small
amounts of catalyst
trapped in polymer.

Summary of polymerisation methods

19
1.7 Summary of polymer classification

The early plastics such as casein, cellulose ethanoate and cellulose nitrate
are semi-synthetic because the naturally occurring base polymer is
subsequently modified in a manufacturing process. Modern plastics are
almost totally synthetic and are derived mainly from oil. Many polymers
are also used as synthetic fibres. Polymer classifications can be shown as
follows:

CIassification Notes

Thermoplas tics Soften when heated and harden on

cooling. Cycle can be repeated over
and over again withou t chemical
change. Linear or branched chain
structure without cross links between
the chains.
Effect of heat
Thermosets Cannot be resoftened by heating.
Extensive three-dimensional cross
linking occurs to give permanently
hard materials.

Addition Usually from monomers containing a

-CH=CH- unit. Involves initiation,
propagation and termination
reactions. Initiation may be by
(1) free-radical e.g in
poly(chloroethene),
poly(phenylethene), low density
poly(ethene), phenylethenelbuta -1,3-
diene rubber and poly(methyl-2-
Method of methylpropenoate) production.
polymerisation (2) protonation by a Lewis acid
(cationic) e.g. in butyl rubber
production.
(3) carbanion formation e.g. in
poly(buta-1,3-diene) production.
(4) coordination complex formation to
give a linear highly stereospecific
product e.g. in high density
poly(ethene) and poly(propene)
production.
Condensation Generally gives different alternating
structural units from condensation
reactions between different molecules.
Nylon-6,6, polyesters, and phenolic,
urea and methanal resins are
examples, as also are the silicone
rubbers.
 Classification Notes

Elastomers Low. Rubber, polychloroprene.

Plastics Modulus of Medi um. Poly( chloroethene),

elasticity (for poly(ethenyl ethanoate)
linear polymers)
Fibres High. Polyamides, silk, polyesters,
cellulose.
Homopolymer Contain one monomer unit, e.g.
polytethene), poly(chloroethene).

Copolymer Formula Block alternating or random

arrangement of two or more
monomers. Or side-chains may be of
one monomer, the main chain another
(graft).

Linear Linear chains may take up straight,

zig-zag, coiled or random spatial
arrangemen ts.

Branched Long or short branched chains

attached to main chain.

Chemical Two- or three-dimensional cross-

Cross-linked
structure linking between chains.
Such polymers are produced by
Ziegler-N atta catalyst systems which
give stereospecific orientation of
polymers.

Isotactic All side groups are on same side of

chain.

Syndiotactic Steric structure Each alternate side group has same

orien tation.

Atactic No specific orientation of side groups -

randomly arranged.

21
1.8 Additives
It is possible to modify the properties of polymers to suit specific
applications, by the use of additives. This is less expensive than developing
new monomers and polymerisation processes. As the term suggests,
additives are other substances mixed in specific proportions with a polymer
to improve or create the properties required for a particular application.

Function Additives

Extend working • antioxidants to prevent reaction with oxygen

life
• light stabilisers to prevent colours from fading
• stabilisers to inhibit undesirable degradation in use
• absorbers to protect against harmful effects of UV light
• flame retardants to help prevent ignition or spread of flame

Improve working • fibres to improve mechanical strength

properties
• antistatic agents to prevent build up of dust through static
• impact modifiers to help plastic mouldings absorb shocks

Assist processing • waxes and lubricants as heat stabilisers to prevent

decomposition during processing
• plasticisers to make plastics softer and easier to mould
• blowing agents to produce foamed materials
• compatibilisers to blend different waste plastics for recycling

Enhance • pigmen ts for colour

appearance

Reduce cost • fillers such as talc or powdered minerals

Function of Additives
Plasticisers, which are usually liquids, are particularly useful materials
since they can be used to lower the Tg value of a particular material to make
it easier to process. On blending, the plasticiser molecules separate the
polymer chains and act like a lubricant, allowing the chains to slide around
on one another more easily. This is illustrated below.
~

~
Without plasticiser With plasticiser

22
Plasticisers are added to plastic films, such as those used in food wrapping,
to give the flexibility required. Other examples of additives will be found in
the sections referring to specific polymers.

1.9 Formulation of plastics

One of the most versatile plastics is poly(chloroethene) (polyvinyl chloride,

PVC). It can be made in either a flexible or a rigid form (and every
combination between these extremes) by varying its formulation. The table
below illustrates this.

Constituents Notes

the polymer main ingredient

plasticiser Acts as a lubricant for polymer chains.

Large amounts give flexible product, low
e.g. esters of benzene-1 ,2-dicarboxylic
quantities give rigid product.
acid

stabiliser Poly(chloroethene) is heat sensitive. It

decomposes on heating, in the absence of
e.g. lead carbonate «1%) or, for non-toxic
a stabiliser, to give a brittle product and
requirements, mixtures of metal
hydrogen chloride.
octadecanoates and epoxidised oil

extenders 'Extend' the plasticiser action but

generally cannot plasticise alone.
e.g. chlorinated hydrocarbons
Cheaper than plasticisers.

fillers To tailor the plastic for special

requirements or to make it cheaper.
e.g. chalk, glass fibre

miscellaneous _ Poly(chloroethene) products also contain:

flame retardants
UV stabilisers
antistatics
processing aids
pigments.

The formulation of PVC

1.10 Processing of plastics

Polymers are processed using different mechanisms to accommodate their

differing physical properties.

Notes

Compression moulding Usually for thermosets - powder of

polymer is moulded under heat and
pressure.

Injection moulding Usually for thermoplastics - molten

plastics are injected into a mould under
pressure. The mould surface detail
(profile of product) can be accurately
reproduced. Very widely used.

Rotational moulding Usually with thermoplastics - the powder

is heated in a closed mould which is
rotated, fairly slowly, simultaneously
about two axes. Surface detail is poor but
this method can be used to make very
large hollow articles.

Extrusion Usually for thermoplastics - the molten

plastics are fed by a screw through a die,
which for sheet or film for instance, is a
slit. Various extensions to the process
are possible - e.g. a tube may be inflated
by air, whilst still hot, to produce a
tubular film (for bags etc.), or short
lengths of hot extruded tube can be
inflated in moulds to form bottles.

Calendering Usually for thermoplastics - molten

plastics are squeezed between hot rollers
to form foil and sheet.

Thermoforming Heat-softened thermoplastic sheet is

drawn into or over a mould. If a vacuum
is used to suck the sheet into a mould, the
process is known as vacuum forming.
This process is used for a variety of
articles, ranging from chocolate box
liners to acrylic baths.

2A
1.11 Examples of Polymers

~
o
..j.)

en
~
o
~
~
o en
••...•
~bD
~.~
~ .5
......•.....

J-o J-o J-o J-o

CiS CiS CiS CiS
CL> CL> CL> CL>
~ ~ ~ ~
•....•
.f""I
•....•
.f""I
,.....
.f""I
•....•
.f""I

o
C\I

II
s
C')

~ (;
e I z ,~ Z
~()
I
~ 0
o o
C\I
I
o o ~ ~~O
\I II II \I II II II II
o
C\I

o o
C\I C\I C\I

o
C\I C\I C\I C\I

0 000

,.....
CL>
,.....
CL>
..j.)

5o
o
~..
•....•
CiS
• f""I
J-o

<
 1. 11 Exam pies of Polymers
bD

CIl
Q,) CIl
=
-6h

-=
CIl CIl C) ctS
eo -.-4
J.,. ~C)
=
~

=
Q,) ..0
rI.l -.-4
.+0)
CIl ctS
CIl ui CIl~ .+0) ~ C!

-
0
~
J.,. S :E~
Q,)
CIl bD ro
~
a~
..0 ctS Q,)

G-Sbtl
Q,)

t::= bn ctS .+0) CIl Q,)

-
:;j.+o)
ctS
a
C)
-.-4 ....
-
Q,)
ctS J.,. C)
-.-4
C) CIl

- -
CIl~
-.-4
.+0)
Q,)~
J.,.
.+0) Q,) .+0)
S 0
~ ~ctS ..0 ctS
C) C)
Q,) ..0 CIl
ctS ctS,.c::
C!
Q,)
.+0) CIl ~C! Q,)
ctS
.+0) Q,) cE :;j

j~
C)
-.-4 C)
-.-4 C)
-.-4 btl btl btl

CS
- - - = = =
.+0) .+0) .+0)
CIl CIl CIl -.-4
.+0) -.-4
.+0) -.-4
.+0)
~ ~ ctS .+0) .+0) J.,. .+0)
Q,) Q,) Q,) Q,)
C! C! C! CIl CIl CIl
0 0 0 0 0 S 0
S S S S S S

-
0
.+0)
~ J.< J.,. J.< J.,. J.,. CIl J.<
Q,) Q,) Q,) Q,) Q,) Q,)
ctS
..c=
~ ~ ~ .+0) ~ Q,)
~

i-
.+0)
~-.-4 :;j

~ 0
J.<
ctS
J.<
ctS
J.,.
ctS
.ro
CIl CIl
.ro
Q,)
J.,. cb CIl CIl
• ro ib:;j

=
Q,) Q,)
ctS

-= -= -= = = =
Q,) Q,) Q,) CIl~ CIl~ Q,) CIl~ CIl~ 0

-=
J.,._.-4
o o -.-4 oJ.,.-.-4 oJ.,. -.-4,...c:J.,.
-.-4 -.-4 -.-4 C) _ J.,.
C) _
-.-4 C) C) •••• .+0)
••••

rI.l
):;' 25 N

e
~¢~
~
I
0 :r: 0=0 8z
6 80 0
:r: I
e
ra
0 z
€-O-§
¢ § ¢8 6 6
:r: :r: :r:
N

-- 8 0-0-0
rI.l 0 N :r: a

)(
:r: 0N :r: :r:
z:>.

1
C\i 0 0
:r:
0
g <1
N
0 :r: :r: :r:
8
N
0 N
:r:
z <1
~ :r:
N
:r: ~ ~ :r: 0- -0

-
rI.l -==.
0
~

1 -.-4
J.,.
j:Q

- =
Q,)
-.-4
= -
Q,)

Z CIl~ Q,)
.+0)
-.-4 CIl
Q,)

-==~
J.< ctS
~
J.,.
Q,) J.<
~ctS ~.
0 C)
Q,)
E-4 ~
....:I
j:Q ::s

fI.)
~
i@ -=
.ae 81 -=
0

~ ctS
~ ctS
~

J
CIl Q,)

.~§ Q,)
.+0)
~ ~ !l
ctS
,.c:: S
CIl
Q,)

oS=
til ~
of=
~~ Q,) Q,) cU ctS
ro ~~ -e
.
CIl
~

1-8
,.Q~ 0
S

1~
J.<
-.-4 Q,) -.-4
S

~ 8 -
S

-
.+0) Q,)

ctS ctS CIl 0 ctS

J.<

=
C) Q,)

Q ~
~ ~ .0 Q,)
,.c::
..0
J.< ....~
0
C!
0
C!
0
C! ~8 C!
ctS
C)
0
C!
 ACTIVITIES

A1.1 Comparison of two types of plastic

Polymers are chosen for certain applications according to their chemical
and physical properties. This investigation demonstrates how different two
polymers can be.

CARE - any heating of plastics must be carried out in a fume cupboard as

many decompose to give toxic fumes.
eye protection must be worn

Requirements
sample of nylon (nylon tights are one source)
sample of carbamide-methanal (u-F resin) (buttons or fragments of
electrical fittings)
tongs
tin lid or porcelain dish
What to do
First draw up a table of results to record your observations. The table below
shows one way to do this - of course you will need more room for your
answers.

Plastic Does the Is the plastic Does the Does the Is the plastic
plastic rigid or plastic have a plastic burn thermosetting
stretch flexible? high melting orcbar? ora
easily? point? thermoplastic?

Nylon

u-F resin

1. a) Compare the nylon and u-F samples for ease of stretching and
note your observations in the table.
b) Compare the nylon and u-F samples for hardness, rigidity and
flexibility. Note your observations in the table.
c) Place the nylon sample in a tin lid or porcelain dish and heat
gently over a bunsen in a fume cupboard. Observe all the
changes that occur. Note whether the sample melts or burns and
chars. Charring indicates that the heating is causing the
polymer to decompose. Note your observations in the table.
d) Repeat the heating process with the sample of u-F and note your
observations in the table.
• Using the summary of polymers in Section 1.11, decide which, if
either, of these plastics is thermoplastic and which, if either, is
thermosetting.
• Explain the behaviour of the two samples in terms of the
molecular structure in the polymers.
A 1.2 The effect of "chain length" on tensile strength

This activity uses cotton to illustrate the effect on tensile strength of having
large numbers of fairly short chains in a polymer compared with fewer
long chains.

BACKGROUND
Chain entanglement - millions of polymer chains are mixed together
in a piece of plastic. The length of polymer chains is important in
determining the properties of a particular material.

Requirements
reel of cotton
scissors
ruler
250 cm3 conical flask
glass rod

What to do
1. a) Cut six pieces of cotton from the reel, each about 40 em long.
Then cut each 40 cm piece into four pieces of equal length.
b) Add each length of cotton separately to a 250 em" conical flask
containing 100 em" water. Stopper the flask and shake well for
about 1 minute.
c) Remove the cotton bundle with a glass rod and squeeze out the
excess water. Pull the end of one thread and note how easily it
pulls out from the entanglement. Try this several times with
different threads.
d) Now cut another six pieces of cotton from the reel, each about
40 cm long. Add these six lengths separately to a conical flask
containing water as above. Stopper and shake the flask for about
1 minute.
e) Remove this second bundle of cotton from the flask and try to pull
individual threads from the entanglement as before.
• What differences do you observe?
• Relate your findings to the molecular explanation of tensile
strength in polymers.
2. You could take this investigation further by altering the length to
thickness ratio of the cotton or other sewing fibre.

28
A 1.3 The effect of low temperature on polymers

This is an activity to investigate the effect of temperature on polymers using

bubble gum as an example.

CARE - Do not handle other people's bubble gum. After initial chewing of
gum - which should preferably be done outside the laboratory - do
NOT replace into the mouth.

Requirements
bubble gum
plastic film
freezer

BACKGROUND
If a piece of rubber tubing is cooled in liquid nitrogen and then hit with
a hammer it will shatter into fragments because it has become brittle
and glassy. Some margarine tubs are made of poly(propene) which
becomes brittle at about -10°C. When these have been stored in a freezer
the tub splits apart when attempts are made to remove the contents.

The reason for both these phenomena is that most polymers are a
mixture of crystalline and amorphous regions. At sufficiently low
temperatures the tangle of polymer chains in the amorphous regions
are frozen so that easy movement of the chains is not possible. If the
polymer has to change shape whilst in this glassy state it will do so by
breaking. Normally this will occur when a polymer is at a temperature
below its glass transition temperature (Tg).

What to do
1. a) Chew a piece of bubble gum until all the taste has gone. Remove
the gum from the mouth.
b) Gently pull the gum between your hands to stretch it a little and
then release it - does it exhibit any elastic property?
c) Now pull the gum so it stretches to about 8 times its original
length.
• does it still show elastic properties?
• does it completely return to its original length when
released?
• what term is used to describe this irreversible change?
2. a) With your fingers, work the piece of bubble gum into a shape
similar to a lOp coin.
b) Wrap in plastic film and place in the coldest part of the freezer.
c) Remove the gum from the freezer after about 15 minutes and
bend it quickly.
• what happens?
• what happens as the gum returns to room temperature?
• explain this in terms of molecular structure and Tg.
A1.4 An Illustration of "cold-drawing" of a plastic

This short activity investigates the necking effect produced by stretching a

thin strip of polymer sheet, illustrating the principle of cold-drawing.
Requirements
strips of polymer sheet 250 mm x 15 mm - cut from a carrier bag

What to do
1. a) Hold the ends of one strip of polymer between the finger and
thumb of both hands and gently stretch the material. When
necking appears continue stretching gently and this will cause
an increase in the size of the necked region.
b) Measure the length of the necked region just before it breaks.
• Is this region more or less opaque than the original plastic?

All polymers contain some crystalline regions. When you stretched the
polymer a neck was formed. This illustrates the principle of cold-
drawing. In the necked region the polymer chains which existed in the
the undrawn material have now aligned to form a more crystalline
region. As the neck increased, more of the polymer chains aligned,
except at the ends which were being pulled.

necked region

~ - -==- ~~~~t=§~~~
-== ~--=--==-
-~-~
4
F ~
chains aligned
~
4
amorphous (crystalline) amorphous
region region

Drawn polymers are more opaque because of the residual presence of a

small percentage of non-crystalline regions with a different refractive
index.

c) Repeat the experiment using a strip of the same plastic cut at

right angles to the first cut.
• What happens?
• What does this tell you about the polymer molecules in the
plastic?
d) Now repeat the experiment with as many different thermoplastic
materials as you can find.
Tabulate your results to show
the extension length of the plastic in one direction
the extension length of the plastic in the other direction
the extent of opacity in the drawn region
• Explain all.your results in terms of the apparent length and
alignment of the polymer molecules in each plastic.

31
A 1.5 Two forms of a natural polymer (casein)

This practical activity examines the precipitation of casein (a long chain

molecule from milk protein) to produce a natural polymer and compares a
cross-linked sample with a non cross-linked sample. After the initial
process the samples will need to be stored for a period of about six weeks,
during which time observations can be made at specified intervals.

CARE· the methanal solution must be used in a fume cupboard

CARE· If the fumes of hydrochloric acid and methanal combine a
powerful carcinogen is produced. Therefore hydrochloric acid
should not be near the experiment.
For stage (d), wear protective gloves arid at stage (f) work in a fume
cupboard.
wear protective gloves and eye protection

Requirements
dilute (2 mol dm:") ethanoic (acetic) acid - IRRITANT
dilute (8%) methanal (formaldehyde) solution - HARMFUL
100 em" skimmed milk (one or two days old but not 'long-life')
food dye or ink
250 em" beaker
stirring thermometer
glass stirring rod
two petri dishes and one lid
dropping pipette
absorbent cloth or paper

What to do
1. a) Place 100 em" of milk into the beaker and gradually heat to 50°C
using the stirring thermometer to check the temperature.
b) At 50°C turn off the heat source and add drops of dilute ethanoic
acid using the dropping pipette while stirring with the glass rod.
This will cause the casein to precipitate in the bottom of the
beaker.
c) Continue adding drops of dilute ethanoic acid until no more
casein is precipitated.
d) Remove the casein from the beaker and knead it in warm water
with your finger and thumb.
e) After kneading squeeze the casein to remove excess water and
wipe dry with a cloth or absorbent paper (newspaper is adequate
for this). At this point colouring can be added if so wished by
mixing the casein with a few drops of food dye or ink.

32
 f) Separate the casein into two samples (it will shrink up to 500/0 on
drying) and place the samples in separate petri dishes. Cover
one of the samples with 8% methanal solution and then place the
lid on the petri dish. This sample should be left in the fume
cupboard for 2 days, after which the methanal solution should be
poured off. Wash the sample in water, taking care not to handle
it with your fingers. Leave the other sample uncovered to harden
in air.
g) Both samples should now be left for a few weeks to harden. After
three weeks examine both samples. The untreated casein will
harden more quickly whereas the methanal treated casein will
still be soft at this point.
h) After six weeks both sam ples should be hard enough for sanding
with fine glass paper and polishing with a metal polish if
required.
2. Test both samples by immersing in water.
• Which sample is more likely to contain cross-linking?
• Give a reason for your answer.
A 1.6 Making an unusual polymer

This practical activity investigates the production of a novel polymeric

material with some unusual properties.

CARE - Eye protection and disposable gloves must be worn.

Avoid breathing polyethanol dust.

Requirements
dis odium tetraborate solution, 4% (10 em")
poly(ethenol) solution, 4% (50 em")
polystyrene drinks cup
disposable gloves
flat wooden sticks for stirring (lollipop sticks)
50 cm3 measuring cylinder
10 em" measuring cylinder
food colouring or fluorescen t dye (optional)

What to do
1. a) Put 50 em" of the poly(ethenol) solution into the polystyrene cup
and stir the solution, noting its appearance.· You could add a few
drops of food colouring or fluorescent dye at this stage if you wish
to make it visually more attractive.
b) Add 10 cm3 of the sodium borate solution and stir the mixture
vigorously until it sets to a gel. Once the gel has formed remove it
from the cup and continue to shape it with your hands.
Wear gloves for this part of the experiment.
2. Investigate what happens to the gel when:
you pull it slowly
you pull it abruptly
you suspend it from your hand
it is left on a flat surface for a short time
it is left in a petri dish for a short time
it is dropped on the floor
chunks of separated gel are squeezed together
a small portion of the gel is immersed in water
3. Explain your observations of the behaviour of the gel in terms of the
intermolecular forces present.
• How do you think the cross-links present in the gel differ from
the cross-links in a thermosetting polymer?
• What do you think is the essential difference between the
intermolecular bonding in the 'slime' and that between the
polymer molecules in polythene?
• What type of intermolecular bond would account for the observed
behaviour in your 'slime'?
 SECTION 2
Thermoplastics
Thermoplastics are polymers without chemical crosslinks between their
chains. Generally, they can be heated and remoulded many times.

The following polymers are described in this section:

0 polycarbonates

" poly(chloroethene)
0 poly(ethene)
0 poly(methyl-2-methylpropenoate)
(I
poly(phenylethene)
e poly(propene)
• poly(tetrafl uoroethene)

2.1 POLYCARBONATES

Repeating unit Polycarbonates are characterised by the group:

o
II
-o-c-o-
Most (over 90%) of the world production is based on
bisphenol A

~-o-FO-OH
0-13

0-13

4,4 'dihydroxyphenyl-2,2' propane

t
In this case the repeating unit is:

t-9-°-
0-1
I 3 II
0
c-o

poly [2,2'-propane-bis-(4-phenyl carbonate):

The general formula of the repeating unit is:

All production involves carbonyl chloride (phosgene)

COC12•

35
Monomers In commercial production polycondensation occurs
during the process so the monomer which undergoes
condensation is usually not isolated.

200H
0
Manufooture of + H3C-C-
II
a-t3
monomer
phenol propanone

~ oo-Q-f-o-OH a-t3
+ H2O
a-t3

Manufooture of See text below.

polymer

Reaction type Polycondensation Bond Type carbonate ester

Physical density 1.2 g cm=: Tg422 K; Tm -505 K;

properties dielectric loss 0.0021
Very tough, transparent, fire retardant, dimensionally
stable and strong over temperature range 170 K to 420 K.

Principal uses Shatterproof windows, sterilisable utensils, feeding

bottles, safety spectacles, compact discs.

Manufooture of polymer

There are three methods available.

a) Interfacial
Bisphenol A in solution in dichloromethane and aqueous NaOH.

n NaO-o-?-o-ONa CH3
+ n
CI,

CI
/
c=o
CH3
 The reaction is highly exothermic and the polymer chains can grow
to extreme lengths, coagulating the whole reaction mixture. In
practice, chain termination agents are added to control the chain
length.

b) Solution (equation similar to (a) )

Bisphenol A in solution in dichloromethane with a catalyst (a tertiary

amine, pyridine). Carbonyl chloride is bubbled into this homogeneous
mixture; the polymer is formed rapidly and is soluble in the reaction
solution.

c) Transesterification
This is carried out in the melt phase. Carbonyl groups are provided by
a carbonate ester.

o UOH, NaOH or KOH o

II catalyst II
HO-R - OH + R'O- C- OR' HO-R - 0- c- OR' + R'OH
150 -320°C
1atm -1 mm Hg
aromatic dial carbonate ester

The intermediate product undergoes immediate polycondensation.

This is the most technically difficult and expensive route. A high
temperature is required to keep all the components in the molten
phase and a reduced pressure is required to avoid loss of reactants.
This is followed by high vacuum distillation when high molecular
weight polymer is produced as a molten stream.

Resin finishing

Few articles are made of pure polycarbonate. To achieve engineering

specifications, compounding with modifying agents, ("finishing") is
necessary.

Use of dichloromethane

Demand for polycarbonate resins continues to grow but the use of

dichloromethane (used here as a solvent) is being restricted by governments
because of the effect of volatile chlorinated hydrocarbons (CHCs) on the
ozone layer. A ban on this solvent would preclude the interfacial and
solution syntheses. Fortunately the third route, although technically more
difficult, is available.
2.2 POLV{CHLOROETHENE) (Polyvinyl chloride, PVC)

Repeating unit ta-t2-CHOt

Monomer chloroethene, (vinyl chloride),

a-t2=0i-O
(also known as VCM - vinyl chloride monomer)

Manufacture of Raw materials: ethene, chlorine or hydrogen chloride, air

monomer
Two processes (see text for detail)

a-t2= 0i2 + CI2 CI- 0i2- 0i2- CI

or
1
0i2=0i2 + 2HCI + '202

catalyst
CI- a-t2- 0i2- CI + H2O

followed by cracking:

720- 870 K
+ HO

peroxide initiator
Manufacture of monomer in aqueous suspension polymer
polymer 325 K. 13 atm

centrifuge to separate and dry

or bulk polymerisation giving purer product

Reaction type Addition Bond type Alkane

Physical Density 1.20-1.44 gem-a; Tg 354 K; Tm 403-433 K; brittle

properties

Principal uses Pipes and fittings 31; Windows etc 18; film and sheet 11;
(%) bottles 9. PIasticised: cables 10; film and sheet 8; flooring
7; coating (paper + fabrics) 9; tubing and windows 4.

Modified fonns Plasticised

Tonnage World, 9.7 x 1()6 (1992); W Europe, 4.9 x 1()6 (1993);

UK, 0.6 x 1()6 (1992)

38
2.2.1 Manufacture of monomer

The monomer 1,2-dichloroethene is obtained from 1,2 dichloroethane.

a) 1,2-dichloroethane production
Two processes are in operation for the manufacture of 1,2-dichloroethane:
Direct chlorination
Ethene is reacted with chlorine in the liquid phase, using excess
product as solvent. The reaction is very exothermic, so no heat has to
be supplied. The reaction temperature is maintained at
320-340 K as higher temperatures give unwanted polychlorinated
compounds.

Oxychlorination route

Ethene is reacted, in the gaseous phase, with hydrogen chloride and

air in the presence of a copper(II) chloride/potassium chloride catalyst
at 490-550 K under 5 atm pressure. As the reaction is highly
exothermic, the reactor vessel is cooled to give the optimum reaction
temperature and to reduce unwanted by-product formation e.g. of
chloroethane and 1,1,1,2-tetrachloroethane. 95% conversion of ethene
to 1,2-dichloroethane is obtained. Unreacted hydrogen chloride is
removed by scrubbing with aqueous sodium hydroxide.

Impurities, such as unreacted ethene and unwanted chlorinated

hydrocarbons, are removed by distillation. Unreacted ethene is
recycled.

b) Chloroethene production
The purified 1,2-dichloroethane (from either route) is pyrolysed (thermally
cracked) to give chloroethene.

720 -870 K
+ Hel AI-P = + 74 kJ mol "
Free-radical reactions are involved:

initiation

propagation
.
CI- 0i2- Oi- CI + HCI

Chloroethene is separated from hydrogen chloride and unconverted 1,2-

dichloroethane in a two-stage distillation process. Hydrogen chloride is
removed in the first stage and recycled to the oxychlorination process. The
second stage separates chloroethene from unreacted 1,2-dichloroethane,
which is recycled to the cracker.

2.2.2 Polymerisation
PVC is manufactured by free-radical polymerisation in either suspension
or bulk processes. In the suspension process (most common) the monomer
(bp 259 K) is polymerised in aqueous dispersion at 325 K. Pressure (10 atm)
is used to keep the monomer in a liquid phase. A peroxy initiator such as
dodecyl peroxide is used. After reaction, excess monomer is removed and
the polymer is separated by centrifuging, and dried.

In bulk polymerisation of monomer, the polymer precipitates out as it is

formed, since it is insoluble in the monomer.

A purer product (free from suspending agents) is produced by the bulk

process.

PVC is a porous, white powder and, used without plasticisers, gives a rigid
but not brittle moulded product.

2.2.3 Economics
The approximate make up of production costs per tonne is as follows:-

Vinyl Suspension
Chloride PVC %
Monomer %
Ethene 45
Chlorine zo
Vinyl chloride monomer a2
(VCM)
Catalysts and additions 2 3
Utilities 5 4

Selling Expenses, 3 6
Transport, Packaging
Fixed Costs, Labour, 25 25
Overheads, Depreciation

The most important factor affecting the cost of PVC is the price of oil. This
directly affects the cost of ethene. It also changes the energy costs and
consequently affects the cost of production of chlorine.

40
2.3 POLY(ETHENE) (Polyethylene, Polythene)

Repeating unit

Monomer ~2=~2

ethene (ethylene)

distil steam
Manufacture of crude oil naphtha fraction ethene
cracking
monomer
or
steam
natural gas liquids ethene
cracking

Manufacture of i) LDPE
>0.1% 020r
polymer peroxide initiator

420 - 570 K
1000 - 3000 atm
low density form

ii) HDPE

Ziegler - Natta catalyst

310-360K
1-SOatm
high density form

Reaction type Addition Bond type Alkane

Physical LDPE density 0.92 g cnr", Tg 148 K; Tm 395 K;

properties
crystallinity low

HDPE density 0.96 g cnr=, Tg 188 K; Tm 409 K; 70%

crys talline
Principal uses
LDPE Film (shrink wrap, carrier bags, bin liners, moisture
(%)
barriers) 67; injection moulding 12; wire and cable
insulation 8; extrusion and coating 8; other 5.

HDPE Blow moulding (containers for household and

industrial chemicals) 41; injection moulding
(buckets, bowls, hospital sanitary ware, food boxes)
27; film 14; pipe 10; other 8.
Modified forms LLDPE (linear low density polytethene) formed by co-
polymerising ethene with higher alkanes (e.g.
butene). This introduces some side chains into
polymer molecule, preventing close-packing.
Tonnage
World: LDPE 5.7 x 106; LLDPE 4.9 x 1()6;HDPE 7.4 x 1()6
(1992)
W Europe LDPE 4.6 x 106; LLDPE 1.0 x 106; HDPE 3.2 x 106,
(1993)

41
2.3.1 Manufacturing processes

a) Low density form (LDPE)

Low density poly(ethene) was discovered in 1932 during a research

programme at ICI to investigate reactions under high pressure. The
process used today operates under very high pressure (1000-3000atm) at
moderate temperatures (570 K). Under these conditions ethene will yield a
polymer which has a high relative molecular mass.

Ethene (purity in excess of 99.9%) is compressed and passed into a reactor

together with an initiator. The molten poly(ethene) is removed, extruded and
cut into granules. Unreacted ethene (75%) is recycled. The polymerisation
process involves a free radical mechanism. The free radical process can
operate in the liquid phase, the gas phase, in emulsion or in solution. It uses
an initiator such as O2(>0.1%) or benzoyl peroxide to generate the free radicals,
as shown by the equations below:

The free radicals resulting from this repeating process build very long
chains of polymer molecules.

It can be seen that the molecule is now very long - it is a polymer.

However, there is an interesting reaction in which the polymer chain does

not react with another molecule of ethene (an intermolecular reaction) but
reacts with itself (an intramolecular reaction), thus:

RO~ a-t2- a-t2- a-t2- a-t2-

.
a-t2 ~ RO~
.
a-t- a-t2- a-t2- a-t2- a-t3
chair
x y

The radical X forms a ring and the end CH2 group abstracts a hydrogen
atom from further down the ring;

42
The unpaired electron is now along the chain so that it is a side chain that
begins to grow.

.
a-t2
I

RO..tV'\I'
.
C"""'" a-t 3 + H2C = Oi 2 ~ RO..tV'\l'
a-t2
I
C"""'" a-t 3
I I
H H

When a termination reaction occurs it still leads to a polymer molecule, but

one with side chains that are alkyl groups.

For exam ple,

a-t3
I
a-t2
I
a-t2
- a-t2- a-t2- a-t2-
I
a-t- a-t2- a-t2- r- a-t3

a-t2
I
a-t2
I
a-t2
~
a-t3

As we will see later, these side chains give polyethene some very important
properties.

The total concentration of all types of branches is about 20 per 1000 carbon
atoms. The relative molecular mass, long-chain branching and short-chain
branching all influence the physical properties of low density poly(ethene).
The short-chain branching affects the degree of crystallinity which in turn
affects the density of the material. LDPE is generally amorphous and
transparent with a density in the region of 0.91 to 0.93 g cm-3 and about 500/0
crystallini ty.

LDPE

As the density of poly(ethene) increases, properties such as stiffness, tear

strength, hardness, chemical resistance, softening temperature and point
at which the polymer will deform increase whereas permeability to liquids
and gases will decrease.

43
A decrease in the long-chain branching makes processing more difficult
but produces an increase in tensile strength, toughness, impact strength
and softening temperature.

b) High density forms (HDPE)

Two methods are available using different types of catalyst.

Ziegler-Natta catalysis - Ethene is polymerised, at low temperatures

(320 - 350 K) and pressure (1-50atm), in suspension with a catalyst. An
example of the catalyst is aluminium triethyl containing a very low
concentration of a transition metal salt prepared from the reaction of an
aluminium alkyl and titanium(lV) chloride in a solvent such as heptane.
This produces the polymer in a powdered or granular form which is
insoluble in the reaction mixture. The heat generated during
polymerisation is removed by a cooling process.

After polymerisation, unreacted ethene is removed from the product and

recycled. Water (or alcohol) is used to destroy the catalyst and the polymer
is then filtered off, washed, to remove any remaining solvent, and dried. In
most processes the catalyst residue in the polymer is very small and
remains in the product. The high density poly(ethene) powder is generally
converted into pellets.

The high density poly(ethene) produced is virtually unbranched and has

greater tensile strength, rigidity and a higher melting point than low
density poly(ethene). The polymer is therefore highly crystalline and on
average contains less than one side-chain per 200 carbon atoms in the main
chain structure.

HOPE

High density poly(ethene) has a density in the region of 0.95 to 0.97 g cm-3
and is about 95% crystalline. It shows an improvement on the low-
temperature brittleness and low permeability to gases and vapours
characteristic of low density poly(ethene). High density poly(ethene) also
has better chemical resistance.

Inorganic catalysis - The catalyst is a transition metal oxide, such as

chromium(lII) oxide, on an alumina-silica or silica support. The pressure
and temperature (30atm, 350 K) involved are similar to those for the Ziegler-
Natta method.

c) Linear low density form (LLDPE)

Linear low density poly(ethene) is manufactured by processes similar to

those used for high density poly(ethene). Its low density is obtained by
copolymerising ethene with comonomers such as but-l-ene or hex-l-ene.

44
This introduces a larger number of side chains (butyl, or hexyl pendant
groups) into the polymer giving the material much better resilience, tear
strength and flexibility without the addition of plasticisers. This makes
linear low density poly(ethene) an ideal material for the manufacture of
film products, such as those used in wrappings.

LLDPE

A growing number of companies are now producing linear low density

poly(ethene) using low pressure solution/slurry or low pressure gas phase
processes. These processes are represented diagrammatically below and
on the next page. The relative simplicity of these low pressure processes
means that capital and operating costs are lower than those of the high
pressure alternatives. In addition the gas-phase process eliminates the
need to use a solvent in the reaction.

Recycle

Low Pressure Solution/Slurry Process

45
 Granular
poly(ethene)

Low Pressure Gas-Phase Process

2.3.2 Economics
The cost ofpoly(ethene) is dependent on the cost of ethene, which in turn
depends on crude oil or gas prices, and on the supply demand balance. By
1989 demand in Western Europe exceeded supply. Since then, new
production capacity has come into effect, reducing poly(ethene) prices. The
product is not significantly at risk from substitution by other materials.
In the early 1990s, production moved towards low pressure gas-phase
processes for the manufacture of linear low density poly(ethene) since they
are more economical to operate. Now nearly all new major poly(ethene)
plant development is within the gas-phase field of operations.

46
2.4 POLY(METHYL-2-METHYLPROPENOATE)
(Polymethylmethacrylate, acrylate ester, Perspex)

Repeating unit

Monomer Methyl-2-methylpropenoate, (methyl methacrylate)

Manufacture of Raw materials: propanone (acetone), CH COCH

3 3
, and
monomer hydrogen cyanide, HCN.

HCN
NaOH

98%H,pJy
/Q-Ipt

COp-l3
I
H2C=C\ + H20
0-13

The second stage is carried out without separation of the

product from the first stage.
Manufacture of Bulk or suspension polymerisation using a free radical
polymer initiator dissolved in the .monomer at 330-340 K. (This reduces
shrinkage and evolution of heat).

Reaction type Addition Bond type alkane

Physical Density 1.08-1.18g cm=, Tg 266-399 K; Tm 433-473 K.

properties

Principal uses Illuminated signs 18; lighting 16; general 16; automotive
(%) industry 15; glazing 11; multiwall sheet 8; displays 8; sanitary
ware 5; medical 2; lenses 1.
Tonnage World 1.5 x 106 tonnes (1991).

47
Uses related to properties
Poly(methyl-2-methylpropenoate) is a linear thermoplastic, about 70-75%
syndiotactic (Section 1.5.4). Because of its lack of complete stereoregularity
and its bulky side groups, it is amorphous. It is resistant to attack by dilute
acids and alkalis and has excellent outdoor weathering qualities. It has a
high tensile strength and can be readily fabricated.
The outstanding property of acrylate esters (e.g. Perspex) is optical clarity
and lack of colour so they are particularly useful where light transmission
is important. High molar mass cast sheet is used as a replacement for
glass in glazing and illuminated signs. Lower molar mass products are
used in domestic lighting and car lights. Unfortunately, compared with
glass, Perspex scratches easily and any improvement in surface hardness
is accompanied by a deterioration in impact strength. It cannot therefore be
used as a replacement for glass very often.

2.5 POLV(PHENVLETHENE) (Polystyrene)

&peating unit or

Monomer Phenylethene (styrene),

~HsCH= a-i2
Manufacture of Raw materials: ethene, benzene
monomer
AICI3cat
CsHs - a-f2- a-f3
600 K. 40atm
ethylbenzene

C6HS - a-f =a-f 2 + H2

phenylethene

peroxide initiator in
Manufacture of n C6H 5 - a-i = a-i 2
aqueous suspension
polymer

Reaction type Addition

Physical Density 1.04-1.11 g em-3; Tg 300 K; degrades >350 K;

IV

propertks brittle; transparent (unless toughened).

48
Principal uses Packaging 37; cups, cartons 32; household including
(%) refrigerators, 27; toys 5.

Modified forms (i) Polymerisation with 8% dissolved poly(buta-1,3-diene)

gives toughened translucent polymer.
(ii) Co-polymerisation with propenonitrile and poly(buta-1,3-
diene) gives ABS rubber. This is tougher and more
resistant to chemicals.
(iii) Expandable poly(phenylethene) is manufactured as beads
containing pentane.

Tonnage World, 4.0 x 106 (1992); UK, 0.2 x 105, W Europe, 1.8 x 106
(1993)

2.5.1 Polymerisation
Radical polymerisation is used to produce the polymer. This can be
thermally initiated in bulk (a peroxide may be used as an initiator), or by
solution polymerisation (table p19) using ethylbenzene as a solvent to
dissolve the initiator, monomer and polymer. Alternatively phenylethene
monomer is polymerised in aqueous suspension, using a peroxide as an
initiator, and poly(phenylethene) is deposited as tiny beads because it is
immiscible with water.

Expandable poly(phenylethene) is manufactured as beads containing a

gaseous hydrocarbon blowing agent such as pentane (or hexane). Pentane,
typically 5-70/0 by weight, may be incorporated before polymerisation or the
beads can be impregnated under heat and pressure in a post-
polymerisation process.

Pentane is a liquid at room temperature with a boiling point of 307 K. When

the beads are heated in steam the hydrocarbon volatilises to create a 50-fold
increase in the volume of the foamed polymer particles. These are
subsequently blown into moulds and fused by further steaming and then
cooling. The expanded polytphenylethene) has good thermal insulation and
energy absorbing properties. It is used in the construction industry as a
thermal insulator. It is also widely used for packaging.

2.5.2 Economics
Poly(phenylethene) costs are dominated by the price of benzene and, to a
lesser extent that of ethene. Both are related to crude oil costs. However, in
1988, although crude oil prices were low, benzene was in short supply and
had become rather costly. Poly(phenylethene) prices thus rose to a level
(about £800/tonne) at which point substitution by poly(propene) began to take
place in some applications. The price of poly(phenylethene) is volatile and
this coupled with an uncertain supply situation constrains the growth
potential of this industry.

49
2.6 POLV(PROPENE) (Polypropylene)

Repeating unit

Monomer Propene, (propylene),

distil steam
Manufacture of crude oil naphtha fraction
cracking
propene
monomer

Manufacture of n a-ts - a-t = a-t 2

polymer

Reaction type Addition Bond type: Alkane

Physkal Density 0.905 gm-3; Tg 270 K; Tm 440 K; 70% crystalline

properlies

Structure Three basic chain structures (p10). Commercial polymer is

predominantly isotactic, containing about 1-5% by weight of
atactic material.
Principal uses Fibre 36; film 18; packaging 11; household 10; building 3.
(%)

Modified forms Co-polymerisation with ethene ----7 ethene/propene rubber

Tonnage World, 8.1 x 1()6(1992) ; UK, 0.3 x lOS,(1992), W.Europe, 4.7 x 106
(1993)

2.6.1 Manufacturing processes

a) Slurry process

Propene is polymerised in an inert hydrocarbon solvent, e.g. heptane, at

temperatures of 320-360 K and pressures of 1-15 atmospheres. After the
polymerisation, the solvent is separated from the solid polymer, purified
and recycled.

b) Bulk process

Polymerisation takes place in liquid propene, in the absence of solvent, at a

temperature of 320-360 K and pressure of 20-40 atmospheres. After
polymerisation, the solid polymer particles are separated from liquid
propene, which is then recycled.
This process is more cost effective than the slurry process since there is no
solvent to purify and the catalyst productivity is higher, because of the
higher pressures. However, this process cannot be used for the production
of block copolymers.

c) Gas Phase Process

Propene is polymerised in a fluid bed or stirred bed gas phase reactor at
temperatures of 320-360 K and a pressure of 8-35 atmospheres. Polymer is
separated from the gaseous propene using cyclones and the unreacted gas
is recycled. This process, like the bulk process, is more cost effective than
the slurry process. It can be used for making the full range of polymers,
like the slurry process, and is usually used in conjunction with the bulk
process for making block copolymers.

All three processes can be operated continuously and use 'stereospecific'

Ziegler-Natta catalysts to effect the polymerisation. The catalyst remains in
the product and needs to be destroyed using water or alcohols, before the
polymer is converted into pellets.

2.6.2 Copolymerisation involving propene

There are two main types of copolymer. The simplest are the random
copolymers, produced by polymerising together propene and ethene.
Ethene units, usually up to 6% by mass, are incorporated randomly in the
poly(propene) chains. Crystallinity and melting point are reduced and the
products are more flexible, with much enhanced clarity.

The second type of copolymers are the so-called 'block' copolymers. These
are made by following the poly(propene) homopolymerisation with a
further, separate stage, in which propene and ethene are copolymerised.
Copolymerisation produces an elastomeric phase of ethene/propene rubber,
which increases the toughness of the polymer and can reduce the
embrittlement temperature to values as low as 213 K.

2.6.3 Structural isomerism ofpoly(propene)

The structures and consequent properties of isotactic, atactic and

syndiotactic poly(propene) are described in Section 1.5.4.

51
2.7 POLV(TETRAFLUOROETHENE) (PTFE, Teflon)

&peating unlt f a=2- a=2+

Monomer Tetrafluoroethene,

Manufiwture of Raw materials: methane, chlorinelhydrochloric acid,

monomer hydrogen fluoride

Methane is converted into trichloromethane, either in the

liquid phase or in the gas phase. In the liquid phase, zinc
chloride is used as a catalyst and the temperature of
reaction is 370 - 420 K. In the gas phase, alumina gel is
often used as the solid catalyst and the temperature of
reaction is 620 - 720 K.
a-t4 + 3CI2 ~ CHCI3 + 3HCI

Trichloromethane is then converted in to tetrafl uoroethene

in two processes:
SbCI3
CHCI3 + 2HF ~ CHCIF2 + 2HCI

1000K
2CHCIF 2(g) ~
1 atm
F2C= a=2 (g) + 2 HCI (g)

LlJ-{J = + 127.6 kJ mol"

(Product must be cooled immediately to prevent reverse

reaction)

Manufiwture of TFE is usually manufactured during a continuous

polymer polymerization process (see text)

water-containing
initiator

20 atm, 310-350 K

Reaction type Addition

Physical Density 2.10 - 2.30 g cm-3, Tg 160 K (2 major transitions

propertks involved); Tm -600 K; electrical resistivity high.
Principal uses Cable insulation; reactor linings; non-stick domestic
utensils; medical e.g. joint replacement coatings;
construction e.g. bridge slide-bearings.
Tonnage World, 75 x 103; (1992) ,W Europe, 11 x 103 (1992),
UK, 1.8 x 103 (1992)

52
2.7.1 The Process

Since tetrafluoroethene is a reactive gas (bp 197 K), it is usually made for
polymerization when and where required, so that there is minimum
storage time of the monomer.

Steam, preheated to 1220 K, and chlorodifluoromethane, at 670 K, are fed

into a reactor. Steam is used to dilute the reaction mixture and hence
reduce the reactant partial pressure, and also to supply all the heat
required by the reaction.

In the reactor (1020 K) chlorodifluoromethane is thermally decomposed to

give TFE. The product is rapidly cooled by passage through a water-cooled
heat exchanger. This is made of graphite to resist chemical attack and
thermal shock. Reactor residence time is 1 second.

Polymerisation is carried out by passing TFE into water containing an

initiator (e.g. ammonium persulphate) at 310-350 K and a pressure of 20
atm.

Two different procedures are used:

• suspension polymerisation to give granular resins, used for

mouldings.
• emulsion polymerisation to give fine-powder (dispersion) resins,
used for extrusion processes.

Valuable characteristics
PTFE is a highly stable compound whose properties remain virtually
constant between 200-620 K. It has very low friction, good non-stick
properties, and is hydrophobic and highly resistant to chemical attack. It
also possesses high electrical resistivity.
 ACTIVITIES

A2.1 Production of poly(ethene)

Photocopy the diagrams below which represent the various stages in the
production of poly(ethene). From the copy cut out each diagrammatical
stage and paste onto a blank sheet to build up a correctly linked linear
sequence diagram of the process.

Ethene 1 2
Filter
./ Solvent
, Catalyst
Polymer/Solvent
Suspension Mixture

Reactor under Used

heat & pressure Catalyst

Precipitation 3
Tank
A ,. A ,. ,. ,. ,. ,.
A ,. ,. ,. ,. ,. ,.

: A: Alcohol: A:
,. A ,. ,. fA ,. fA
A ,. A ,. ,. A ,. ,.
A ,. ,. A ", ,. ,.

Reaction
A ,. ,. ,. ,. ,. A A
A ,. ,. ,. ,. ,. A
,. ,. ,. ,. ,. Ie ,. ,.

Mixture
,. ,. ,. A ,. ,. ,.
A ,. ,. At ", fA ,. ,.

-
,. ..• ,. ,. ", ,. ,. ,.
A A A ,. til. <lie ,.

A ,. A
,. ,. ,. ,. ,. A ". ,.
A ,. ,. ", Polymer/Solvent
,. ,. ,. ,. ,. ,. ,. ,.
,. ,. A ,. ,. A ,.

,. ,. ,. ,. ,. ,. ,. Mixture
'" ,. ".A."
,. ,. A .•... A

Unreacted Ethene 4
removed and recycled

J Centrifuge 5

x 'f
~ Pol:tmer/Catal:tsV
Solvent Mixture
••
.~ ~ :~ Clean
Polymer
Separator
Solvent
Out

Drier

Pol:tmer Read:t For ••

Product Processing

Poly(ethene)

54
A2.2 Investigating poly(ethene)
In this activity you will compare some properties of LDPE and HDPE, and
relate them to the structures of the two plastics.
A2.2 Comparing two forms ofpoly(ethene)

Requirements
samples ofHDPE and LDPE
250 em" beakers
tongs
access to a balance
What to do

1. Plan experiments to compare the two forms ofpoly(ethene). Identify

potential hazards and the precautions you need to take. Discuss your
plans with your teacher before you carry out any experiments. You
may wish to ask for extra apparatus.

You should compare the following properties:

texture, density, flexibility, softening
Try to make your comparisons as fair as possible.
• How can the properties of the two forms ofpoly(ethene), and the
differences between them, be explained in terms of their
structures?

Density Tensile Elongation at Price (1992)

PolymerType
(g cm=) strength (MPa) fracture (%) (£ / tonne)

LDPE 0.92 15 ax> 440465

HDPE 0.96 2:) 350 460485

2. Use the information on LDPE and HDPE provided in the table above
to help you answer the following questions:
• Will either polymer sink in water?
• Explain why the tensile strength of LDPE is lower than that of
HDPE.
• Identify the factors you think influence the cost ofHDPE and
make it more expensive than LDPE.

The discovery ofa polymer that was easy to work with and one that was
such a good insulator was seized upon by the scientists developing Radar
during the Second World War. A little earlier, it was used to sheath the
first telephone cable laid at the bottom of the sea, between the mainland and
the Isle of Wight. Later it was used to connect continents by telephone.

• Which properties of poly(ethene) made it an ideal material for

the two applications described above?
A2.3 The depolymerlsatlon of poly(ethene)

CARE - do not allow the delivery tube to get blocked. Remove it from the
beaker of water before you stop heating, in order to prevent suck
back.
- eye protection must be wom

Requirements
small samples of polythene
bromine water - HARMFUL
4 test tubes
delivery tube with bung to fit test tube
400 cm3 beaker
broken pot
What to do
1. Set up the apparatus as shown.
2. Heat the broken pot strongly, then heat the polythene gently.
3. Repeat this cycle to keep the pot hot so it will then act as a catalyst.
4. Collect 3 test tubes of the gas given off. Test the gas by shaking with
Icm" of dilute bromine water and with a lighted splint.

polyethene
/
pieces

tube full of water

ready to collect
more gas

5. Record what happens when you:

apply a lighted splint to the mouth of one tube.
add a few drops of bromine water to another tube, stopper it and
shake well.
• What properties distinguish the product from the original
polymer?
• What properties lead you to conclude that this gas may be
ethene?
• Wha t other gases might react in this way?
• Write an equation for the reaction of ethene with (a) bromine
and (b) bromine water.

56
A2.4 Some properties of expanded poly(ethene)

This activity examines the cell structure of plastazote foam and investigates
some of the properties and applications of this unusual poly(ethene)
material.

Requirements
plastazote foam sample
scalpel
microscope slide
microscope (magnification x 40 x 100)

PLASTAZOTE FOAM

Plastazote foam is an expanded poly(ethene) foam which was first made

in the early 1960s and is available in a range of densities. Current UK
consumption is in the region of 75 000m3 per year. To make plastazote
foam, poly(ethene) is heated in a high pressure vessel and nitrogen gas is
then pumped in. After a period of soaking at the appropriate temperature
the pressure is rapidly reduced. The nitrogen bubbles expand inside the
molten poly(ethene) and this produces the plastazote foam when cooled.

Both poly(ethene) and nitrogen are non-poisonous, and as there are no

chemical blowing agents involved with production, plastazote foam is
non-toxic. Plastazote foam will not allow the passage of liquids through its
cell structure and is therefore very buoyant and resistant to oils and
solvents. However, it will allow gases and vapours to pass through.
Unlike many other foams it will recover repeatedly from impact since the
cell structure is highly energy absorbent with a good cushioning
performance. Plastazote foam is also lightweight, a good thermal
insulator (use of nitrogen), tough and flexible. It maintains a stable
condition from -70°C to +70°C.

The most rigid plastazote foam is made from HDPE and can be as stiff as
wood with a density of 115 kg nr", However the more flexible versions are
made from LDPE with a density range as shown below:
Plastazote foam LD24 grade - produced from LDPE at 24 kg m-3
Plastazote foam LD33 grade - produced from LDPE at 33 kg m-3
Plastazote foam LD45 grade - produced from LDPE at 45 kg m-3
Plastazote foam LD60 grade - produced from LDPE at 60 kg m-3

1. Cut a small sliver from the edge of a piece of plastazote foam and
examine it under a microscope first at x40 magnification and then at
x100 magnification.
• What are the geometrical shapes of the cells you can see?
• Are the cells connected to each other or unconnected ?
• Would you describe plastazote as a closed cell cross-linked foam or
an open cell cross-linked foam ?

57
2. The rolled-up material, often seen on the top of rucksacks and used
by backpackers to put under their sleeping bags, is made from
plastazote foam.
• Which property of the plastazote foam makes it ideal for this type of
application?
• Explain in terms of cell structure what gives the foam this
property?
3. What makes plastazote foam a very good thermal insulator?
Suggest some possible applications of plastazote foam which make
use of the thermal insulation properties.
4. How might plastazote foam find an application in stereo hifi music
systems and which properties make it suitable for this use?

58
A2.5 An example of addition polymerlsatlon

You will use a peroxide compound to initiate the polymerisation of an

alkene. Phenylethene is a convenient alkene to use because it is a liquid
with a boiling point of 145°C. Di(dodecanoyl) peroxide (lauroyl peroxide) is
the ini tia tor.

CARE - Eye protection should be worn

CARE - Note the hazardous materials indicated below
CARE - Carry out this experiment in a fume cupboard
CARE· Di(dodecanoyl) peroxide - irritant
Phenylethene - flammable and toxic

Requirements
10 em" phenylethene (styrene) - Toxic/Flammable/ Irritant
0.2 g diedodecanoyl) peroxide - Oxidising/Irritant
10 cm3 measuring cylinder
5 cm3 methylbenzene - FlammableIHarmfullIrritant
2 em" bromine water - HarmfullIrritant
boiling tube and 2 test tubes
250 em" beaker
cotton wool
silver foil bun casing

What to do
1. a) Place 10 em" ofphenylethene in a boiling tube.
(CARE - Phenylethene is flammable and toxic - avoid breathing the
vapour)

b) Add about 0.2g of diedodecanoyl) peroxide (CARE - Irritant) and

shake the tube until the solid has dissolved.

c) Plug the tube with cotton wool and then heat it in a beaker of boiling
water in a fume cupboard for about 20 minutes.

• Compare the contents of the tube with the original

pheny lethene.
• Is there evidence that polymerisation is taking place?

d) Pour the contents of the boiling tube into a silver foil bun casing
(mould) and leave it in an oven at about 50°C until it is set hard.

e) Dissolve some of the solid formed in methylbenzene and then add a

few drops of the solution to Lcm" of bromine water in a test tube.
Stopper the tube and shake. Note what happens.

59
f) Now add a few drops of the monomer (phenylethene) to 1 em" of
bromine water in a separate test tube. Stopper the tube and shake.
Note what happens.

• . What do your observations in Ie) and f) tell you about the structures
of the polymer and monomer respectively? Give a reason for your
answer.

• The structure of phenylethene is

H H
\ I

~C=C'H

Using the monomer structure as a starting point draw out the

structure for poly(phenylethene) showing five repeat units.

• The structure of di(dodecanoyl) peroxide is shown below:

o 0
II II
R-C-O-O-C-R

Explain how this compound acts as an initiator for the

polymerization process.

00
A2.6 Blowing agents and expanded poly(phenylethene)
A supply of beads that can be used to illustrate how expanded
poly(phenylethene) is made is available in the kit 'What a gas', distributed
from the Chemical Industry Education Centre, University of York,
Heslington, York Y01 5DD. The kit gives instructions on how to make an
expanded poly(phenylethene) sphere. Once the expanded
poly(phenylethene) sphere has been made, answer these questions.

The structure and physical properties of some alkanes are shown below.
1. Complete the table.

Molecular
Name Structural formula formula mp/oC bpfC
Propane a-f3- a-f2- a-f3 C3HS -190 42
Butane C4HlO -138 0
Pentane C5H12 -130 36
Hexane C6H14 -95 00
2-methylpropane C4HlO -160 -12
2-methy lbutane a-f3- CH(CH 3)- a-f2- a-f3 C5H12 -158 28
2,2-dimethylpropane C5H12 -16 9

2. a) Write the displayed structural formulas of two pairs of isomers in

the table.

b) Suggest why 2,2-dimethylpropane has a higher mp and lower bp

than pentane.

c) What properties make pentane and 2-methylbutane particularly

suitable as blowing agents?

d) During the pre-foaming stages (c) and (d) in the activity, both
hydrocarbons volatilise but only one escapes through the
poly(phenylethene) leaving tiny pores.
Which hydrocarbon is more likely to escape? Why?

e) During the drying stage (e), what happens to the remaining

hydrocarbon?
What else is likely to get in to the poly(phenylethene) beads through
the pores?

f) During the expansion stage, what gases are causing this

expansion?

61
A2.7 Some properties and uses of plastic foams

Plastic Foams
Plastic foams can be hard or soft, rigid or flexible, or somewhere in
between. They can also have varying degrees of open (interconnecting)
cell structures or closed (non-interconnecting) cell structures. Closed-cell
structures are preferred for insulation applications because they greatly
reduce the convection of gas in the cells. Therefore optimum thermal
insulation will be obtained at low foam densities with higher proportions
of closed cells. Closed-cell structures are also necessary for energy
absorbing applications since they act like minute cushions of air.

The ability of expanded poly(phenylethene) to protect packaged goods from

impact, and its ability to reduce head injury when used as a liner in cycle
crash helmets, depends on its density.

1. a) Measure the mass and volume of the poly(phenylethene) sample

produced in activity M.S. Then calculate its density from the
following equation:

. mass
density = voIume

b) Obtain a sample of manufactured expanded poly(phenylethene) and

measure its mass and volume. Then use the equation shown above
to calculate the density of the sample.

c) Draw up a simple table of results for the information obtained in

a) and b) using as headings:

Sample 1 Mass in g 1Volume in em31 Density in g em-3 -I

2. a) Using the information you have compiled, how could the

experiment in activity M.S be altered to produce expanded
poly(phenylethene) with a density similar to that of the
manufactured sample?

b) What is the advantage to manufacturers of being able to produce a

very low density expanded poly(phenylethene) material ?

c) 97% of the volume of expanded poly(phenylethene) is air that is

trapped in the closed cells. Explain how this enables the material to
absorb the energy of impacts.

d) Would a more dense expanded poly(phenylethene) be better or worse

at absorbing the impact energy? Explain your answer.
3. Read the information below and answer the questions which follow.

Poly(pbenylethene) Roads
In recent years expanded poly(phenylethene) has found a use in the
construction of roads and embankments. Traditional fill materials could
have a density of 1000 kg m-3, representing a load of 1 tonne/m- for each
metre of height. If a road or embankment is built on soft ground, the
sheer weight of the materials involved can cause failure in the earth
below, resulting in subsidence.

Expanded poly(phenylethene) blocks with a density of 20 kg m-3 have been

used as a lightweight alternative in areas of the Netherlands where
subsoil conditions are particularly difficult. This reduces the load on the
subsoil to about 60 kg m-3 for each metre of height and the predicted
subsidence over a period of 30 years is 80 mm as opposed to 3 m if
traditional materials had been used. The blocks were positioned as
required and glued together to prevent displacement. Thin layers of
furnace slag and the final road surface were then applied.

a) Explain the properties of expanded poly(phenylethene) which

permit its use in road construction.

b) Why do you think it might have been easier for the construction
workers to build the road in this way?

c) Expanded poly(phenylethene) can be damaged by contact with oil,

petrol, diesel and other harmful substances which might seep
down through the road surface. How do you think the civil
engineers overcame this problem in the example described above?

63
 SECTION 3

Thermosetting plastics
Thermosetting plastics are those which usually have strong cross-linked
structures which once formed cannot be broken down without the polymer
decomposing. However, some polyurethanes can be formatted to have
elastic properties.

Thermosets described here are:

3.1 Methanal plastics

3.i.1 Phenol-methanal
3.1.2 Carbamide-methanal
3.1.3 Melamine-methanal

3.2 Polyurethanes

3. 1 Methanal plastics

These comprise a family of thermosetting plastics formed by condensation

reactions (1.6.2) between methanal (formaldehyde) and phenol, carbamide
(urea) or melamine.

3.1.1 Phenol-methanal plastics (phenol-formaldehyde)

In 1910 Baekeland patented a process for producing resins from phenol and
methanal (formaldehyde). These are still known as Bakelite.
a) Manufacture of monomers

Phenol is made from benzene and propene via 1-methylethylbenzene

(cumene).

The aromatic hydrocarbon is oxidised with air and the resulting

hydroperoxide decomposed with warm, dilute sulphuric acid to give phenol
and prop an one (acetone).

64
Methanal is obtained from synthesis gas (CO + H2) via methanol:
Ni catalyst
a-t 4 (9) + H2 (9) CO (9) + 3 H2 (9)
1178 K, 30 atm

ZnO, Cr20:3
CO (9) + 2 H2 (9) a-t30H (9)
570 K, 300 atm

H
Ag catalyst 4 \
a-t30H (9) + ~ O2 (9) C=O (9) + H20 (9)
nOK /
H

b) Manufacture of polymer

Phenol and methanal react together when heated in sodium hydroxide

solution. The reaction can be used to illustrate how the formation of a
thermosetting resin takes place in two stages:

Stage 1 Forming the polymer chains

The first step in forming a polymer chain involves substitution of methanal
in the phenol ring in the 2 or 4 position:

OH

:6:
H
\
c=o +
I
H
4

The product then undergoes a condensation reaction in which a molecule of

water is eliminated between it and another molecule of phenoL

This product may be substituted by another molecule of methanal.

Condensation can then occur with afurther molecule of phenol - and so on.
The process continues to build up a chain of the type:

'&~~~~
OH OH OH

a 'resole' resin
Stage 2 Forming the covalent cross-links between the chains (known
as curing)

In the second stage, the benzene ring in phenol reacts at further positions to
form a 3-dimensional cross-linked structure. Part of this is illustrated
below:

It may help to follow these stages through by making a model of Bakelite.

c) Properties
The giant 3-dimensional cross-linked structure is similar to that of
diamond. It would require a large amount of energy to melt it; long before
this occurs, the covalent bonds break down and the Bakelite decomposes
and chars. The very high number of bonds and their strength also results
in Bakelite being very insoluble and generally unreactive.

Bakelite also has high electrical insulation and heat resistance.

Unfortunately, all the resins in this group are difficult to process and are
usually dark coloured.

d) Uses

The resins are moulded with fillers such as woodflour or mica (an
aluminium silicate) and a pigment. Their principal uses are in worktops,
printed circuit boards and household electrical fittings. Because of the dark
colour these fittings are now more usually made from poly(chloroethene).
Phenol-methanal plastics are also used as heat shields and on rocket nose-
cones.
3.1.2 Carbamide-methanal plastics (urea-formaldehyde)

a) Manufacture of monomers
Methanal (see 3.1.1)

Carbamide (urea) is manufactured from ammonia and carbon dioxide

under pressure:
450K
200atm
ammonium carbamate

!
H2N- CO- NH2 + H20

carbamide

b) Manufacture of polymer

Reaction between methanal and carbamide in alkaline solution gives mono-

and di-methylol carbamides:

t-i-i2 H
I \
2 Q=C + 2 C=Q +
\ I
t-.J-j2 H

These products condense together in acid conditions to give a linear

polymer similar to a resole resin (3.1.1). Water is eliminated:

H+ / heat /- H ,p
mono- and di- methylol carbamides

Further heating (curing) causes further condensation, with elimination of

water between the hydroxyl groups, resulting in a, cross-linked 3-
dimensional structure.

c) Uses
About 90% is used as adhesives, mostly in the manufacture of chipboard.
They are also used to make electrical fittings.
3.1.3 Melamine-methanalplastics

a) Manufacture of monomers
Methanal (see 3.1.1)
Melamine is obtained from carbamide (urea):

600K
+ SNH3 +
100atm \
V
recycled to make urea

melamine

b) Manufacture of polymer
The melamine is reacted with methanal and undergoes condensation
polymerisation in a manner similar to that of urea with methanal:

H
\
C=Q
I
H

c) Uses
Melamine resins combine the best of phenolic and carbamide resin
properties. They are stable to heat, light and moisture and are colourless.
The polymer absorbs dyes easily and the powder can be moulded under
pressure. Light-weight picnicware and tableware (e.g. Melaware) can be
made from melamine. Kitchen worktops can be made using a cheaper
phenolic resin to form the base, which is then coated with a more expensive
melamine surface.

Carbamide and melamine resins are also used, in solution, to strengthen

paper and to improve the shrink resistance of cotton, wool and rayon. Both
are used as ion-exchange resins to demineralise water.

3.2. Polyurethanes

The polymeric materials known as polyurethanes form a family of

thermoset addition polymers which includes elastomers, rigid and foamed
plastics, depending on the starting materials and the degree of cross-
linking, in the polymer. They are usually created during the manufacture
of a particular object.

Polyurethanes are made by the exothermic reactions between polyols

(alcohols with two or more reactive hydroxyl groups per molecule) and
polyisocyanates with two or more isocyanate (-N=C=O)groups per molecule.

68
a) Manufacture of monomers
Polyo1s

The polyols used are either polyethers or polyesters with hydroxyl groups at
the ends of the chains.

A triol often used is made from ethane-l,2,3-triol (glycerol) and

epoxypropane:

0-13 0-13
I I
H2C-0-(CH2CHO)n- CH2CHOH

I
He - 0-
0-13
I
(CH 2CHO) n-
CH3
I
CH 2CHOH

I
H2C - 0-
0-13
I
(CH 2CHO) n-
CH3
I
CH 2CHOH

Polyols are common industrial chemicals with a very wide range of uses.
Those used in the polyurethanes industry have been developed to have the
necessary reactivity with the isocyanate that will be used and hence produce
polyurethanes with specific properties. The choice of polyol, especially its
functionality (the number of reactive hydroxyl groups per polyol molecule)
and the size and flexibility of its molecular structure, very largely controls
the degree of cross-linking between molecules. This has an important effect
on the stiffness of the polymer.

Isocyanates

Although several aromatic and aliphatic polyisocyanates can be made only

two are of major industrial importance. Each of them has variants and
together they form the basis of about 95% of all polyurethane production.

• TDI (toluene di -isocyanate; methylbenzene- 2,4-di -isocyanate)

H3C-p--NCO
OCN

This was developed first and is now used mainly in the production of low
density flexible foams, for example, for cushions.

• MDI (biphenylmethane-4,4'-di-isocyanate)

OCN-o-~-o-NCO H
This is more complex structurally, and hence permits the polyurethane
manufacturer more process and product versatility. Also, as it is less
volatile, less vapour is produced in factory atmospheres. It is used more
widely than TDI.

b) Manufacture of polymer
In principle this is simple. As an example consider the manufacture of a
moulded item that might otherwise be made of a thermoplastic polymer by
injection moulding. To make it of polyurethane, it is necessary to mix
exactly the right masses of the two major components (isocyanate and
polyol) which must exist as liquids. The reaction starts immediately and is
usually completed, giving the solid polymer, in about 50 to 60 seconds. In
this time, therefore, it is essential to dispense the reacting liquid mixture
into the mould and also to clean the combined 'mixing & dispensing'
equipment ready for the next operation. The exothermic chemical reaction
is completed within the mould and the manufactured article is then
removed from the mould immediately.

n [OCN-R'-Nc&) :(fo-R-+ 01-1]

di-isocyanate diol
~ fCO-N-J-R'-NH-CO-O-R-O+
n
polyurethane

The group formed by the reaction between the two molecules is known as
the 'urethane linkage'.
-N-C-O-
I II
H 0
It is the essential part of the polyurethane molecule.

Selection of different polyols (hence different R) and different

polyisocyanates (hence different R') will give different polymer molecules
and, therefore, different properties. They are all, however, polyurethanes.
The polymer may be elastic with properties similar to those of a rubber
band, a 'hard' plastic suitable for use in computer cabinets or somewhere
in between.

c) Structure
When a di-isocyanate is mixed with a dial a linear polyurethane is formed:

n HOJ'VVV'OH+ n 0= C=N.JVVV'N=C=O

!
1 c-
()J\Jvv' 0-

o
II
N.JVVV' N-
I
H
I
H
ct
II
0
n

70
These polymers are elastomers and are used in the production of elasticated
fabrics in foundation garments, swim wear and the waistbands of pants.
(Lycra is a registered trade name of an elastomeric polyurethane).

If, however, a polyol with more than two hydroxyl groups is used the
product is cross-linked giving a rigid 3-dimensional network:

+ 0= C=N.JVVV"N=C= 0

OH HO o-
Il I I 11",,.,.,./
HO jO-C-NJvvv'N-C-Ovvvv~o_

VVVV\ 0-

O-W-r~-W-O~
OH HO 0-

d) Additives
A wide variety of auxiliary chemicals may also be added to control both the
polyurethane reaction and the properties of the final polymer. These
include catalysts, cross-linking agents, chain extending agents, blowing
agents, surfactants, pigments, fillers, flame retardants and smoke
suppressants. They are usually introduced by pre-mixing them with the
polyol to form a 'polyol blend'.

e) Foamed polyurethanes
Because, during the critical stages of the polyurethane-forming reaction,
the mixture is liquid, and is generating heat, any additive which creates a
gas can be used to form a foam structure. Bubbles of gas are formed within
the liquid and expand until the completion of the reaction creates the solid
polymer. The result is a cellular solid material - a solid foam. It is difficult
to keep water out during the manufacture of polyurethanes. Water reacts
with isocyanates to give an amine and carbon dioxide gas:
R-N=C=O + H20 R- NH2 + 002(9)

The gas causes foaming in the product and this first showed the
possibilities of "polyurethane foams". Unfortunately the amine produced
gives undesirable properties of rigidity to the product; also the expensive
isocyanate is destroyed.

For forty years chlorofluorohydrocarbons (CFCs) were used as cheap and

effective foaming agents. Now that the harmful effect of CFCs on the ozone
layer is recognised, their manufacture and use is being phased out across
the world and the search is on for new foaming agents. Water is again
being used in some processes.

71
If the choice of polyol has given a solid polymer with elastomeric properties
(a flexible polyurethane), the resulting foam may be suitable for cushions or
mattresses. In such cases, the cells are usually encouraged to burst,
releasing the gaseous 'blowing agent' which can be collected and reused.
The resulting foam is said to have an 'open cell' structure.

If, on the other hand, the polymer is a cross-linked rigid polyurethane it is

usual to trap the blowing agent within the cells (a 'closed cell' structure). If
the gas has a thermal conductivity that is lower, even than that of air, the
result is a foam particularly suitable as a thermal insulation material.

f) Adhesion

In the final stages of the polyurethane-forming reaction, the mixture

becomes a gel with very effective surface adhesion. Hence polyurethanes
can be used as adhesives. Equally important is the fact that polyurethanes,
which are being created as, for instance, cushioning or insulation
materials can be bonded to surface materials without the introduction of
separate adhesives.

Flexible foam and fabric together can create a composite cushion or rigid
foam and sheet building materials. For example, plasterboard, steel sheet
and plywood can provide composite building insulation panels.

g) The manufacture of refrigerator cabinets

As an example of the combination of chemical reaction, foaming and

adhesion, consider the manufacture of fridge and freezer cabinets. 95% of
world production is based on polyurethanes technology.

The outer cabinet (made of steel) and the inner liner (usually a
thermoplastic) are held in position so that there is a cavity between them.
Neither of these thin shells is strong enough to be self-supporting. A
predetermined quantity of reacting polyurethane mixture is injected into
the cavity. If there were no foaming, this liquid would fill only about 3% of
the space. The heat produced by the reaction expands the blowing agent
within the mixture, forcing the resulting foam to fill every nook and cranny
of the cavity, however complicated the shapes might be. Finally the
adhesive bonds the two shells together, creating a composite structure that
will withstand external loads and provide efficient thermal insulation.

h) Application
The combined effects of controlling the polymer properties and the density
lead to the existence of a very wide range of different materials so that
polyurethanes are used in very many applications in many industries.

i) Uses (%) Furniture and mattresses 32, Automotive 20,

Construction 15, Refrigeration 6, Coatings and adhesives 4,
Footwear 4, Packaging 2.

Production (tonnes) World: 6 x 106 (1992)

'i2
 ACTIVITIES

A3.1 The preparation of a methanal resin

CARE· Carry out this experiment in a fume cupboard

CARE· Make sure there is no hydrochloric acid near this experiment.
Fumes from hydrochloric acid and methanal mix to produce a
powerful carcinogen.
CARE • Wear eye protection and gloves
CARE • Use tongs to hold the boiling tube

Requirements
carbamide (urea) 3 g
methanal (formaldehyde) solution (40%) Scm" . Irritant vapour
concentrated sulphuric acid- Corrosive
boiling tube
glass stirring rod
measuring cylinder, 10 em"
rack for boiling tube
beaker, 100 em 3
dropping pipette for acid

What to do
1. a) Weigh 3 g carbamide into the boiling tube.
b) Measure S em" methanal solution from the cylinder into the
carbamide.
c) Stir well and hold the boiling tube with tongs.
d) Carefully run a few drops of concentrated sulphuric acid down the
side of the tube and continue stirring until no further reaction
occurs.
e) Place the boiling tube in rack.
f) When the reaction is finished and the tube has cooled, tip the
contents of the tube into the beaker about half full with water.
Stir well. Drain and allow to dry.
• What did you observe in the tube?
• What happened to the glass rod?
• What type ofpolymerisation reaction took place?
• What was the purpose of the concentrated sulphuric acid?
• Describe the appearance of the polymer
• What difficulties might arise during the industrial process of
manufacturing this polymer?
• This polymer is often used to make electrical fittings. How
could it be made into the shape of a plug or socket?
(See Section 1.10)

73
A3.2 The preparation of another methanal resin

CARE - Carry out this experiment in a fume cupboard.

CARE - Make sure there is no hydrochloric acid near this experiment.
Fumes from hydrochloric acid and methanal mix to produce a
powerful carcinogen.
CARE - Wear eye protection and gloves, phenol can cause severe bums.
CARE - Use tongs to hold the boiling tube.

Requirements
phenol 4 g - Skin toxic
methanal (formaldehyde) solution (40%) 10 em" - Irritant vapour
concentrated sulphuric acid - Corrosive
old (throwaway) boiling tube
measuring cylinder 25 em"
tongs
glass stirring rod
rack for boiling tube
teat pipette for acid

What to do

1. a) Weigh out 4 g phenol

b) Pour 10 em" methanal solution into the boiling tube
c) Holding the tube in tongs drip about 1 em" concentrated sulphuric
acid down the side of the tube and stir well.
d) Place the tube in the rack and leave for a few days.
• What evidence did you have, if any, of an immediate reaction?
• What do you observe after a few days?

It is possible to speed up this reaction by boiling the mixture under reflux

for an hour. Water is then removed by vacuum distillation. The resulting
resin syrup is poured into moulds which are placed in an oven at 70°C for
several days. This stage is the Bakelite process which gave the polymer
its trade-mark.

• Read the information in the box and then explain why the
processes in italics are necessary.

74
A3.3 Hazards of burning plastics

Headlines and an extract from a recent newspaper article stated:

ANOTHER FIRE CAUSES DEATH BY SUFFOCATION

Chief Fire Officer Newton
explained
"Many household articles are
made from synthetic polymeric
materials. Some of these are very
flammable but, in house fires, most
deaths are caused by inhilation of
smoke.
Several toxic gases may be
present in the smoke given off by
burning, or even smouldering,
plastics.
These include:
carbon monoxide, hydrogen
cyanide, hydrogen chloride"

1. a) From your knowledge of the formulae of the polymers detailed in

Sections 2 and 3 suggest which might be responsible for each of
these gases?
b) Which one of these gases is likely to be given off during the
burning of all flammable polymers? Explain why it is formed.
2. a) Why are certain types of foam filling in furnishings now banned
in the UK?
b) What precautions can be taken by the manufacturers of such
foam-filled furniture to prevent domestic fire tragedies?
c) What precautions should be taken by the householder?

75
 SECTION 4
Elastomers
Elastomers are a group of polymers that are elastic. They can be stretched
or deformed under pressure and then recover their original length or shape
when the pressure is released. Elastomers can be either natural or
synthetic and the particular ones dealt with in this section are shown
below.

ELASTOMERS

I I
NATURAL RUBBER SYNTHETIC RUBBERS
I
cis trans
structure structure

POly(Buta-1,3-diene) Styrene-butadiene Polysulphide Nitrile Neoprene Silicones

(SBR)

All of them have low glass transition temperatures, Tg below 273 K

4. 1 Natural rubbers
Rubbers occur in the sap of many plants as a white milky fluid called latex.
The highest yields are from the tropical trees, Hevea Brisiliensis, originally
found in Brazil, but now grown in the Far East in countries such as
Malaysia and Indonesia. Cuts are made in the bark and drops of latex (a
colloidal dispersion of rubber particles in water) are collected. Addition of
ethanoic or methanoic acid to latex precipitates rubber as a gel. This can be
filtered, washed and dried.
4.1.1 Molecular structure and isomerism

The monomer unit of natural rubber is 2-methylbuta-l,3-diene, known as

isoprene, with molecular formula C5HS.:

76
Natural rubber is the polymer in a cis configuration; each polymer
molecule contains between 3 000 and 6 000 monomer units. Its structure is
thus:

There is also a naturally occurring polymer in a trans configuration. This

comes from a different species of tree and is a hard, greyish material called
Gutta percha. This substance, unlike rubber, is crystalline at room
temperature. It was once used to make the outer covering of golf balls.

poly (trans-2-methylbuta-1,3--diene)
Gutta percha

The difference in physical properties between rubber and Gutta-percha

results from the different possibilities of close packing, and thus
intermolecular attraction, between molecules in the two different isomers.
4.1.2 Molecular structure and physical properties

The physical properties and structures of elastomers have been introduced

in Section 1.5.2. Elastomers contain tangled long chain molecules with a
limited amount of cross-linking. Stretching causes the chains to straighten
out and disentangle but the cross-links ensure that the chains return to
their original tangle once the force is released. For example, rubber can be
stretched reversibly by up to six times its original length. Prolonged or
further stretching causes permanent extension called 'creep'. This is due
to slippage between polymer chains. Further stretching will cause
breaking as the chains themselves break up. The degree of 'creep' is
limited by the amount of cross-linking in the rubber.

71
 Chains straight and
disentangled

Unvulcanised
rubber

Unstretched Stretched

The molecules of raw natural rubber are too large for it to 'melt' and
although rubber becomes tough at about 273K its Tg is much lower. It
therefore becomes soft and sticky in hot weather and hard and brittle in
cold. It is also softened or dissolved by various common solvents. Because
of these properties, natural rubber is of no commercial use (e.g. in tyres)
unless treated to overcome these defects.
When rubber is heated it contracts and, conversely, gives out heat when
stretched.

4.1.3 Vulcanization

Both the problems of creep and climate-related instability were overcome

when Charles Goodyear discovered the process of vulcanization in 1839. He
found that when raw rubber was mixed with sulphur and then heated, the
mixture was converted into an elastic material which became stable over a
much wider temperature range and resistant to flow (creep) under load.

Nowadays 1 '- 3% of sulphur (by mass) is added to rubber and the mixture
heated under pressure at 400-450 K in metal moulds for a few minutes
(depending on the vulcanizing system being used).

It is thought that polymer chains become linked at intervals by sulphur

atoms. This prevents slippage (creep) while retaining elasticity.

78
 H3C, /H
C=C
H2 H2 / ,
-C C-C C-
, / H2 H2
C=C
H3C/ 'H

heat
+ 2S

H3C, /H
C=C
/ 'H2 H2
-C C-C C-
H2 H2'

H3C
/
C=C
,
/

rubber + sulphur vulcanised rubber

Excessive vulcanization reduces the length of the chains between the cross-
links and prevents the polymer chain from uncoiling, thus reducing the
elasticity. This occurs in the production of Ebonite, a brittle, infusible solid
with no elastic properties.

Vulcanised rubber Ebonite

(elastic) (non stretch)

A wide range of chemicals are used today in the production of rubber. Some
of these are used in vulcanization and others to give specific properties to
the material. In particular, carbon-black is used as a filler to reinforce
rubber and increase its tensile strength, tear strength and abrasion
resistance. Natural rubber also deteriorates on exposure to ultraviolet
radiation, oxygen and ozone and the carbon-black acts as a UV-absorber.
Natural rubber loses its useful elastomeric properties when oxygen is
absorbed. To counter this, certain organic bases are added during the
compounding stage to prevent free-radical oxidation by oxygen and to
prevent attack of the double bonds by ozone. This reduces the problem of
degradation both during the production processes and the service life of the
finished product.

79
4.2 Synthetic Rubbers

There are several major synthetic rubbers but only the following are dealt
with here:

• Poly(buta-l,3-diene)
• Styrene-butadiene (SBR, a copolymer)
• Polysulphide rubbers
• Nitrile rubbers (NBR)
• Polychloroprene (Neoprene)

4.2.1 Poly(buta.-1,3-diene) (butadiene rubber)

Repeating unit

t 2-
0-1 0-1= ~- ~2+n
a) Manufacture of monomer

Buta-l,3-diene is produced, with other alkenes, during steam cracking of

naphtha and gas oil feedstocks. It is widely used in the production of a
number of synthetic rubbers.

Two methods are used for extracting buta-l,3-diene from the mixture of
alkenes produced by cracking:

(i) Solvent extraction by chemical reaction with aqueous tetra-ammine

copper(1) ethanoate (cuprous ammonium acetate). The absorption
takes place at low temperature (260 K) in large static mixer/settler
vessels. The copper-diene complex is heated to liberate the diene and
the free copper salt is recycled. Fractionation gives pure (99 mass %)
buta-l,3-diene.

(ii) More modern processes rely on extractive distillation, where various

proprietary solvents are used to enhance the relative volatilities of the
C4 alkenes in the crude steam cracking product mixture. This
allows the closely boiling components to be separated by distillation
with the solvent recovered and recycled. These processes are
generally capable of producing a higher quality product (99.5
mass %).

Alternatively, straight chain butene/butane mixtures derived from

fractionation of oil can be catalytically dehydrogenated in the
presence of large volumes of diluent steam to give buta-l,3-diene.
 AI~3/Cr~3

catalyst, 873 K

b) Manufacture of polymer

Hundreds of different sets of reaction conditions are recorded in the

literature. For example, cis-polyisoprene, cis-poly(buta-1,4-diene) and
ethene/propene elastomers can be produced using a Ziegler-Natta catalyst.
Whereas trans-polyisoprene can be produced using titanium and vanadium
catalysts in conjunction with an alkyl aluminium cocatalyst. Diene
polymers are produced by addition reactions which, in the case ofbuta-1,3-
diene usually involve 1,4 addition. The process includes a compound such
as alfin (allylsodium + sodium isopropoxide + sodium chloride), to produce
a radical (see section 1.6.1) to initiate the reaction. The use of chromium
hexakis(benzonitrile) chromium(O) Cr(C6H5CN)6 as a catalyst in the
polymerisation of buta-1,3-diene, produces stereospecific polymers.

c) Properties

Poly(buta-1,3-diene) has high abrasion resistance and good low temperature

properties. Like all rubbers it must be vulcanized to provide practical
materials.

d) Uses

Polybutadienes are used to manufacture:

• V-belts (driving belts for car engines, washing machines etc.) and anti-
vibration mountings
• adhesives and coatings
• additives in rigid polymers (e.g. polystyrene) for toughness

In order to achieve specific properties, buta-1,3-diene is co-polymerised with

other alkenes and substituted alkenes.

4.2.2 Styrene-butadiene Co-polymer(SBR)

SBR is a random co-polymer of the monomers buta-1,3-diene and

phenylethene (styrene). It normally contains about 25% phenylethene. SBR
is one of the oldest synthetic rubbers as it was developed during World War
2 when the United States found it difficult to obtain supplies of natural
rubber. It continues to be produced in larger quantities than all other
rubbers since at present it is the only one which compares favourably in
price with natural rubber.

81
a) Manufacture of monomers

Manufacture ofbuta-l,3-diene is described in section 4.2.1, page 80.

Manufacture of phenylethene is described in section 2.5, page 48.

b) Manufacture of polymer

SBR is produced by a free-radical emulsion polymerisation process. The

relative reactivities are such that buta-1,3-diene is consumed more rapidly
than phenylethene and consequently a feed concentration of about 30%
phenylethene must be used to achieve a 25% phenylethene polymer. Two
types of SBR are produced - 'emulsion' and 'solution'.

'Solution' polymers are produced like poly(buta-1,3-diene) using, for

example, alkylllithium catalysts. Variations of these are the block
copolymers used as thermoplastic rubbers.

The 'emulsion' version is usually made by using initiators which will yield
radicals at low temperatures. This is achieved by use of a redox couple at
5°C and typical combinations are hydroperoxides and iron(I1) sulphate.

Fe 2+ + R-O-O-H ~ RO· + OH- + Fe3+-

The concentration of cations is controlled by the addition of buffers and

sequestering agents (compounds which are very effective in forming
complexes with metal cations thus preventing the metal cations from
forming hydrated cations).

After reaching 75% conversion, reactions are terminated by the addition of

benzene-1,4-diol (hydroquinone) which reacts rapidly with radicals and the
initiator. Any unreacted monomer is then removed. Butadiene is removed
first by flash distillation at atmospheric and reduced pressure, following
which the styrene is removed by steam stripping in a column. An
antioxidant such as N-phenylnaphthalen-2-amine is added in a proportion
of 1:25 parts of antioxidant to reactants.

The latex produced is partially coagulated by the addition of brine and then
fully coagulated using sulphuric acid or aluminium sulphate. The
resultant crumb is washed, dried and baled for distribution.

Carbon black is added to SBR as reinforcement and oil is added as an

extender-plasticiser. Common proportions are 20 to 50 parts of oil and 40 to
100 parts of carbon black per 75 parts of rubber.

82
c) Uses
SBR is used in components for:
• car tyres (because of low heat build-up)
• industrial belting and hose
• cycle tyres
• carpet-backing
• adhesives
• footwear (soles and heels)
• floor tiles
• coated fabrics

About 70% of the SBR produced is used in tyre manufacture. SBR latex has
been used to spray loose soil and sand to produce a film to combat erosion.

4.2.3 Polysulphide rubber

Polysulphide rubber was first introduced in the United States in 1930 in the
form of'Thiokol A'. It came about as a result of a development programme
to produce rubbers which would be more resistant than natural rubber to oil
and the swelling caused by solvents.

a) Manufacturing process

Thiokol A is produced by condensing 1,2-dichloroethane and sodium

polysulphide in an aqueous emulsion in the presence of magnesium
hydroxide. The reaction can be represented by the equation:

The slow oxidation of the end groups by lead(IV) oxide at room temperature
produces a cross-linked polymer with a high relative molecular mass. The
reaction is similar to the vulcanisation of natural rubber but produces
desirable properties when the liquid polymers are cast or applied as pastes
for sealants.
Other thiokols can be produced using 1,4-dichlorobenzene or
1,4-dichloroethoxyethane [CICH2CH20CH2CH2Cl] with sodium
polysul phide.
b) Uses
Although polysulphide rubbers are mechanically inferior to other rubbers
they are more resistant to oils and solvents. They are, therefore, more
suitable for use where contact with oils and solvents is involved, e.g.
• protective clothing
• sealant on aircraft runways
• sealant on bridges, dams and reservoirs
• sealant for high-rise and curtain-wall buildings
• gaskets and hoses which make contact with oils and solvents

4.2.4 Nitrile robbers(NBR)

a) Manufacture of monomers

Nitrile rubbers are copolymers of propenonitrile and buta-l,3-diene in

which the proportion of acrylonitrile can vary from 18 to 40%.

Manufacture ofpropenonitrile is described in section 5.5, page 105.

Manufacture ofbuta-l,3-diene is described in section 4.2.1, page 80.

b) Manufacturing process

Nitrile rubbers are produced using emulsion systems similar to those used
to produce SBR. The monomer composition ratios are different and the
composition is adjusted during polymerisation to produce the particular
nitrile rubber required.

c) Uses

These rubbers have excellent resistance to oils and antifreeze (ethane-l,2-

diol) but are not suitable for vehicle tyres. Increasing the proportion of
acrylonitrile in the copolymer produces poorer physical properties but
improves oil resistance.

Uses include:

• fuel hoses (vehicles and aircraft)

• fuel tanks
• flexible hoppers in bakery equipment
• adhesives
• latex impregnation of paper, textiles and leather
• oil resistant protective gloves
• coatings on metal rollers used in colour printing
4.2.5 Polychloroprene(Neoprene)(eR)

Neoprene is the generic name given to rubber-like polymers and copolymers

of chloroprene (2-chlorobuta-l,3-diene) which were the first synthetic
rubbers developed. They have excellent oil resistance and are good general
purpose rubbers which can be used in place of natural rubbers for most
applications.
a) Manufacturing process

Neoprenes are produced by emulsion polymerisation. In some cases

sulphur is introduced to the polymerisation process to induce some cross-
linking in the polymer. The latex produced in this process is allowed to age
in the presence of emulsified tetraethylthiuram disulphide to restore the
plasticity of the material. It is then coagulated by acidification followedby a
freezing process. The polymerisation takes place in the trans-l,4 form and
the neoprenes produced can therefore be crystallised.

Neoprene is different from other elastomers in that it can be vulcanised by

heat alone but normally zinc oxide and magnesium oxide are used in the
process.
b) Uses

Neoprene vulcanizates have a high tensile strength with good weather and
ozone resistance. They have good dynamic properties; comparable to
natural rubber and superior to most other synthetic elastomers. Major
uses are:
• wire and cable coatings
• industrial hoses and belting
• shoe heels
• solid tyres
• adhesives
• gloves
• wet suits, hot air balloon suits

85
4.3 Silicone polymers

Silicone polymers were developed after research carried out by F. S. Kipping

(1863 - 1949) in Britain. This research examined the close relationship
between organic compounds of carbon and silicon. Like carbon, silicon has
the ability to form covalent compounds. Unlike carbon, however, silicon
does not form double or triple bonds and silicone polymers are therefore
usually produced by condensation methods. Today there is a large variety of
silicone polymers available, from low viscosity oils to hard resinous
materials. In this section we will consider silicone fluids, silicone resins
and silicone rubbers. Although production costs are high, silicones are
now used extensively in domestic and industrial applications.

Polymeric silanes (silicon hydrides) are unknown but the following siloxane
link is more stable and is the basis of silicone polymers.

I
-Si-O-Si-
I I
a) Manufacture of monomer

Silicone polymers are made from organosilicon intermediates (monomers),

usually produced by the direct reaction of alkyl and aryl chlorides with
silicon. This produces compounds of the type SiRnX4-n, where R is the
alkyl or aryl group and X a group (such as chlorine or alkoxy) which can be
hydrolyzed into a silanol. This requires a high temperature reaction of a
halide with silicon in the presence of a metal catalyst and normally involves
the reduction of quartz in an electric furnace. The main reaction is shown
by the equation below but it should be noted that a number of side reactions
will also occur.

b) Manufacture of polymer
Silicone polymers are then produced by condensation polymerisation of
silanols, formed from the halide or alkoxy intermediates by hydrolysis.

-Si-CI + H2O ~ -Si-QH + HCI

I I

I
-Si-OH + HQ-Si- ~ -Si-O-Si- + H2O
I I I I

Individual siloxane structures are obtained by use of silanols with different

functionalities (the alkyl groups in the monomers are unreactive).
 R-~iR1 RI lR~i-R
O-~i-O
R R RI
I
n

The value of In' determines the physical properties of the polymer produced.
When n is small the polymer is liquid, when n is large the viscosity
increases and the polymer is a resin.

c) General Properties

• Water-repellant as a result of large numbers of hydrocarbon side

chains with strong hydrophobic character.
• High thermal stability (up to 420K) as a result of a basic structure of
alternating silicon and oxygen atoms with organic side chains. As
the side chain length increases the thermal stability decreases.
• Liquid silicones exhibit only small changes in viscosity with
changes in temperature.
• High resistance to attack by ozone and ultra-violet radiation but no
resistance to aromatic solvents such as methylbenzene and
dimethylbenzenes.
• Excellent dielectric properties.

4.3.1 Bilicone fluids

a) Manufacturing process

These polymers are produced as described above (4.3 a & b) but with a
predetermined mix of chlorosilanes fed into water with stirring.

b) Uses related to properties

• Lubricants for systems operating at high temperatures (e.g. aero

engines)
• Used in heating baths and for damping electrical equipment,
because of their thermal stability.
• Used in polishes and waxes, waterproof clothing, shop blinds and to
render furnishing fabrics and carpets stain resistant, because they
are water repellent.
• Additives to cosmetics, antifoam agents, non-stick coatings for
papers used in cooking, release agents when moulding metals and
plastics.
4.3.2 Silicone resins

These contain Si-O chains with one or more organic substituents.

They have cross-linked three-dimensional structures.

a) Manufacturing process

Silicone resins are produced by polymerising mixtures of R2SiCl2 and

RSiCla or SiCl4 by hydrolysis of the required chlorosilane blend in the
presence of a solvent such as mineral spirits, butyl acetate or
methylbenzene. The material produced is hard and brittle.

b) Uses
• Insulating varnishes (used to coat transformer windings etc.),
encapsulating agents and paints.
• Non-stick surfaces on cooking utensils.
• Impregnating agents to waterproof brick, concrete and stone.

4.3.3 Silicone rubbers

Silicone rubbers differ from other synthetic elastomers in that they are not
organic compounds. They are usually polydimethylsiloxanes (linear
polymers of high molecular mass). To obtain useful properties, silicone
rubbers are usually reinforced with materials such as silica.

a) Manufacturing process
Silicone rubbers are normally made in one of three ways:

• By a free-radical crosslinking process forming bridges between chains.

• By crosslinking vinyl or allyl groups attached to silicon using a
reaction with silylhydride groups.
• By crosslinking siloxane chains which have reactive end groups
such as silanols.

b) Uses

Reinforced silicone rubbers have excellent low temperature flexibility (to -

80°C) and stability at high temperatures (to 250°C). In addition they have
good electrical properties, good resistance to ageing, weathering and ozone
and excellent colour consistency.
• Gaskets, seals, cable insulation (extensive use in aerospace industry).
• Seals in commercial freezers.
• Flexible seals in the building construction industry.
• Surgical and prosthetic devices (artificial heart valves, transfusion
tubing, dialytic membranes in kidney machines).
• Heat resistant and non-stick coatings for rollers and internal
surfaces of piping for chemicals.
• Conveyor belting for food processing industry.

88
 o
N

o
N

o
(')

II II
o
N

II o I o
o
o=U I
I
a
N

I o b~ o
II
a ~o
N II
I II
a II
II
<& OU '&
II II :z:: I
II £
a I
q, o~
I ._ o
N
'&
J: (')
o-
<:5
I o
N

NI I
o
N

MM M II .- ~
os a o
II
II
Q.Q. NI
UU U 0 I o~ oI N

I
II II II II II) II II
UUU
N N N ~<& I
cf <&U I
III I I ILl:' <:5
 ACTIVITIES

A4.1 The effect of temperature on natural rubber

This short activity investigates the effect of temperature on polymer

crystallisation in natural rubber.

Requirements
2 strips of natural rubber

Strips of natural rubber can be prepared in advance from Copydex

adhesive or a latex emulsion. Paint a thick layer of Copydex onto a
smooth non-porous thin material (material from a polythene carrier
bag is suitable for this) and leave overnight to solidify. Sprinkle the
outer surface of the solid Copydex with talc before handling and then
with a craft knife, cut into strips (with straight edges), each about
1 cm x 10 em, leaving the polythene backing in place.

2 large boiling tubes

quantity of ice
warm water (hand hot)

What to do
1. a) Fill one boiling tube with ice and the other boiling tube about half-
full with warm water (hand hot).
b) Peel off the polythene backing from one of the Copydex strips,
gently stretch the strip and fix it around the outer surface of the
boiling tube containing ice.
c) Repeat the process for the second Copydex strip but this time fix it
around the half of the boiling tube containing warm water.
• Observe the different effects on the two strips of rubber
(Copydex)
• Explain in terms of Tg, crystalline and amorphous regions,
what has happened to the molecular structure of the rubber
(Copydex) in both cases.
• Why was it necessary to stretch the Copydex strip to begin
with?

00
A4.2 Synthetic and natural rubbers

1. Most rubber in use today is synthetic, not natural. One type of

synthetic rubber is poly(buta-l,3-diene).

• Draw the molecular structure of the monomer, buta-l,3-diene.

• Draw a section of the polymer chain produced by joining three
poly(buta-l,3-diene) monomers.
• Comment on the possibilities for isomerism in poly(buta-l,3-
diene).

2. Poly(buta-l,3-diene) is not very easy to process. However, this problem

can be improved by making a copolymer between buta-l,3-diene and
phenylethene. This produces a polymer called SBR rubber.

• Draw a section of an SBR rubber polymer chain assuming the

copolymer contains 50% of each monomer. The structure of
phenylethene is:

Q-a-J=a-J2

• Discuss the advantages and disadvantages of using synthetic

rubber compared to natural rubber.

• Historically, the major advances in synthetic rubber technology

occurred during the First and Second World Wars. Suggest
reasons for this.

91
 SECTION 5
Fibres
Semi-synthetic and synthetic fibres were produced originally to provide an
alternative (and cheaper) source of fabrics to replace natural fibres, such as
wool and cotton. Structures were designed to match those of natural fibres,
but it was soon realised that fibres with more desirable properties (such as
resistance to sunlight, and increased strength and stretch) could be
produced, for example by modifying cellulose and by synthesizing
polyamides.
Cellulosic fibres (viscose rayon, "artificial silk"), made from wood pulp,
were first produced commercially in France in 1891. Nylon 6,6, the first
entirely synthetic fibre to be commercially viable, was marketed from 1938.
Since then many synthetic textile fibres have been made in the laboratory
and some are produced on a large scale. Others are designed only for very
limited and specific purposes. The world manufacture of fibres in 1992/3 is
given in Table 5.1:

Table: 5.1 World Consumption of Fibres (tonnes) 1993 1992

Cotton 20.1 x loa 18 x loa
Polyester not known 9.9 x loa
Polyamide not known 3.7 x loa
Chemically-modified celluloses not known 2.7 x loa
Acrylic 2.3 x loa 2.4 x loa
Wool 1.7 x 1()6 1.8 x 1()6
Poly(propene) 1.1 x loa 0.6 x loa

'Man-made' fibres are mainly used by clothing, carpet and furnishings

industries but are also used by other industries such as the automobile
industry. The following fibres are described in this chapter:
• fibres based on cellulose
• polyamides
• polyesters
• polyaramids
• poly(propenonitrile)
5.1 Fibres based on cellulose
Cellulose is the principal constituent of the cell wall of plants. It consists of
a three-dimensional network of chains of glucose units.
The structure of a glucose unit is

92
and the structure of cellulose is

H OH

-0 o 0-

o o
H OH H OH

Cotton is almost pure cellulose, but cellulose is usually obtained from a

cheaper source, wood, which is a mixture of cellulose and a material
known as lignin. Two industrial processes for extracting cellulose from
wood pulp are outlined in Activity 5A.1

Rayon is the name given to the various fibres made from cellulose. Two
important examples will be considered here: viscose rayon and cellulose
triethanoate (Tricel).

5.1 .1 Viscose rayon

Viscose rayon is manufactured by treating cellulose with sodium hydroxide

and carbon disulphide.

O-x
/
X-OH + NaOH + cs2 •• s=c + H2O
\
s Na+
cellulose cellulose xanthate

The solution is forced through fine jets into a bath of sulphuric acid giving
fine fibres of viscose rayon. Fabrics made from the spun fibres have the feel
and appearance of silk, hence the name "artificial silk". They are not,
however, as light or as durable as silk.

The large number of hydroxyl groups causes viscose rayon to absorb and
retain water. In this respect it resembles -the natural cellulose fibre, cotton
(Table 5, page 104).

5.1.2 Cellulose trlethanoate (Trlcel)

Tricel is manufactured by ethanoylating (acetylating) cellulose with

ethanoic anhydride. The hydroxyl groups are esterified in stages so
cellulose monoethanoate and cellulose diethanoate (Dicel) can be isolated, if
required, by using the appropriate stoichiometric proportion of ethanoic
anhydride. These fibres are, however, not commonly used.

As the -OH groups are esterified to CH3C02- groups the polymers become
increasingly hydrophobic (water repelling). Once all the hydroxyl groups
have been ethanoylated the polymer (and the fibres and fabrics containing
it) has properties different from the original viscose rayon (Table 5,
page 104).
This is particularly evident in the ease of drying of the fabric and
determines the choice of dye. Cellulose triethanoate is now used more
frequently than viscose rayon for dress fabrics.

5.2 Polyamldes (Nylons)

Repeating unit

Nomenclature
1 0
II
C- (CH 2)n-
°II
C-
H
I
N- (CH 2)m-
H+
I
N

Nomenclature for describing polyamides is based on the number of carbon

atoms (n and m) in the repeating monomers and is as follows:

Nylon Repeat monomer

6 - NH(CH 2)SCQ-
6,6 - NH(CH 2)sNHCO(CH 2)4CQ-
6,10 - NH(CH 2)sNHCO(CH 2)SCQ-
11 - NH(CH 2)10CO-
12 - NH(CH 2)11CQ-

Monomer{s}

In the school or college laboratory these are usually an alkane dicarboxylic

acid, or its acid chloride, with a diamine such as 1,6-diaminohexane
(Section 1.6.2 and activity A5.3).
In the industrial process these are combined as a single monomer as the
ammonium salt.

Manufacture of monomer
(i) The monomer for nylon 6
Caprolactam, the monomer for nylon 6, is made from benzene by the
following reactions:
Ni catalyst
CSH12 (I)
5OOK.40atm
cyclohexane

450K
20(1) +
10atm

cyclohexane air cyclohexanol cyclohexanone

\ I

"mixed oil"
 CuO + Cr P3 catalyst

500 K, pressure

0 H
0 N-OH

6 6
\\ I
c-N
[NH30Hr HS04-
400K

an oxime
20% oleum

heat
U
caprolactam

The ketone reacts with a salt of hydroxylamine (NH20H) to form an oxime

by a condensation reaction. When the oxime is heated with acid (oleum,
which is sulphur trioxide dissolved in sulphuric acid), the atoms in
molecules of the oxime rearrange to form a seven-membered ring, known
as caprolactam, the monomer for nylon 6. The reaction is an example of a
Beckmann rearrangement.

(ii) The monomer for nylon 6,6

Oi -Oi -COOH
mixed oil 60% HNO 3, 350 K, catalyst I 2 2
(as above) or air, 370 K, catalyst
0i2- 0i2- COOH

hexanedioic acid

l=
ofNH4+ salt

hexamethylene
diammonium
hexanedioate

t.s-dlamlnohexane

The neutralisation of the dibasic acid by the diamine gives a diammonium

salt which is the monomer for nylon 6,6.
Manufacture of polymer
heat in steam
capro lactam nylon 6
530K

hexamethylene diammonium heat in steam

nylon 6,6
hexanedioate 530K

Principal uses: clothing, hosiery, carpets, sailcloth, parachutes, rubber

. reinforcement, sewing thread, computer ribbons,
engineering plastics.

Modified forms: compounded with fillers, glass fibre, toughening

agents, etc in order to obtain specific properties for
engineering applications.

Tonnage (1992) World, 3.7 x 106; Western Europe, 0.65 x 106

5.3 Polyesters

General and repeating unit

QII Q
II
~ C-R-C-Q-R'-Q
J
Polyesters are formed by condensation of a polybasic carboxylic acid with a
polyhydric alcohol.

5.3.1 Terylene

The most commonly manufactured polyester is poly(ethene-1,4-

benzoate )(Terylene)

Repeating unit

Monomers
Q Q
11-0-11
HO-C C-QH

benzene-1,4-dicarboxylic acid ethane-1,2-diol

(terephthalic acid)

(This is often used as its dimethyl ester.)

00
As in the manufacture of polyamides, the single monomers are first
condensed together to give the industrial "monomer".

Manufacture of Monomers

HaC-O-
(i)

0-13 + 302

1,4-dimethylbenzene
(from cracking naphtha fraction)

o 0
11-0-11
Co 2+ salt as catalY~
500 K, 20atm
HO-C U C-OH

benzene-1,4-dicarboxylic acid

(ii)
Ag catalyst H2C-CH2
\/
550K
o
ethene epoxyethane

acid solution
+ HO- 0i2- CH2- OH
350 K, pressure
ethane-1,2-diol

Industrial monomer
Ethane-l,2-diol is reacted with benzene 1,4-dicarboxylic acid, or its dimethyl
ester, in the presence of a catalyst to produce initially a monomer and low
molecular mass oligomers. .

Using the acid provides a direct esterification reaction «i) below). Using the
dimethyl ester, an ester interchange reaction is involved (Iii) below).

Until recently, the dimethyl ester route was preferred as the ester could be
purified more readily than the acid. However, very pure acid is now
available in commercial quantities, so direct esterification is used.
(i) Direct esterification reaction:

o 0
11-0-11
HO-C C-OH +

j autocatalysed
by -COOH group

Terylene monomer

(ii) Ester interchange reaction:

o 0
11-0-11
H3CO-C C-OCH3 +

j catalyst

o 0
11-0-11
HO-~2-~2-0-C C-O-~2-~2-OH + 2CHsOH

Manufacture of polymer
SJ A catalyst
550 K. low pressure
monomer polymer
(as above) or in melt or solid
using stream of dry inert gas

The monomer undergoes polycondensation to:

Ethane-l,2-diol is eliminated and is recycled.

Physical properties

Density 1.38 g cm-3; Tg 340 K; Tm 535 K; high crystallinity; high tensile

strength; low water retention; high stability to light.
Processing

Polyester production involves both a batch and a continuous process. In the

production of fibres, the products of a continuous process can be fed directly
into melt-spinning heads, thus avoiding the casting, chipping, blending
and drying stages which are necessary with batch processing. Granules
from both the batch and the continuous routes are used as feedstocks for the
extrusion and moulding of film, bottles, other moulded articles, and for the
solid phase route which produces polymer known as PET for food
packaging such as carbonated soft drink bottles.

Principal uses

Fibre (83%): clothing and household (either alone or with other

fibres e.g. "polycotton"); anorak and duvet filling; car
tyre cording; conveyor belts; industrial hoses.

Packaging (10%): including carbonated soft drinks bottles as PET

(polyethyleneterephthalate) - see below

Sheet (7%): video tape; electrical insulation; photographic and

X-ray film

Modified fonns

Recent developments in Japan have produced a polyester which can be

injection moulded at 10 times the rate of conventional polyesters. To
synthesise the new polyester, ethane-1,2-diol and benzene-1,4-dicarboxylic
acid are copolymerised with diphenylcarboxylic acid in a molar ratio of
5:2:3. The new polyester has a 10-30% higher glass transition temperature
and three to four times the elasticity of PET.

Tonnage of PET (1992)

World, 75 x 103, Western Europe, 53 x loa

5.3.2 Unsaturated polyester resins

Branched polyesters are made from benzene-1,2-dicarboxylic anhydride

(phthalic anhydride) or from cis-butene-1,4-dioic anhydride (maleic
anhydride), and a diol. For example:

"Go o
+

cis-butenedioic anhydride ethane-1,2-diol

polymer (Mr = 1000-3000)

The polymers are widely used with glass fibre as a filler in glass reinforced
plastics (GRP-fibreglass). They have high strength, low density and are
weather and fire resistant.

Unsaturated bonds allow rapid cross-linking between the linear chains of

the polymer to take place in the cold. The cross-linking agent, divinyl
benzene, and a free-radical initiator are used.

5.4 Polyaramlds

After the invention of nylon, chemists began to make sense of the

relationship between the structure of a polymer and its properties. They
were able to predict strengths for particular structures, and research was
directed at inventing a 'super fibre'. In the early 1960s, Du Pont, a major US
chemical company which had been in the forefront of the development of
Nylon 30 years earlier, were looking for a fibre with the heat resistance of
asbestos and the stiffness of glass. This resulted in the discovery of Kevlar.

Monomers
o 0
11-0-11
HO-C C-OH and

benzene-1 ,4-dicarboxylic acid 1,4-diaminobenzene

See Section 5.3.1 for their manufacture.

100
Processing
Kevlar is produced by the condensation polymerisation of 1,4-diamino
benzene and 1,4-benzenedioyl chloride. A solvent maintains the polymer in
solution for a long time thus increasing the molar mass of the product to
levels suitable for fibre production. The end product is insoluble in most
solvents but can be dissolved in 98% sulphuric acid from which it is
precipitated.

Principal uses
Kevlar is a fibre that is fire resistant, flexible and extremely strong. It also
has a low density because it is made from light atoms: carbon, hydrogen,
oxygen and nitrogen. Mass for mass, Kevlar is around five times stronger
than steel. One of its early uses was to replace steel cords in car tyres,
making them lighter and longer lasting than the steel reinforced versions.
Other uses of Kevlar include fabric for bullet proofvests, safety gloves, space
suits and high tension snare drum skins.

Structure
Kevlar is strong because of the way the rigid, linear molecules are packed
together. The chains line up parallel to one another, held together by
hydrogen bonds.

<, ~o
C~

¢
fibre
axis

This leads to sheets of molecules. The sheets then stack together regularly
around the fibre axis to give an almost perfectly ordered structure.

101
 Stack of
sheets
Sheets stack
together

Alignment of molecules into sheets

along the fibre axis is achieved by
the spinning method

The fibre achieves perfect radial and

perfect longitudinal order

The important thing to realise about Kevlar is that it takes this structure
because of the way the polymer is processed to produce the fibre.

5.5 Poly(propenonitrile) (Polyacrylonitrile)

Repeating unit

Monomer
H2C= ~- CN propenonitrile (acrylonitrile)

Manufacture of'monomer
bismuth
molybdate

700 K. 3atm

Newer catalysts, based on antimony(v) oxides, are being formulated and

used.

Manufacture of polymer

Propenonitrile is dissolved, partially, in water to which a radical initiator,

potassium persulphate is added.

The precipitate is filtered, washed and dried.

102
Physical properties
Density 1.18 g cm-3; Tg 363-378K; Tm 591 K. Exists in crystalline form.

Principal uses
Textile fibre (Orton) and as co-polymers 90%; in synthetic rubbers 10%.

Modified forms
Acrylic fibres are polymers containing at least 85% propenonitrile
(acrylonitrile). Co-monomers are used to make the polymer more amenable
to dyeing. They have high strength, abrasion resistance and resilience.
They also have good resistance to weather, stains, chemicals, insects and
fungi.
Copolymerisation with 50% ethenyl ethanoate produces the textile fibre
Acrilan.

Copolymerisation with 4% chloroethene produces the textile fibre Courtelle.

Copolymerisation with buta-1,3-diene gives nitrile rubber (used in strong
but flexible gloves).
Copolymerisation with buta-1,3-diene (20%) and phenylethene (50%) gives
ABS rubber which is used in car bodies.

Tonnage (1993)
World, 3.7 x 106; W Europe, 1.0 x 106; UK, 0.2 x 1()6

5.6 Processing synthetic fibres

Methods of spinning developed for natural fibres are not suitable for
synthetic fibres. There are two commonly used methods:

(i) Melt spinning Chips of solid polymer (e.g. nylon) are melted
and the liquid polymer passed through a
spinneret which contains a number of fine
holes. Fibres form as the polymer solidifies and
these are pulled together over a pulley.

(ii) Solvent-spinning A solution of the polymer in an appropriate

solvent (e.g. cellulose ethanoate in propanone)
is passed through a solvent into warm air.
Solvents evaporate leaving fine fibres which are
pulled together over a pulley.

1m
TABLE 5. PROPERTIES OF TEXTILE FIBRES

~
(I,) ~
>-
,..= •....•0
fIl ~

::s fIl
..0

•....•
.+0)

(I,)

~ S
o .+0)

o o
to
l =
fIl
(I,)

"C
o

11
~
o
•....•
~ ~ ~ ~ ~
o
•....• o
•....• o
•....• o
•....• o
•....•
~
(I,)

>

~ ~ ~ ~ ~
o
•....• o
•....• o
•....• o
•....• o
•....•

,.. ,.. ,.. ,..

o o o o
o o
c, o o
~ ~ ~

J 8 8o
"C "C
o 8
o
o
o
8
o
o o
btl ~ btl ~ ~ ~

=o
~,..
•....•
:§=
(I,)
•....• fIl
o (I,)
o ~
,..
(.) (.)
o •....• fIl 01""4

>
o
o i3:
01""4

00 E-t

101
 ACTIVITIES
AS.1 Discovery of rayon
Read the short article and answer the questions below.

DISCOVERY OF RAYON

Rayon was the first man-made fibre to be produced commercially and is a reconstituted and
purified cellulose material. Nearly all plants have a cellulose constituent and natural cellulose
can be readily produced from wood through chemical and thermochemical separation
processes. In 1846 it was discovered that by treating natural cellulose with nitric acid a
substance called nitrocellulose could be formed which readily dissolved in organic solvents.
Fibres could be produced by squeezing the resultant solution through tiny holes. Unfortunately
nitrocellulose is extremely flammable and the fibres could not be used to make fabrics. Later, in
France, Count Hilare de Chardonnet found an answer to this problem. He converted the fibre of
nitrocellulose into cellulose by chemical treatment and Chardonnet silk or rayon was invented.
This was first produced commercially in France in 1891.

The method was superseded a few years later by a method in which cellulose xanthate is
formed and then dissolved in dilute caustic soda solution producing a viscous liquid (called
viscose). Extrusion of the viscose solution through jets produced filaments or fibres which
readily coagulated in acid solution in the form of cellulose. The process was cheaper and better
and reflects the production of viscose-rayon today. Fast colouring matter can be added to the
viscose solution prior to spinning and thus produce a dyed fibre in one stage. Chemically the
fibres are made up oflong straight chains of (C6HlO05) monomers.

0-
cellulose

-0

NaOH
CS2 NaSH

cellulose xanthate extrusion

solution separation

1. a) Why was nitrocellulose fibre not suitable for the manufacture of

textiles?
b) Explain some advantages of the viscose method over the
Chardonnet method.
c) Work out the chemistry involved in the Chardonnet process and
write up a descriptive account of it.
d) Describe briefly the process of extrusion.
AS.2 Preparing rayon

Follow the instructions carefully to prepare a small quantity of rayon.

CARE - Eye protection should be worn

CARE - Ammonia solution gives off a strong vapour
CARE - Carry out this experiment in a fume cupboard

Requirements
50 em" freshly prepared aqueous ammonia solution (equal volumes of 0.880
ammonia and water) - Irritant at this concentration
4 g of copper(ll) carbonate - Harmful
dilute sulphuric acid - Irritant, corrosive
2 small glass beakers (100 em")
glass stirring rod
syringe - 10 em"
petri dish
11 em diameter filter paper
access to fume cupboard

What to do
1. a) Place the 50 em" of ammonia solution in one of the small beakers.
Add the copper(ll) carbonate a little at a time, stirring well, until
no more dissolves.

b) Allow any undissolved copper carbonate to settle and then pour

off the blue liquid into the second small beaker (leaving the solid
in the first beaker).

c) Now tear the filter paper into tiny pieces and stir them into the
blue liquid until they completely dissolve and form a blue syrup.

d) Place a small quantity of dilute sulphuric acid into the petri dish
to give a depth of 5 mm.

e) Draw some of the blue syrup into the syringe and then carefully
inject it into the sulphuric acid in the petri dish.

f) Leave the thread in the sulphuric acid until it changes colour at

which point it can be removed with a glass rod and carefully
washed.
• What is the chemical constituent of filter paper?
• Copper carbonate is insoluble in water. Explain why it
dissolves in ammonia solution.
• Suggest why filter paper dissolves in this blue solution.
• Explain why rayon is formed when this solution is extruded
into dilute acid.
• Describe the appearance, feel and strength of the rayon
formed. How could it be made stronger?

100
A5.3 Making a nylon

Follow the instructions to prepare a sample of a nylon.

CARE - Eye protection and disposable gloves must be worn.

CARE - Decanedioyl dichloride has an irritating vapour.
The vapour is a powerful lachrymator (eye irritant) and this
effect is often delayed.
CARE - Perform Part 1a) in a fume cupboard.

Requirements
decanedioyl dichloride - corrosive liquid, 5% solution in cyclohexane (1 em")
- irritant vapour (See note below)
1,6-diaminohexane - irritant, 5% solution in 0.5 M sodium carbonate
solution (1 em")
5 cm'' beaker
glass rod or test tube
tweezers
access to fume cupboard

:Note
The solution of decanedioyl chloride (corrosive) must be made up freshly for
each series of experiments.

What to do
1. a) Pour about 1 em" of the decanedioyl dichloride solution into a
5 em" beaker.

b) Carefully add an equal volume of the 1,6-diaminohexane solution

to the beaker. Ensure that the two layers do not mix.

c) Use a pair of tweezers to remove the nylon film which forms

where the two layers are in contact. Do this slowly and hook the
nylon thread which forms onto a glass rod or test tube.

d) Slowly wind the thread around the rod or test tube. As the nylon
is removed, more forms at the solution interface so you should be
able to keep on winding for some time.

e) Once you have made some nylon it needs to be washed thoroughly

with tap water. Take care not to touch the nylon because it forms
as a hollow tube, and there will still be some reactants trapped in
the middle.

• Write out an equation to show the formation of nylon in this

activity.

• What is the name of the nylon you have made?

1(17
AS.4 Isomerism of a polyester
This practical activity compares a polymer made up of linear monomer
chains with one made up of zig-zag monomer chains.

CARE - Eye protection must be worn.

CARE· This experiment must be carried out in a fume cupboard.
CARE - Precautions must be taken to ensure that the oil bath cannot be
upset.

Requirements
ethane-l,2-diol (6 g; 5.6cm3) - FlammablelHarmful
benzene-l,2-dicarboxylic acid (8 g) - Harmful
benzene-l,4-dicarboxylic acid (8 g) - Harmful
Dow Coming silicone oil 210H/II0cs (propane-l,2,3-triol is an acceptable
and cheaper alternative)
2 old boiling tubes
100 em" beaker for oil bath
thermometer to read to 180°C
access to fume cupboard

What to do
1. a) Label the two boiling tubes 1 and 2. Put 3 g (2.8cm3) of ethane-
1,2-diol into each tube.
b) Into tube 1 place 8 g of benzene- 1,2-dicarboxylic acid. Into tube 2
place 8 g ofbenzene-l,4-dicarboxylic acid.
c) Heat both tubes in a silicone oil bath at 180°C for 1 hour.
d) Leave the whole assembly to cool. Allow the tubes to stand
overnight and then examine the contents of each tube.
• Describe the contents of each tube.
• Does one appear to be more crystalline than the other? If so,
which?

Remember
• crystalline polymers are usually opaque with high melting points
• non-crystalline polymers are usually transparent and glassy and
have lower melting points.

• Draw the structural formula of each acid.

• Draw the structures of part of each polymer (including at
least four benzene rings in each case), representing:
o 0
II II
- c- 0- 0i2- 0i2- 0- C- as

• Explain the difference in appearance of the polymers in

tubes 1 and 2 in terms of the structures you have drawn.

100
AS.S Development of Kevlar

Read the short article and answer the questions below.

DEVELOPMENT OF KEVLAR
The first polymeric aromatic amide - aramid - was made from
3-aminobenzoic acid. It could be made into fibres and was fire-resistant, but
it was not particularly strong. The zig-zag nature of the chains prevented
the molecules aligning themselves properly. A polymer was needed with
straighter chains which could be made from readily available and
reasonably cheap starting materials. One which could be made in this way
is shown below:

11-0-11-0-
o
-c~c-~~~-c~c-
0
11-0-11
0 0

H H

This substance turned out to have all the required properties except one.
The problem was its insolubility, which made it precipitate out of solution
before the polymer chains had been able to grow long enough. Eventually a
suitable solvent was found, sulphuric acid. Fibres were produced by
squirting the solution in concentrated sulphuric acid into water. The
resultant precipitated polymer was called Kevlar.

1. Draw the repeating unit for Kevlar.

2. Draw the structure of the monomers for Kevlar.

3. What are their systematic names?

4. a) What type of bond links the monomer units together in the polymer?
b) What is the name for this group of atoms?

5. What other families of polymers has .this structure?

6. Draw out a small section of the structure of the polymer which could
be made from 3-aminobenzoic acid.

7. Explain in terms of the intermolecular forces between polymer chains,

why Kevlar is stronger than its isomer which was prepared from 3-
aminobenzoic acid. (It might help to make models of the two isomers.)

8. The intermolecular forces in Kevlar are disrupted by concentrated

sulphuric acid. That is why it dissolves. How do you think the forces
are affected ?

100
A5.6 To compare the effects of natural and commercially produced
dyes on natural and synthetic fibres.

This activity is suitable for an extended project.

Requirements
two or more samples of plain
two or more samples of plain
small quantity of commercial
plants, berries, vegetables or
up a natural dye
a suitable mordant (fixer) for
2 beakers (500 em")
fabric made from different natural fibres
fabric made from different synthetic fibres
chemical dye
other natural materials suitable for making
the natural.dye

What to do

1. a) Work out a process for producing a natural dye from the

materials available. Carry out a risk assessment for any of the
chemicals you are using or making, e.g. remember the mordant.

b) Prepare the natural dye and commercial chemical dye in

separate beakers.

c) Dye one piece of plain natural fabric and one piece of plain
synthetic fabric in natural dye. (Allow at least 30 minutes contact
time between the dye and fabric).

d) Dye one piece of plain natural fabric and one piece of plain
synthetic fabric in commercial chemical dye. (Follow the
instructions on the dye packet).

e) Compare the quality of colour between the different dyes and

fibres.

f) Test for colour fastness by washing the dyed samples and

observing any fading which might result.

• Write a report on your activity and findings, with particular

reference to the types of bonding and reactive groups in the
textile fibres in the fabrics used, and to the nature of the
reactive group in the dyes (where known). The table of
information in Activity A5.7 may be useful.

110
AS.7 Textile fabrics and dyes

Successful dyeing depends on the bonding between dye molecules and

available functional groups in the polymer(s) in the fibres of the fabric.
Polymer molecules with no reactive or polar groups (e.g. polyesters) are
hydrophobic and fabrics containing such fibres can only be dyed using an
aqueous suspension of very small particles of dye which become absorbed
into the fibres forming a "solid solution". Such dyes are known as disperse
dyes.
A brief summary of some types of dye with their reactive groups and an
appropriate fabric in each case is given below. The suggested dyes are not
exclusive to the particular fabric shown. Detailed information will be found
on each packet.

Fabric Reactive ~ofdye Example of Reactive Dyeing

group ~ group(s) conditions

Cotton -OH Direct CI Direct - Sea-Na+Aqueous

Brown 138 solution

Viscose -OH Reactive Procion dyes -S03-Na+ Aqueous

rayon bonds with solution
-CI (solubility of
and large
-OH molecule due
to Na+ salt)

Cellulose hydrophobic
triethanoate
(Tricel)

Polyamide \ Acid CI Acid -COOH Used in

(e.g. Nylon) NH Orange 7 dilute
/ -S03H
solution of a
weak acid

Poly(propeno -C=N Basic CI Basic -NH2 Dye used as

nitrile) (hydrolysed Green 4 ammonium
(e.g. (Malachite -NR2 salt in
to
Acrilan) -COOH) green) aqueous
solution
Polyester hydrophobic Disperse CI Disperse Used in
(e.g. Yellow 3 aqueous
Terylene) suspension

Textile fabrics and dyes

Answer the questions below with reference to this table which relates types
of dyes to the reactive groups in different textile fibres.

111
1. What type(s) of dye, other than that shown in the table, might be
sui table for
a) nylon,
b) viscose rayon
c) cotton?

2. What type of dye should be suitable for Tricel? Give a reason for your
answer.

3. a) Name two natural fibres other than cotton.

b) What type of bond is present in each of these?
c) What is the name for this group of atoms?
d) What type(s) of dye would you expect to bond with these?

4. This question could be extended into a project.

How would you judge a dye to be "successful" with a particular fabric?
Try one type of dye with as many neutral coloured fabrics as you can
obtain. Devise a programme to assess the success or otherwise of the
dye on each fabric. Tabulate your results and relate them to the
active group(s) in the dye and the structure of the polymer(s) in the
fibres of the fabric.

112
 SECTION 6

Composite Materials
A composite material consists of two principal components: the matrix and
the reinforcement. In reinforced concrete, for example, the matrix is an
aggregate of cement and sand and the reinforcement consists of steel wires
or bars. The area of interface (or interphase) between the two components
is also important in determining the properties of a composite material.
The combination of these relatively cheap materials, the matrix which is
weak in tension and brittle, with a reinforcement, which is strong in
tension, gives a tough material suitable for large-scale construction.

6.1 Reinforcing fibres

The development of new and improved fibres has been the main driving
force of the 'composites revolution'. By drawing materials into very fine
fibres (usually about 10J..Lm diameter), faults within their structure, which
might otherwise weaken them, can be eliminated. By this means,
materials like glass and ceramics, that are usually considered to be
relatively fragile substances, can be made exceptionally strong.

Drawing processes can also realign the molecules which increases,

further, the strength and stiffness of the polymer. The exploitation of this
orientation process allows polymers like poly(ethene), usually considered to
be one of the 'softer' plastics, to be made into strands from which even
bullet-proof jackets can be constructed.

Heat treatment is a further method of enhancing the properties of fibres.

For example, poly(propenonitrile) fibres, whose acrylic cousins are familiar
as clothing materials, can be fired into carbon fibres with equivalent
stiffness, strength and temperature performance to steel but with far lower
mass.

The major reinforcing fibres used in structural composites include carbon,

glass, aramid (e.g. Kevlar) and ceramic.

6.2 Matrix materials

The functions of the matrix are to support the fibres, to transfer load
between neighbouring fibres and to define the shape of the material.

A matrix must possess the property of being able to infiltrate the

reinforcement and then be solidified. It is usually a thermosetting polymer
such as a polyester, an epoxy resin or a phenolic resin. In certain
composites ceramic, metal or thermoplastic materials are more
appropriate.

Polymers are usually preferred for use at temperatures up to 475 K but for
high temperature performance (e.g. carbon-fibre-reinforced composite for
rocket nose-cones) a ceramic matrix must be used.

113
6.3 The Interface

A typical composite material consists of 60% by volume of 6 urn diameter

fibres. 10 em" of such a composite, weighing about 16 g, will contain about
four square metres of interface area between the fibres and the matrix.

In some composites, where a brittle matrix is used, it may not be desirable

to have strong bonding between the fibres and matrix so that energy is
absorbed by creating surfaces. In other systems, with tough matrices, a
very strong interface may be designed into the structure. Control of that
interface can be achieved by a blend of physical and chemical means.
Because the mean thickness of resin between fibres is only of the order of
2J..llIl, the effect of the interface on the matrix may often be felt throughout a
substantial part of its thickness, giving rise to the concept of an interphase.

6.4 Classes of composite material

There are three distinct families of polymer matrix composite. The

classification of these families depends on how they are made into
structures.

In the first family the fibres are assembled into the required preform and
the matrix is then infiltrated into place: this technique requires highly
mobile matrices and examples include chemical vapour deposition,
infiltration by liquid metals, and injection of monomeric resins which can
be subsequently polymerised.

In the second family, the fibres in collimated tape, woven fabric or random
mat form are preimpregnated with a partially polymerised matrix to form
an intermediate material which can be conveniently assembled into
structures where the matrix, often an epoxy or polyester resin, is cured,
usually by crosslinking, into its final form.

In the third family the preimpregnated product form is based on linear

chain polymers, such as poly(propene) or poly(ether etherketone) (PEEK),
which can be rapidly shaped by simple physical processes. Each of these
product forms has different advantages depending on the application
envisaged.

6.5 The properties and applications of composite materials

The most important property of composite materials is stiffness at low

weight. Further, with a composite material based on highly aligned fibres,
the stiffness of a structure can be designed to meet the loads which it must
bear. In some cases it is possible to design a structure which is very stiffin
one direction but highly flexible in another. High stiffness at low weight
are properties which are very useful in making aircraft. A well-known
composite family of this type is the carbon-fibre-reinforced epoxy resins
used in tennis racquets and air frames used in aircraft construction.
These composites are much lighter and stronger than conventional
materials such as the best aluminium alloys.

114
While stiffness per unit mass is the major property, other properties can be
designed into a structure. One of the earliest uses of modern composite
materials was to make radomes for aircraft: effects such as the electrical
properties of composites continue to be of great significance and can be
tailored in the same way as stiffness.

There are many other properties which can be designed into composite
materials. Highly oriented reinforcing fibres can have a negative or zero
thermal coefficient of expansion. This is important when making precision
instruments and structures, particularly in satellites, where there are
rapid changes of temperature as the satellite goes from full sunlight to total
darkness very rapidly.

Composite materials can be designed to withstand other hostile

environments. Water is one such environment and some of the largest
composite structures are used at sea. An appropriate composite for small
boat-building and skis is the so-called "fibre glass", a glass-fibre-reinforced
polyester or epoxy resin. The glass fibres are strong but brittle whereas the
polymer matrix is weaker but flexible. This combination of materials
results in a strong, tough composite. Because of the combination of
stiffness, ease of manufacture, non-magnetic properties and water
resistance, modern mine-sweepers are made from composites.

Although polymer matrix composite materials may still be more expensive

than metals, which they often seek to replace, the cost of manufacture can
be dramatically reduced because the number of parts that are involved in
building a structure can be reduced. In addition, corrosion resistance is a
significant factor, allowing composite materials to compete in terms of
costs over the lifetime of the article.

115
 ACTIVITIES

A6.1 Dental Composites

Read all the information and then answer the questions which follow. If the
questions require a more advanced knowledge of chemistry than you have
yet acquired, they will become useful for revision at a later stage.
Alternative CFCs
CFCs; no, not chlorofluorocarbons, but cavities, fillings and cements,
most of us experience at some stage of our lives.
When dental enamel and dentine become decalcified by the action of
certain bacteria (streptococcus mutans) which are present in plaque, the
result is the formation of dental cavities (tooth decay).
A visit to the dentist to repair the damage results in the removal of the
decayed area forming a cavity which has to be filled. The material used
in filling the cavity may be one of several types: amalgams containing
mercury and other metals, gold alloy inlays, or dental cements which are
similar in colour and texture to the original tooth.
Some dental cements involve the use of polymers. Ideally the material
used must adhere strongly to the tooth and also resist disintegration.
One of the techniques used involves substances which polymerise in the
cavity. Most of the materials formed are the result of addition
polymerisation. Some examples of monomers which have been used to
form polymeric cements are shown in Fig. 1.

Fig. 1
MONOMER POLYMER

1~-~::t.
H H
\ /
C=C
/ \
H COli H CO;:H
n
acrylic acid polyacrylic acid

HO~

H
\
I
C=C
/
\
H

CO;:H
1YO~~::t.
C-C
I
H
I
COli
n
fumaric acid polyfumaric acid

1H ~
H CH3
\ / I I
C=C C-C
I \
H CO~3 ~ ~:Pi3 n

methyl methacrylate polymethyl methacrylate

116
 One of the problems encountered in the use of materials like the ones
mentioned above is that the polymer shrinks when the monomers
polymerise. This can result in gaps forming between the filling and the
tooth which would allow foods, saliva and eventually bacteria to
accumulate.
Some of these polymers are also not very resistant to wear and have now
been replaced by dental composites.
Dental composites involve the use of dimethacrylate polymers in
conjunction with inert fillers as reinforcement. These inert fillers
consist of particles of silica (Si02), alumina (Al203) and various glasses,
of a specific size (40-1000 nm), The inclusion of inert particles gives
strength to the composite and reduces the problem of shrinkage.
However, because of their inert nature they need to be coated with a
silane bonding agent which forms a link with the polymer at one end and
with the ceramic filler at the other.

Questions
1. a) Give the systematic names (lUPAC convention) of the monomers
in Figure 1. Their trivial names are acrylic acid, fumaric acid and
methyl methacrylate.
b) i) Which of these three molecules is one of a pair of geometric
isomers?
ii) What feature of these molecules is responsible for geometric
isomerism?
iii) Give the structural formula and systematic name of the
other geometric isomer.
iv) Which of these isomers would you expect to polymerise
most easily? Explain your answer.

2. a) Monomers of the type mentioned in Q.1 have carbon-carbon double

bonds. Describe their nature.
b) Which part of the carbon-carbon double bond is disrupted when
polymerisation occurs?
c) What is the most common type of reaction in which alkenes take
part?

3. Addition polymerisation does not usually occur spontaneously and has

to be started by the use of other chemicals called initiators.
A typical initiator is dibenzoyl peroxide.
Giving reasons, state what type of reaction mechanism is likely to be
induced by the use of dibenzoyl peroxide.

117
4. In the polymerisation process, bond breaking and bond formation
occur:

\ /
n C=C
/ \

The bond energies of the carbon-carbon double bond and the carbon-carbon
single bond are 610 kJ mol-l and 350 kJ mol-l respectively.

What is the net gain or loss in energy for each mole of ethene
polymerised when polymerisation occurs?

5. Consider the two polymers whose structures are given below.

a)
t F~r~
C-C
I
H
I
co~ n tHI
C-C
a-J~
I

~ bo~3 n

Which of these two polymers is likely to have the stronger forces of

attraction between adjacent molecules? Explain your answer.

b) Draw a diagram to show how the cross-linking of polymer chains

may be possible.

Is this cross-linking likely to be strong or weak? Explain your

answer.

6.
During the past few years two-paste chemically-activated composite
materials have been superseded by one-paste light-activated materials.
These contain a photo-initiator which is used in combination with a
reducing agent. The polymerisation process is started when the initiator
is exposed to intense visible light. The ideal wavelength of such light is
470nm.

a) Explain the term photo-initiator.

b) In what part of the visible spectrum does light have a wavelength of

470nm?

c) Use the relationship u = ~ to calculate the frequency of

"-
radiation used, where "-is the wave-length and u is the frequency
and c, the speed of light is 3 x 108ms-1•

d) Why should infra-red radiation be unsuitable for the process of

initiating polymerisation?

118
7. The group of atoms -C02CH3 is present in dimethacrylate and methyl
methacrylate molecules.

a) What type of organic compound does this group of atoms represent?

b) Draw out the displayed formula (depicting each bond) for this group
of atoms.

119
A6.2 Use of two polymers but not a composite!
Read the information below and then answer the questions which follow.

Compact Disc Manufacture

During the production of CDs, the manufacturers prepare a master disc.
This is prepared from an optically ground glass plate, which is polished,
spotlessly cleaned, and coated with a thin and even layer of photo-resist.
Cleanliness at this stage is of paramount importance. In the production of
the master disc, Class 100 conditions are required. This means that no
more than 100 particles, which are ~ 0.5 microns per cubic foot of air, are
allowed; the conditions allowed in hospital operating theatres is one
hundred times greater than this!
The coated glass master is placed on a laser beam recorder. The master
tape containing the recorded music is played and the signal from the tape
modulates the laser beam which writes a series of pits and bumps onto the
photo-resist layer. After development, the master is coated with a thin layer
of silver using a technique known as vacuum deposition.
For the replication process a 'stamper', containing an exact replica of the
information on the master disc, is required. To accomplish this a uniform
layer of nickel is 'grown' onto the silvered master. This plating is separated
from the glass master, forming a metal negative known as the 'father'.
The 'father' is used to produce a number of 'mothers' which in turn are
used to make a number of 'sons'. The 'sons' are used to produce large
quantities of perfect CDs.
Two polymers are used in the manufacture of CDs. The main bulk of the
disc is made from optical grade clear polycarbonate using a technique
known as injection moulding. This involves melting the polycarbonate
granules at a high temperature and injecting the molten polymer at high
pressure against the stamper. A plastic replica approximately 1.2 mm
thick is produced.
A reflective aluminium coating is placed on the surface of the polycarbonate
disc to enable the laser in the CD player to read the information stored on
the disc. This aluminium coating is protected by a thin film of an acrylic
polymer.
label printed on
this side protective layer of acrylic aluminium

•
coating

,r ,

clear polycarbonate disc

t
laser "reads" disc
from this side
 Polycarbonates are polymers produced from carbonyl chloride
(phosgene) and bisphenol A as follows:

dissolved in
0i2C~

to-Q-[9-0-~t. + 2n Hel

- and the acrylic polymer, thus:

H H
\ /
n C=C
/ \
H CN

Questions
1. N arne one other use of acrylic polymers.

2. Use the general formula for acrylic polymers depicted below to explain
the terms
a) ISOTACTIC b) ATACTIC· c) SYNDIOTACTIC

t~-~t.
H X n
X = - CN, - COi"i,

(It will be necessary to show several repeating units to illustrate your

- CONH2

answers).

3. a) Give two reasons why the aluminium layer on a CD is protected

with a coating of an acrylic polymer.
b) Give two advantages of a CD over an LP record.

121
4. Acrylonitrile is manufactured from propene, ammonia and oxygen
using a catalyst.

670-nOK
2-3atm

a) Balance the above equation.

b) Propene is also used to manufacture poly(propene). Write an

equation to describe the formation of the polymer.
 SECTION 7

Degradable polymers
There has been considerable research in industrial and university
laboratories into the development of degradable polymers, which will
decompose, under natural conditions, within a relatively short period of
time. Problems to be solved include how to maintain the original properties
yet allow for degrading after the polymer has been used.

The basic concept is that the chain structure of the polymer is broken down
during decomposition. The material first becomes brittle and then
crumbles into increasingly smaller pieces as the molecular chains get
shorter and shorter. Ideally, the polymer will eventually yield carbon
dioxide and water. Two main categories of degradable plastics have been
developed, biopolymers and synthetic degradable polymers.

Biopolymers are made by living organisms and in tum can be broken down
by fungus and bacteria (i.e. microbically).

There are three types of synthetic degradable polymers in current use

which are designed to break down under natural conditions:
• Photodegradable - polymers which break up in sunlight
• Water soluble - polymers which dissolve in water
• Synthetic biodegradable - polymers with encapsulated starch
granules which can be attacked by micro-organisms in the soil.

One disadvantage of some degradable plastics is that they cannot be re-used

or recycled and are therefore a drain on non-renewable resources.
Degradable polymers are not intended to be alternatives to standard plastics
such as those used in construction applications (e.g. automotive industry).
However, they have a role to play in applications where recycling, either as
material or energy recovery, is not feasible for economic or ecological
reasons.

7.1 Blopol: an example of a Biopolymer

'Biopol'is a butanoate trade mark used by Zeneca for a family of polyesters,

chiefly poly(hydroxybutanoate) or PHB and its copolymers with

O-f-f-~°t
poly(hydroxypentanoate) or PHV.

t ~3H

H H n
the structure of PHB
n = 4,000 to 20,000
a) Manufacture
The polyesters are synthesized by some bacteria and, under certain
conditions, the polymer material will accumulate within the cells for use as
an energy store, in much the same way that animals store fat.

It is manufactured by inoculating a fermentation medium with a non-

pathogenic bacterium called Alcaligenes eutrophus. The bacteria grow until
the limiting nutrient (phosphate) is exhausted. At that point, a glucose feed
is introduced and fermentation is allowed to continue. The source of the
glucose is starch from cereal crops, an annually renewable source. There is
little further growth of cells after this point and the subsequent increase in
biomass is due to the synthesis and storage ofPHB. Up to 80% of the total
biomass dry weight may be PHB. The 'plastic' is harvested by breaking open
the cells and extracting the polymer.

The addition of organic acids (e.g. propanoic acid) to the glucose feed can be
used to manipulate the PRV content of the polymers stored within the cells.
This produces 5-hydroxypentanoic acid (the old name for this was
hydroxyvaleric acid) which becomes incorporated into the polymer chain to
produce poly(hydroxybutyrate)-poly(hydroxyvalerate), otherwise known as
PHB-V, which is stronger and more flexible than PHB.

Biopol is a thermoplastic and can be processed in the same way as more

familiar polymers, including using additives, to produce bottles,
mouldings, fibres and films. It has potential to be recycled or incinerated in
the same way as conventional thermoplastics.

b) Uses

Biopol is likely to appear first in UK markets as packaging for cosmetics

and biodegradable motor oils. For example, Wella 'Sanara' shampoo bottles
are made of Biopol. Packaging applications where reuse and recycling are
considered inappropriate, such as extrusion coated composite materials or
blown films, also appear to be promising early applications.

The bulk price of Biopol in1994 is over £10000 per ton. It is the combination
of renewable feedstock and biodegradability that is stimulating the search
for applications which will lead to larger volumes being manufactured.
Potential markets are in the production of hygiene products and in the
agricul tural sector.

c) Degradability

Natural polyesters of the Biopol type are normal components of soil

ecosystems and are released when bacteria die. Other organisms
metabolise the polymers as a source of carbon and energy. In aerobic
conditions, the polymers will biodegrade fully, as part of a complex carbon
cycle, to carbon dioxide and water. In anaerobic conditions, methane is
produced.

12A
Municipal composting trials, in a properly managed land fill site, indicate
that a Biopol bottle loses 80% of its mass in 15 weeks and a Biopol film of 100
mm thickness biodegrades fully in approximately 10 weeks in soil, or in
about one week in anaerobic sewage. However, the polymer is stable in
humid air alone.

7.2 Degradable synthetic polymers

7.2.1 Photodegradable low iknsity poly( ethene)

Low density polyethene can be modified so that when it is exposed to direct

sunlight, it can lose about 75% of its structural integrity within a matter of
days.

a) Manufacture

The basic concept of photodegradable polymers is that they contain an

unstable structural element in the molecular chain which acts as a weak
spot, sensitive to light. These elements are usually called photosensitizers
and are introduced at the manufacturing stage.

Carbonyl groups (C = 0) are introduced into the molecule during the

manufacture of low density poly(ethene). They absorb radiation in the
wavelength range of 270-360 nm, corresponding to light in the near ultra-
violet region of the spectrum. Sunlight of this wavelength is absorbed
causing the bonds to break in the neighbourhood of the carbonyl group.

b) Uses

Photodegradable polymers find applications in the plastic rings round six-

packs of beer and a thin film which is used as a mulch by farmers and
gardeners.

c) Degradability

Continued exposure to sunlight causes the material to disintegrate into

increasingly smaller pieces. By varying the amount of photosensitizer
additive the disintegration process can be 'relatively well controlled.

7.2.2 Poly('ethenol): an example of a water soluble polymer

A synthetic polymer, poly(ethenol) (also known as polyvinyl alcohol),

dissolves readily in water.

a) Manufacture

Poly(ethenol) is made from another plastic called poly(ethenyl ethenoate) by

a process known as ester exchange.
 o
II
0i30- C-0i3

poly(ethenyl ethenoate) poly(ethenol) or polyvinyl alcohol

reacts with methanol some of the ester groups on the
side chains of the polymer are
removed and new ester groups
form in methyl ethanoate

The extent of ester exchange can be controlled by warming, heating which

speeds up the process, or by giving the reaction more time.

b) Uses

Hospital laundry bags are made from poly(ethenol). This means that
hospital workers do not need to handle dirty linen, thereby reducing any
risk of infection. The bags dissolve during the washing process.

Other applications of water soluble polymers can be found in surgical

stitches and the protective coatings applied to new cars for the delivery
period, which can be easily 'hosed off afterwards.

c) Solubility

The solubility of the polymer in water depends on the percentage of ester

groups which have been removed. Material is commercially available in
two forms; cold water soluble or hot water soluble, depending on its
structure. They can be made so that they dissolve very rapidly in water.

7.2.8 Syntheticbiodegradable polynrers

Some plastic bags are made from a polythene which has starch granules
I encapsulated in it. The starch is digested by micro-organisms in the soil
when the plastic bag is buried. This breaks down the material to a fine
powdered form and could be considered as pseudo biodegradable since,
unlike Biopol, it is the starch content which comes under immediate attack,
not the synthetic polymeric materials themselves.

A biodegradable cellulose ethanoate is also available under the trade name

'Bioceta'. The material is a cellulose ethanoate with a plasticiser which
causes products to decompose in 6-24 months depending on the
environmental conditions.
As the material breaks down under anaerobic conditions, methane gas may
be formed. However, incineration does not generate any toxic emissions,
only carbon dioxide and water. It is currently used for shrinkwrap films
and blister packs.

7.3 Disposal and recycling of polymers

There is public concern about the impact of synthetic polymers on the

environment. Stringent legislation has resulted in 'Responsible Care'
programmes being set up in many countries which establish codes of
conduct for the industry on environmental responsibility and include a
commitment to responsible product management from 'cradle to grave'.

The question of waste disposal is often thought to be more of a problem for

plastics than for other materials. Plastics waste can be divided into pre-
and post-consumer waste. Most pre-consumer waste, such as material off-
cuts and imperfect products produced during the manufacturing process,
is recycled.
With an increase in consumption has come concern, both from the
consumer and the plastics industry, that urban and industrial waste is
handled properly. Indeed, almost half of post-consumer waste is Municipal
Solid Waste (MSW),often referred to as Domestic Waste.
Plastic packaging is easily seen in household bins and street litter because
of the bright colours involved. Until it has been compressed, it makes up a
quarter of the total volume of waste although it only accounts for seven per
cent by mass.

Proportions of materials found in domestic waste

127
There is also concern that plastics should be recycled so that less fossil
fuels, such as oil and gas, are consumed. However, sometimes the use of
plastic is criticised without considering the impact of using other materials
for, say, packaging. For example, it takes 100 kg of oil to make 1000 one litre
plastic bottles and about 200 kg of oil to make the same number of glass
bottles. Indeed, it is thought that transporting soft drinks in plastic bottles
rather than glass ones can lead to fuel savings of almost 40%.

Glass bottles Plastic bottles

111 Packaging EH}:] Product

Comparison of amount of transportable product depending on packaging material

Nevertheless, durability, the very thing which makes plastics so useful,

creates a problem for disposal, contributing to litter, landfill overflow and
ocean. pollution. Product lifetime also affects the appearance of particular
items in the waste stream. Most packaging has a short use lifetime since it
is discarded almost immediately after the purchase of its contents; thus
leading to an overwhelming contribution (40% of all plastics) in volume to
domestic waste. Other products, such as plastic piping, may have a
lifetime of about 20 years before entering the waste stream. Solutions to the
problem of plastics waste can be considered under the following headings:
• reduction at source
• recycling
• feedstock recovery
• energy recovery
• landfill
• degradable plastics (see earlier section)

a) Reduction at source
It is often possible, with careful thought, to reduce the amount of material
needed to make a specific product. Recent examples are the smaller
cartons for high concentration liquids, refill packs for detergents and
reduction of material thickness, for example in PE film and PET bottles.
b) Recycling
Recycling is one way to recover and re-use synthetic polymers. It can
involve reusing the product (as with milk bottles) or reconstitution of the
material. Recycling not only removes the materials from the waste stream
but also reduces energy needed in production since the original material is
now being used a second time. However, there are serious problems in
recycling plastics and currently only about 7% of plastics waste is dealt with
in this way in Western Europe.

To produce good quality recycled material individual plastics should be

recycled separately and this creates an immediate problem with municipal
waste, for it contains items made from a range of plastics materials. It is
possible to recycle mixed plastics but this produces a lower quality material
which has a limited use.

Some solutions to the problem involve householders separating, for

collection, items in domestic waste. Bottle banks are also being used. The
automotive industries are developing schemes which involve designing
vehicles to enable plastic parts to be removed easily and recycled when the
cars are scrapped.

Reprocessing invariably degrades the plastic, making it unsuitable for high

quality applications, as required in food packaging, but it is more than
adequate for non-food packaging. The use of recycled material as an inner
core, with virgin material providing the outer surface, is another
development for use in household chemical containers but this in turn
creates problems for further recycling.

Recycled
HOPE

Virgin
HOPE

Section through
wall of container

In general, plastics processing equipment is designed to operate at high

levels of speed and efficiency which rely on the use of a consistently high
quality material. The use of lower quality recycled material will probably
lead to slower processing times and loss of material. This, coupled with the
cost of collecting and sorting waste plastics, makes it difficult for recycled
plastics to compete economically with virgin materials.
Plastics recycling needs a partnership between manufacturers,
shopkeepers and householders, so that together they can protect the
environment and the Earth's reserves of raw materials for future
generations. Manufacturers must produce more goods from recycled
plastic and we must be willing to buy them.

c) Feedstock recovery

This operation involves breaking down the plastic waste into monomers or
oillhydrocarbon fractions. This is only suitable when the original
feedstocks can be recovered by simple chemical processes as with PET and
polyurethanes. In spite of considerable research, much plastic still cannot,
at present, be broken down into useful chemical feedstocks.
d) ~nergy recovery

Incineration is another way to reduce waste. Plastic waste has a high

energy content; it can be burnt and the heat generated can be used. The
energy released is compared with other materials in the table below.

Energy Released in
Material
MJIkg-l

Wood 16

Paper 16

PVC 19

Coal 31

Average for plastics 38

Heating Oil 44

LDPE 46

PS 46

One concern about this option is that some polymers give off toxic fumes
when they burn, and control of these emissions has been the subject of a
considerable amount of European legislation. The treatment of the
emissions (electrostatic precipitators, filters and acid gas scrubbers) is
expensive.

100
e) Landfill

Historically, landfill has been the most common method of dealing with
plastic waste because plastics do not produce harmful degradation products
when buried. However, in many areas landfill costs are increasing as new
sites become more and more scarce.

The international perspective

The current trend is to promote recycling and reduce using landfill. In

Europe, the EU Commission is working on proposals to increase the
recovery of packaging from waste across Europe, and to harmonise the
legislation of individual member states. But already, as can be seen from
the following, there are some interesting initiatives.

In 1990 France was recycling about 5% of domestic polymer waste and

incinerating about 27%. A new scheme became effective in January 1993
called the Eco-Emballage through which the French hope to be recycling
20% of domestic polymer waste and incinerating 45% by the year 2000. The
"Pelican project" collects PVC bottles as separate items from municipal
waste by the use of bottle banks and door to door collections.

In Italy "the Tecoplast project" makes use of electronically controlled bottle

banks at supermarkets which issue receipts for use as discount vouchers
against goods purchased in the store. The collection of bottles for recycling
is now compulsory in Italy.

Germany has perhaps the most stringent of legislation. From 1995, 64% of
all waste must be recycled and 80% of all packaging is to be collected
separately from other waste. In response to this, German industries set up
the Duales System Deutschland (DSD) initiative to collect plastic waste from
households for recycling. The scheme is financed by licensing a green dot
which manufacturers can attach to their products indicating that they are
suitable for recycling. Germany is also at the forefront of developments to
introduce 'composting' as a method of recycling biodegradable polymers.

Germany is not the only country to adopt a coding system. For example,
some British companies are using their own system. Unfortunately, this
confuses consumers, and the major trade associations in the plastics
industry are promoting an initiative to adopt the SPI code, originated by the
Society of Plastics Industry Inc in the United States, which has already
been widely adopted elsewhere in Europe. The coding system is illustrated
below:

PETE HDPE v LDPE PP PS OTHER

Note that 'V' (vinyl) represents PVC and 'PETE' represents PET

131
 ACTIVITIES

A7.1 Investigation of a plastic which dissolves In water.

I CARE - Eye protection must be worn

Requirements

samples of poly(ethenol) film - two forms are available, cold/hot water

soluble
250 em-beaker
washing powder
glass rod

DISSOLVING PLASTICS

Hospital laundry bags are made from a plastic which dissolves in water.
This means that hospital workers do not need to handle dirty linen
thereby reducing risk of infection. The bags dissolve during the
washing process.

What to do

1. Plan and carry out an investigation to find out how fast poly(ethenol)
film dissolves in water at different temperatures. Only carry out the
investigation after checking the plans with your teacher.

• What recommendations would you make to hospitals about the

length of wash cycle and temperature of the wash?

2. Some washing detergents contain high proportions of borates which

adversely affect the solubility of the poly(ethenol) material. Devise an
investigation on commonly used washing detergents which would
enable you to make recommendations to hospitals on the most suitable
detergent to use in combination with poly(ethenol) laundry bags. Carry
out the plan after checking it with your teacher.

A7.2 Consideration of photodegradable polymers

The following questions could be discussed in small groups.

1. Suggest some suitable uses for photodegradable polymers.

2. Suggest some situations where their use would be unsuitable.

3. What happens to a photodegradable polymer if it is disposed of by

landfill ?

132
A 7.3 Investigating the recycling of plastics

1. Find out what facilities, if any, are available locally for recycling
household waste plastics.

• Suggest two efficient methods of collecting household waste plastics

for recycling.

• Can assorted plastics materials be separated mechanically or does

it have to be done by hand?

• How could you use the properties of plastics materials to facilitate

separation?

2. Model a system in the laboratory to illustrate how the recycling of

domestic waste might be put into practice.

• Does the recycling of domestic waste plastics cause any

pollution or use up more energy than it saves?

• Describe a suitable strategy for persuading householders,

industrialists, retail outlets, and local councils to work together in
establishing an efficient system for recycling waste plastics.

A7.4 Investigating Biopol

Read the section on Biopol and then answer the following questions.

1. Draw the structural formulae for 3-hydroxybutanoic acid and

3-hydroxypen tanoic acid.

2. Draw out the structure of a small section of the PHB chain, made by
polymerising 3-hydroxybutanoic acid.

3. Describe the characteristics of PHB ?

4. Describe the characteristics of PHB- V·?

5. What are the advantages ofPHB-Vover PHB?

6. Briefly describe the mechanism of biodegradabili ty of Biopol as part of

a soil ecosystem.

133
 SECTION 8 TEACHERS' NOTES

Section 8 contains hints and answers for the activities suggested at the end
of sections 1-7.
The table below may be useful as a reference for sources of the polymers
used in the activities.

Plastic

Poly(chloroethene}, PVC Cling film, transparent bottles for food

Poly(ethene},HDPE Carrier bags, freezer bags
Poly(ethene},LDPE Carrier bags, bread bags
Poly(phenylethene}, polystyrene Yoghurt cups, egg boxes, disposable cups
DO NOT USE EXPANDEDPS
Poly(propene} Transparent crisp bags, agricultural
twine
Poly(methyl-2-methyl propenoate}, Car light covers, brittle rulers
Perspex
Polyamide, Nylon Climbing rope, tights, curtain fittings
Polyester, PET Fizzy drinks bottles
Phenol-methanal resin, phenol- Dark-coloured brittle electric fittings
formaldehyde
Urea-methanal resin, urea- Light-coloured brittle electric fittings
formaldehyde, u-F, Bakelite

Sources of plastics from common objects

8.1 Activities In Section 1

Guidance Notes
A 1.1 Most old plastic electric fittings will be Bakelite. Ensure your
samples are Bakelite by carefully heating a fragment beforehand.
Ensure that only very small fragments are used and keep the
laboratory WELL-VENTILATED. Carry out heating experiments in
a FUME CUPBOARD.

1d} The explanation can be given in terms of long-chain molecules held

together only by H-bonds and Van der Waals forces (nylon,
thermoplastic) contrasted with the 3-dimensional structure held by
single covalent bonds throughout (u-F resin, thermosetting).

A 1 .2 The longer cotton threads become tangled more easily and so will not
draw out as easily as the shorter threads. This is a simple model
demonstrating what is happening at the molecular level. The longer
chains can be drawn out further before breaking. So longer polymer
chains lead to greater tensile strength.

134
A1.3 Hubba-Bubba gum works well. The warm gum is elastic. If it is
pulled too hard it deforms permanently. The cold gum snaps when
it is bent because its temperature is below Tg.

A1.4 Cold-drawing a polymer. A tensile testing apparatus for wires is

expensive but can also be used for other experiments. Students
might compare the different behaviour of metals and plastics. With
metals, there is no increase in strength where necking occurs so, the
concentration of the force at the narrower region leads to sudden
fracture. With plastics, further necking of the weaker, undrawn
region occurs.

1b) Drawn plastic is more opaque because of the residual presence of a

small percentage of non-crystalline regions with a different
refractive index. (Note that highly crystalline polymers are usually
opaque, while non-crystalline ones are transparent.)

Ie/d) Carrier bags from Tesco and Sainsbury work well but it is not always
easy to tell if the "necked" region is more or less opaque. As it is not
obvious just when the stretched region is going to break, measuring
the length 'just before it breaks", requires some planning and at
least one trial run.

Some plastic sheets tear easily in one direction but stretch in the
other indicating that the molecules are aligned and that the forces
between polymer molecules are weaker than those within each
molecule. The longer the individual molecules the greater the
resistance to tearing in the drawn region.

Other possible materials: cling film, freezer bags.

A1.5 Semi-skimmed milk works well. Both samples seem to be equally

hard after 3 weeks but the untreated sample softens slightly when
put in water for a while. This behaviour shows that there is probably
less cross-linking in the untreated sample.

This activity might form the basis of a project in which different

milks and/or concentrations of acid could be used.

A1.6 Care - Avoid breathing poly(ethenol) dust. The experiment works

best with poly(ethenol} (polyvinyl alcohol) of high Mr (samples with
Mr 65 x 1()3or Mr 115 x 1()3;96 - 98% hydrolysed, work well). This
may be obtained from BDH Chemicals or Aldrich Chemical
Company.

135
1. Making a 4% poly(ethenol) solution:
Bring 100 em" water to boil and add 4 g poly(ethenol), a little at time,
while stirring. A colourless viscous solution should be obtained after
10-15 minutes though this may take longer. Do not boil. The
poly(ethenol) degrades to give chains with lower Mr if heated too
strongly.

2. Properties of 'slime':
'Slime' can be stretched by slow pulling, but will break if pulled
abruptly. Chunks of mechanically broken gel can be reworked into a
single mass. Assumes shape of container; if suspended from hand
will flow and stretch; self-siphons. If placed on a flat surface, it
flows to form a film. Bounces to a small extent.
The 'slime' will keep several days if kept in a closed jar but mould
will grow on it eventually.

Do not let SIUDENTS take the 'slime' out of the laboratory. It

removes paint and sticks to carpets.

3. Structure of 'slime':
The poly(ethenol) chains are linked by the borate groups through
hydrogen bonding;
H H

""
H \
'C-O-HIIIIIIIO
I I I H
O-HIIIIIIIO-C/

~C / /
B- \ ~2

\
/c-"Ou",uH-O / /.•.•••
OIllIlIlH-O--C
H I I I \ H
H H

The cross-linking is not fixed, but can break and reform easily. In
Bakelite, the cross-linking is permanent through strong covalent
bonds.

100
8.2 Activities in Section 2

A2.1 Production of poly{ethene)

The boxes should be arranged in the following order: 1~ 4 ~ 2 ~ 3 ~ 5 ~ 6

A2.2 Comparing two forms of poly{ethene)

Comments
Samples of high and low density poly(ethene) can be ordered from
suppliers, or you can obtain them from commercial packaging. Try to
make sure the samples are of similar thickness.

Low density poly(ethene) sheeting is available from garden centres or

hardware stores. High density poly(ethene) can be cut from food containers
such as large plastic milk bottles or'tupperware'. In general, high density
poly(ethene) is stiffer and more opaque. LDPE feels smoother than HDPE.

The softening tests can be performed safely by holding the samples or

placing them in hot but not boiling water.
It is possible to distinguish high density poly(ethene) from poly(propene) by
the hot glass rod test: the hot rod pulls a thread from poly(propene), but not
from poly(ethene).
1. HDPE is virtually unbranched and is therefore highly crystalline. It
also has greater tensile strength (the strands can become closely
entangled to create good intermolecular bonds), rigidity and a higher
melting point.

2. • No
• The chains are more closely packed in HDPE leading to stronger
intermolecular forces.
• Catalyst has to be purchased to make HDPE. It becomes embedded
in the polymer and is not recoverable. Demand for a higher quality
product.
• Excellent electrical insulation properties and has almost no
tendency to absorb electrical signals.

A2.3 The depolymerlsatlon of poly{ethene)

Observations for Part 4
Gas burns with yellowish flame. There may be a 'pop'.

Smells sweet/sickly
Bromine water is decolorised.

1:rl
Answers to Part 5
• Gas/solid; smell/no smell; decolorises bromine water

• Insoluble in water, burns, decolorises bromine water

• Examples: ethyne, propene, other unsaturated hydrocarbons

•
H H
I I
H-C-C-H
I I
Br Br

A2.4 Some properties of expanded poly(ethene)

Quantities of plastazote foam can be obtained from suppliers in appendix 3.

Answers

1. • The cells are pentagon shaped.

• The cells are unconnected.
• Plastazote foam is a closed cell cross-linked foam.

2. • Does not allow moisture through; good heat insulator; lightweight

for carrying; good cushioning performance.
• Closed cells keep gas in so heat is retained; highly energy
absorbent.

3. Nitrogen filling in the cells; poly(ethene) itself.

Note: Uses which involve naked flame or temperatures above 120°C

(the approximate melting poing ofplastazote) are not
acceptable.

4. The energy absorbent properties and cushioning performance make it

an ideal material for use as dampers to absorb any internal or external
physical vibrations in hifi music systems.

138
A2.S An example of addition polymerlsatlon
Safutynote The activity must be carried out in a fume cupboard.

Comments

Questions related to f

• Monomer is unsaturated; polymer is saturated. The success of the

bromine test depends on polymerising all the styrene .

• On heating it forms RCOO radicals which decompose rapidly to R

radicals which initiate the chain reaction.

A2.6 Blowing agents and expanded poly(phenylethene)

Poly(phenylethene) beads are available in many different sizes and

incorporating many different blowing agents. For this activity it is
important not to use flame-retardant beads since these contain toxic volatile
chemicals.

A ready source of the beads is in the kit What a gas!'. The kit also includes
moulds and full details of activity A2.6 and the scientific background. It is
obtainable from:
The Chemical Industry Education Centre
Department of Chemistry
University of York
York YOl 5DD Tel.(0904)432523.

Answers
2. a) Displayed formulas for butane and 2-methylpropane
Displayed formulas for two of pentane, 2-methylbutane
2,2-dimethylpropane

a-t3CHCH 3CH 3
2-m ethylpropane

a-t3CH2CH2CH2CH3 a-t3CI-!CH3CH2CH3 a-t3C(CH3b

pentane 2-methylbutane 2,2-dimethylpropane

b) The more compact molecules will pack closer (higher mp) and
tangle less than the zig-zag linear molecules (lower bp).

l~
 c) Low mp, and bp above room temperature ensures that they will be
liquid under normal handling, delivery and storage conditions.

d) Pentane is more likely to escape because it has long slim molecules

whereas 2-methylbutane is bulkier.

e) 2-Methylbutane condenses. Water vapour may get in and condense.

Air also gets in.

f) 2-Methylbutane, water vapour and air.

A2.7 Some properties and uses of plastic foams

Answers
2. a) Increase the pre-foaming time. Place fewer pre-foamed beads into
the mould.

b) The lower the density, the greater the savings on material costs.

c) The cells crumple and concertina. The pressure of the air inside
the cells helps to resist the crushing force of an impact. If the force
is great enough, the cell walls rupture and collapse.

d) More dense expanded poly(phenylethene) is better at absorbing the

energy of more violent impacts. The cell walls would be thicker and
could withstand greater forces.

3. a) It is composed of millions of air-containing closed

poly(phenylethene) 'cells which make the material able to cope with
high mechanical loads both in the long and short term.

b) Because of the light mass it is easy to handle and use by the

construction workers. Road foundations can therefore be laid very
quickly.

c) Sheets of high density poly(ethene) (HDPE) can be used to cover the

poly(phenylethene) blocks prior to applying the road surface to
protect them from attack by petrol and oil.

140
8.3 Activities In Section 3

A3.1 The preparation of a methanal resin

The warnings on the students' sheet must be strictly observed. Carbamide
vapour is an irritant to all and can be especially dangerous to those with
asthma.

The experiment must be carried out in a fume cupboard in the absence of

any hydrogen chloride. Gloves are essential as phenol can seriously affect
the skin.

The principal hazard is the extremely exothermic nature of the reaction.

Students must use tongs or stand the boiling tube in a rack, from the
moment of adding the sulphuric acid, until the tube cools down.

Answers
1f) • White solid, hissing, tube got very hot.
• Stuck in solid resin.
• Condensation.
• To remove (or eliminate) the water formed during the condensation
reaction and help reaction to completion.
• White powdery/waxy solid.
• Amount of heat given out; having to use batch rather than
continuous process.
• Compression moulding: powder is packed into mould of
appropriate shape and heated under pressure.

A3.2 The preparation of another methanal resin

The experiment must be carried out in a fume cupboard in the absence of

any hydrogen chloride. Gloves are essential as phenol can seriously affect
the skin.
Very little heat is given out so there is less hazard than in A3.1.

Answers
1d)· Some heat given out on mixing the reagents.
• Syrupy/waxy dark layer in tube.
• Under reflux - to prevent reactants and products boiling off when
they are being heated. They condense back into reaction mixture.
Water is removed - to prevent droplets of water in the final product.
Bubbles in plastic/final moulded product might be made brittle by
such imperfections.
In an oven - this heating results in 'curing' i.e. cross-linking of the
linear polymer chains to give a rigid thermoset.

141
A3.3 Hazards of burning plastics
1. a) CO from any (with possible exception ofPTFE)
HCN from polyurethanes, poly(propenonitrile ) (see Section 5)
Hydrogen chloride from PVC.
b) CO forms when a carbon compound burns in limited supply of air.
In a house fire, with windows and doors closed, oxygen quickly
becomes used up.
2. a) Produces highly flammable, toxic products on combustion.
b) Fire retardants added to foam (at manufacturing stage) and to
upholstery. Foamed poly(ethene) instead of polyurethanes to avoid
HCN emission.
Good labelling to indicate fire hazard e.g. safe to smouldering
cigarette; flame retardant; non-flammable.
c) Read labels on upholstery carefully. Make sure cigarettes are out.
Put spark guard up at night. Instal smoke detectors.

8.4 Activities In Section 4

A4.1 The effect of temperature on natural rubber

1. • Natural rubber becomes soft and sticky when warm and hard and
brittle in the cold. This is because the Tm is about 320 K and Tg is
about 273 K. This limits the commercial use of natural rubber.

• As the rubber approaches the Tg the chains can move relative to

each other and so the material becomes soft, and eventually will
melt at the Tm. The crystalline areas will then break down entirely
resulting in the formation of a viscous fluid.

• The strip is stretched in the first place to pull the polymer chains
into line.

A4.2 Synthetic and natural rubbers

• geometrical isomerism is possible.

2. •

142
 • The table in section 4.3 summarises the characteristics of natural
and synthetic rubber. This could be used as a starting point for the
discussion.

• During the World Wars, it became very difficult to transport

natural rubber from countries such as Malaya to the industrialised
nations so synthetic materials had to be developed as an alternative.

8.S Activities In Section S

AS.1 The Discovery of rayon

1. a) Too flammable
b) In the Chardonnet method poisonous H2S is produced, but in the
Viscose method, there is no flammable intermediate and the
reactants are regenerated and can be recovered.
c) Chardonnet converted nitrocellulose to cellulose using NaSH
Nitrocellulose as extruded fibres reduced by NaSH
o-x
/
s=c + H30+
\
S-Na+

x- ON02 + NaSH + H20

d) Squeezing or forcing solution through tiny holes.

AS.2 Preparing a small quantity of rayon

If). Cell ulose.

• Although CuC03 is "insoluble", there is always an equilibrium

between the solid in suspension and a few ions in solution. In the
presence of concentrated NH3(aq) the equilibrium towards the
complex copper am mine allows more CuC03 to dissolve.

CuC03 (s)

1 tfi3 (aq)

[Cu(NH 3)4]2+ (aq)

tetramminecopper(lI) ion

• Cellulose forms a soluble complex with the tetraammine copper

ion.

• The rayon is not soluble in the acidified water.

• Shimmery, silky, brittle; by spinning.

143
AS.3 Making a nylon

Safety notes
(i) Decanedioyl chloride is corrosive and toxic and is a powerful
irritant to the eyes. It should be handled in a fume cupboard.
(ii) 1,1,1-trichloroethane is still available and its use as a solvent in
school laboratories is still permitted. (Some safety myths in
science, P Borrows, SSR 74 (June 1993) p.52).

Ie) •

• nylon 6,10

AS.4 Isomerism of a polyester

Benzene-l,2-dicarboxylic acid may be supplied as phthalic acid; benzene-
1,4-dicarboxylic acid may be supplied as terephthalic acid. Both are
available from either BDH Chemicals or Aldrich Chemical Company.

Silicone oil is expensive and propane-l,2,3-triol (glycerol) provides a

satisfactory material.

Safetynote The experiment must be performed in a fume cupboard. The

oil bath must be securely supported so that it cannot be upset.

Comments
1d)· The contents of tube 1 remain viscous and tacky and then may set to
a hard glass-like resin.

• The polymer in tube 2 should set to a hard brittle opaque solid.

Water boils off during the heating stage.

144
 •
(yCOOH
¢
COOH COOH

COOH

benzene-1,2-dicarboxylic acid benzene-1,4-dicarboxylic acic

• The polymer chains in tube 1 have a zig-zag shape, whereas the

chains in tube 2 are linear.

polymer chains
in tube 1

polymer chains
in tube 2

o 0
II II
~ representsa -C-O-CH2-CH2-O-C- group

• Polymer in tube 2 has a higher melting point because the linear

chains can align and pack more closely and there is greater dipole-
dipole interaction between the carbonyl groups.

AS.S Development of Kevlar

1.

2.

3. 1,4-benzenedicarboxylic acid; 1,4-diaminobenzene.

4. a) covalent
b) amide link.

145
5. Nylons, wool, silk.

6.
H
I

b-~-rq
-N

C-
o"
7. The chain alignment in Kevlar is more regular, allowing stronger
intermolecular bonds to form.

8. Kevlar becomes protonated and the interchain hydrogen bonding is

disrupted.

AS.6 Comparison of dyes and fabrics

The Home Economics or Technology department may have books about
fibres and fabrics, dyes and dyeing. Students should find useful
information about natural (usually plant) dyes and appropriate mordants
in the library. Commercial dyes have a bit of information concerning their
use on and inside the packet. A particularly useful reference source is
Salters'Advamced Chemistry, Colours by Design, Heinemann Educational
(1994).

AS.7 Textile fabrics and dyes

1. a) Disperse.

b) Direct, disperse.

c) Reactive, disperse.

2. Disperse; because the polymer contains no reactive or polar groups to

bond with the reactive groups in the other dyes.

3 a) Wool, silk, cellulose, flax, linen.

b) Amide, amide, ether, ether, ether (or carbohydrate).

c) Acid dyes for wool and silk because the carboxylic or sulphuric
acids bind to the >N-H groups in the fibres.
d) Direct or reactive dyes for cellulose fibres because the S03 - and N a+
bonds with -OH groups in the fibres.

4. Evenness of dyeing.
Fastness to washing with cold or hot water and detergents.
Fastness to light.
Colour.

146
8.6 Activities In Section 6

Because of the complex nature of composite materials and the

impracticability of carrying out many experiments in the school/college
laboratory, this section has been set out in a different form from that of the
preceding sections. After a brief formal introduction there are three
extended DARTs (Directed Activity Related to Text) related to familiar
products of composite technology. Parts of the questions involve a
knowledge of post-16 organic and physical chemistry covered during the
second year of a 2-year course. These exercises might, therefore, be found
particularly suitable for revision towards the end of the course.

AS.1 Dental Composites

ALTERNATIVE CFCs Answers

1. a) i) propenoic acid
ii) trans-but-2-en-l,4-dioic acid
iii) methyl2-methylpropenoate
b) i) fumaric acid (trans butenedioic acid)
ii) Two identical functional groups which can be situated one
on each C atom of the carbon-carbon double bond either on
the same side (cis) or on opposite sides (trans).

iii)
H H
\ I
c=c
I \
HOOC COOH

maleic acid or cis-butenedioic acid

iv) The trans isomer since carboxyl groups will then be

initially on opposite sides of the molecule - less steric
hindrance

2. a) The carbon-carbon double bond consists of a a(sigma) bond and a x

(pi) bond.
b) The m-bond
c) Addition

147
3. A free-radical mechanism

Initiation

20-<
o
0-< >-0
o 0

0-0 O·

Propagation

CsHs- a-f2-
.
a-f2 + H2C= a-f2 CsHs- a-f2- a-f2- a-f2-
.
a-f2

and etc.

4. For every mole of ethene polymerised:

For every 1 C = C (+ 610 kJ) disrupted, 2 moles C-C (-700 kJ) are
formed giving -90kJ mole? ethene polymerised, giving a negative
Il H value.

5. alb Polymer (1) because each repeating unit has two-C02H groups
which can form hydrogen bonds with other chains thus producing
strong cross-linkages although not as strong as covalently bonded
cross-linkages. Polymer (2) will be unable to do this as it has only
-C02CH3 and -CH3groups, neither of which can form hydrogen
bonds.

-c
\ ",
I
~c, H
o 0

~O
I
c
o~ 'c---
I'

148
6. a) A photo-initiator is a molecule which when irradiated with the
appropriate electromagnetic radiation produces free radicals which
help to start polymerisation.

b) Light with a wavelength of 470 nm is in the blue region of the

visible spectrum

c) u _ ~ _ 3 x lOS = 0.00638 X 1017S-1

- A - 470 x 10-9

= 6.38 X 1014 S-1

d) Infra-red radiation has a longer wavelength, lower frequency and

the energy is too small to initiate the polymerisation reaction by
breaking bonds in the initiator.

7. a) An ester.

b)

AS.2 Use of two polymers but not a composltet

1. Generally used to replace glass.

2.

isotactic

\I CN, co 2H, or CONH 2

o C

o H
syndiotactic

atactic

149
3. a) Acrylic polymer is very transparent allowing disc to be visible and
it is resistant to chemical attack. Because of its high tensile
strength, the disc remains flexible and is less likely to crack.

b) The quality of sound is better.

CDs are less easily damaged.

4. a)

670-770 K
2-3atm

b)

100
8.7 Activities in Section 7

A7.1 Investigation of a plastic which dissolves In water

Poly(ethenol) is available from

Aldrich Chemical Co Ltd

The Old Brickyard
New Road
Gillingham
Dorset SP8 4JL Tele No. 01747 822211

Information is also available from:

Aquafilm Ltd
Unit 229
Ikon Trading Estate
Droitwich Road
Hartlebury
Worcestershire DY10 4EU Tele No. 01299 251335

A7.2 Consideration of photodegradable polymers

1. Farminglland use, e.g. poly(ethene) covering crops, mulch.

Some packaging, e.g. the film holding 6 pack cans together.

2. Photodegradable polymers would not be appropriate for products with

long term outdoor use, e.g. drain pipes, insulating wires, etc.

3. Nothing will happen to the polymer if light is excluded.

A7.3 Investigating the recycling of plastics

1. • Will depend on locality - need to look at collection and sorting

procedures.

• i) Curb-side collection with the domestic user sorting.

ii) Bins at suitable locations, e.g. supermarkets for people to dump
rubbish in appropriate containers.

• Some plastics can be identified and separated mechanically using

say differences in density, but most are separated by hand.

The plastics have to be shredded first. Very light plastics can be

'blown' off the rest, then adding the plastics to a series of solutions
of increasing densities and soaping off the floaters can help sort the
rest. Fillers and additives however make this inaccurate as they
change the density of the polymer.

151
2. This is an open-ended question. Students will design a range of
systems. The teacher must look for simplicity and logic.

• Additional journeys to collection points can use up energy. In

Germany where no plastics are burnt, fuel has to be added to the
incinerators to ensure complete combustion of other domestic
waste. In the past, the proportion of plastics in domestic waste
meant the additional fuel was not needed.

Efficient incineration can lead to the recycling of heat, however,

inefficient incinerators can lead to undesirable compounds being
released into the atmosphere.

Land-fill is becoming scarce and polymers do not degrade in these

sites.

A7.4 Investigating Blopol

1.
°II OH
I
HO- c- CH2- CH- CH3

3-hydroxybutanoic acid

3-hydroxypentanoic acid

2.

t.
f
3
o
~-?-?-o
H CH

H H n

3." PHB is a polyester formed by a condensation reaction.

4. PHB-V is a co-polymerofPHB, and is another polyester.

5. PHB-V is stronger and more flexible than PHB.
6. Biopol, is related to natural polyesters produced when bacteria die.
Other organisms metabolise the polymers as a source of carbon and
energy. In aerobic conditions Biopol and methane are produced in the
first stage. The Biopolthen fully biodegrades to CO2 + H20.

152
 Appendix 1

Polymers in Domestic Products

The following product types may be made from the named polymers:
High density poly(ethene}
Plastic bottles for: milk, fruit juices, household cleaners and chemicals.
Motor oil containers. Some carrier bags. Most aerosol caps.
Low density poly(ethene}
Jif lemon juice container. Some squeezy containers for sauces and
cosmetics.
Plastic films - shrink wrap, sacks, freezer bags, carrier bags that are
not crinkly.
Some aerosol caps. Some plant pots. Ink-tubes in ball-point pens.
Poly(chloroethene}
Plastic bottles for mineral water, fruit squash, cooking oil and shampoo.
Sandwich and cake packs. Food packaging trays. DIY blister packs.
Baby care product containers. Stretch film (cling film).
Ring-binder covers, records, watch straps, baby pants.
Weather boards, guttering, electrical conduits. Window frames.
Flooring, hosepipes. Wire and cable insulation. Electrical fittings.
Poly(phenylethene}
Yoghurt pots, margarine tubs, clear egg cartons, food packaging trays.
Ferrero Rocher chocolate boxes. Plastic cutlery and cups.
Clear 'plastic' glasses.
Ball-point pen cases, cassette boxes, plastic coathangers.
Expanded Poly(phenylethene}
Fast food packaging. Meat packaging trays. Egg cartons.
Protective packaging for fragile electronic goods.
Poly(propene}
Plastic straws. Containers for soft cheeses and fats.
Some margarine tubs.
Microwavable food tubs (for custard etc) and trays.
Plastic basins for steamed puddings. Clear plastic jars for pickled
onions.
Film bags for crisps, biscuits and snacks. Ketchup bottles. Bottle caps.
Brush sets. Kitchen ware. Picnic ware. Laboratory ware. Syringes.
Stacking chairs, garden furniture, plant pots, luggage cases.
Poly(ethene benzene-1,4-dlcarboxylate}
Most plastic bottles for fizzy drinks (some are polycarbonate).
Ovenable food trays and roasting bags. Bag-in-wine box. Audio and
video tape.
Insulation fibres in clothing. Coffee makers and toasters.
Society of Plastics Industry (SPI) Identity marks
Containers may be marked with identity codes:
I-PETE, 2-HDPE, 3-V, 4-LDPE, 5-PP, 6-PS, 7-OTHER

153
 Appendix 2

Polymers: Names, densities, Tg, T m

be
co C,O
.S ~ t- 0 0 10 0 0
1"""'4 1"""'4
0') 0') 0') 1"""'4
~ C\1 ~ 0') 10 ~ co
~'a 0
I
0
I
0
I
~
I
~
I
~
1"""'4
r-4
co
1"""'4
r-4
~
I
0
C\1
r-4
~
I
~
I
~
I
~
I
00
~r-4
C\1
10
r-4
C'i
I
0') 1"""'4 10 C\1 't- co ~C\1 C\1 00 0
00 0') 0') ~ 1"""'4 1"""'4 C\1 co co 1"""'4

~~ 0 0 0 ~ ~ ~ ~ ~ ~ ~ C'i

~ gs 1"""'4
~
ur
1"""'4

"1 ~
~
~ ~ ~ ~ ~ l ~ ~ '? ~ ~ ~ ~ ~

~ ~
~~ ~ ~ § ~ ~ ~ ~ ~ ~ ~ ~
•.•.....

~
1"""'4

=
1~
~j ~
f5: f5:
9 @ f£
§)
C,O

~ ~
C,O
C,O
-e
~
~
Po!
0
Po!
<:
0 ft
0
:>
Po! f5:
E-4 ~
~ ~
~

~
i
a,)
- Cl)
.+0)
a:s

I --
0
s:I

-
Cl)
p..
Q) 0
.~ Q)
s:I
s:I f..4
p..
•.....• ~ •..
I

•.....•
1 -
Cl) Q)
•.....•

-
..d ~Q)
Q)
..d .+0) ~
..d
1"""'4
I a:s a:s
.+0) Cl) .+0)
(1)
.+0)
Cl) s:I s:I ..d
'-" Cl) •.....• Cl) s:I tTj tTj .+0)
~

-
(1)
'-" •.....• s:I Cl) tTj
tTj s:I Cl) ..d ..d
e
(1)
~ ~
•.....• (1)
..d S 0
s:I N .+0)
.+0)

£
0
p.. I s:I Cl)
..d s:I_ (1)
0 .+0) C,O C\1 Cl) tTj tTj (1)
p.. 0
(1)
~ Cl)
•.....• cD •.....•
I
.+0)
..d ..d .+0) (1) (1)
,..c.+o)
S S ::s
t e
C,O tTj .+0) Cl)
s:I ~ .+0)
~ ~ .+0) Q) ~ I
~
'..-1
..d s:I Q) s:I ••..••• I
Cl)
c,
Q) .+0) Cl)
~f..4
j
rn s:I Cl) Cl) Q) "tj
',-4
rf
0
S s:I
e
"tj "tj .+0)
rn s:I Q) Cl) 0
•.....• (1)~ '..-1

s~
'..-1 '..-1
..d tn ',-4
r5
.+0)
s:I Q)
•.....•I S
e
(1)
p.. Cl) '"C ~ S tTj 0
•.....• 0 ~~ ~
(1)
.+0)
~ ~ ::s ~f..4
rf
"tj
'-" ..d '-" '-" C) s:I '-" •.....• '-"
~
•.....• b.O ~
•.....• ~
•.....• ~
•.....• ~
•.....• ~
•.....• •.....•
•.....• Cl) ~
•.....• ~tTj
.......C) ~
~ ..d "0
&;a
(1)
0
p.. 0
•.....•
'..-1
..d 0
p.. 0
c, e,
0 0
p.. 0
p.. Q) 0
p.. EI ~C) p..
C) ~

a,)

I6
Q)
Q) .+0)
Cl) s:I ~
•.....•
s:I •.....•
Q)
~ Q)
Q)
~ ..d s:I
..d .+0)
•.....•
(1)
..d
~.+0) .+0)
~
Cl)
~ ~ .s (1) ~ ..d
•.....•
s
Cl) (1) .+0)

.s
'"C
~
•.....• 0
rn
c,
Q)
.~ f..4
~ (1) 0 ~ s:I
',-4
rn
Cl)
tTj
.+0)
0 f..4
0 s:I p.. CIl rn
f..4
.+0) •.....•
~ ~ ~ ..d (1) 0
::s
t •.....•
(1)
.0 .+0)
'..-1
(1) ~ Cl)
s:I ~ C) s:I CIl
~ ',-4 CIl s:I f..4 ~rn rI.l Cl)
•.....• Q)
~
p.. rI.l s:I (1)
Q)
C,O (1) C)
~ ~ s:I ~f..4
0 s:I Cl) .+0) eo C,O••.
C) ~ rI.l
•.....•
',-4
s:I ..d ',-4

~
f..4 Q)
'"C
'"C ~rI.l rn
(1) s:I s:I •.....•
'..-1
~
0
•.....•
::s
0
s:I .~
.+0) EI CIl
.+0)

~ ~ ..d
~ ~
•.....• 0 0
•.....• ~ ~
•.....• •.....•
•.....•
(1)
~
tTj
•.....• tIj
~
•.....• •.....• f..4 •.....• •.....•
1a
b.O Cl) (1)
~
£ <: rf
~ ..d (1) f..4
& & 0
&
'..-1 C) (1)
0
•.....• ..d Po! Z 0 Po! ~ ~

151
 Appendix 3

Suppliers of plastazote foam

Bury Cooper Whitehead Ltd Rubber Astics & Co Ltd
Hudcar Mills Old Park Road
Bury Wednesbury
Lancashire BL9 6HD West Midlands WS10 9LR

0161-764-2262 0121-5564271
0161-797-1459 (FAX) 0121-502-2562 (FAX)

Kaymar Rubber & Plastics Ltd Vitapac Limited

Stanmore Industrial Estate Colinslee Works
Bridgenorth Neilston Road
Shropshire Paisley PA2 6QL

01746-761343 0141-884-7555
01746-767059 (FAX) 0141-884-8256 (FAX)

Plasmar Ltd Bury Cooper Whitehead Ltd

N eachells Lane (Hemisphere)
Wednesfield Trio Works
Wolverhampton 65 Fairview Road
West Midlands WV11 3QG Norbury
London SW16 5PX
01902-307711
01902-305201 (FAX) 0181-679-2126
0181-679-0454 (FAX)
S J Gaskets Ltd
Tything Road Paulamar Company
Arden Forest Industrial Estate Woodilee Industrial Estate
Kinwarton, Alcdester Woodilee Road
Warwickshire B49 6EP Kirkintilloch G66 3TU

01789-763721 0141-776-258819
01789-764070 (FAX) 0141-777-81019FAX)

Declarmink Ltd Polyformes Ltd

Trinity Court Cherrycourt Way
BruneI Road Stanbridge Road
Totton Leighton Buzzard
Southampton Beds LU7 8UH
Hampshire S04 3WX
01525-852444
01525-850484 (FAX)
01703-666432
01703-666433 (FAX)

Kewell Converters Ltd

60A Holmethorpe Avenue
Redhill
Surrey RH1 2NL

01737-771710
01737 769732 (FAX)

155
 Appendix 4

SOURCES

We used a variety of sources for the information in this book, many of which
are the standard texts for the subject. They include:
ComprehensivePolymer Science, Editors G. Allen, J.C. Bevington, Pergamon Press,
Elsevier, 1990
Chemistry for the Future, J. Alper & G. L. Nelson, American Chemical Society,
1989
Moulding Machines and Moulds for Plastic Processing, Negri Bossi
Handbook, 1987
Polymers & Plastics in School Teaching, University of Wales Institute of
Science & Technology, 1983
Synthetic Rubber - The story of an industry, International Institute of
Synthetic Rubber Producers, U.S.A., 1973
Teachers Guidance "Polymers" option, Notes and experiment scripts, J.M.B.
Advanced Chemistry, Alternative syllabus A
Teachers Notes for Guidance - Chemistry 9250 - Polymers, University of
Cambridge Local Examinations Syndicate
Textbook of polymer science (3rd edition), F.W. Billmeyer Jr, John Wiley and
Sons Inc, 1984
Biopol, Biopolymers Group, ICI Biological Products, Cleveland
Plastics Materials; Properties & Applications, A. N. Birley, R.J. Heath, J.M.
Scott, Blackie, 1988
Polymer Handbook, J. Brandrup, E.H. Immergut, Interscience, 1975
Keep Britain Tidy, Brighton Polytechnic, Group Schools Research Project, 1984
The Polymer Revolution, Chemical Stories, Salters' Advanced Chemistry, W.G.
Burton, J.S. Holman, G.M. Pilling, D.J. Waddington, Heinemann, 1994
Polymer Chemistry - An Introduction, G. Challa, Ellis Horwood, 1993
Polymers: Chemistry and Physics of Modern Materials, J.M.G. Cowie, Blackie
Academic and Professional, 1991
Tomorrow's Materials, K Easterling, Institute of Materials, 1988
Polymer chemistry an introduction, Garraher Jnr., Seymour, R.B. Dekker, 1992
Recycling Cities, T. Hilton, Chemical Industry Education Centre, University of
York, 1992
What a Gas, T. Hilton, Chemical Industry Education Centre, University of
York, 1993
The Essential Chemical Industry, E. Hubbard, Chemical Industry Education
Centre, University of York, 1989 .
Man-made fibres, R.W. Moncrieff, Heywood, 1963
High performance polymers and their origin and development, E. Raymond, B.
Seymour, P. Kirshenbaum, S. Gerald, Elsevier Science Publishing Co. Inc,1984

100