17 Polymerisation Notes 2021 PDF

9
22 Mass spectrometry
deduce the molecular mass of an organic molecule from the molecular ion peak in a mass
spectrum
deduce the number of carbon atoms in a compound using the M+1 peak
deduce the presence of bromine and chlorine atoms in a compound using the M+2 peak
suggest the identity of molecules formed by simple fragmentation in a given mass

spectrum
Polymerisation 
Polymerisation
Bilal Hameed Polymerisation

b) interpret gas / liquid chromatograms in terms of the percentage
composition of a mixture
10
22.2 Infra-red a) analyse an infra-red spectrum of a simple molecule to identify functional
spectroscopy groups (see the Data Booklet for the functional groups required)
22.3 Mass spectrometry a) deduce the molecular mass of an organic molecule from the
molecular ion peak in a mass spectrum
b) deduce the number of carbon atoms in a compound using the M+1
peak
c) deduce the presence of bromine and chlorine atoms in a compound
using the M+2 peak
d) suggest the identity of molecules formed by simple fragmentation
in a given mass spectrum
22.4 Carbon-13 NMR a) analyse a carbon-13 NMR spectrum of a simple molecule to deduce:
spectroscopy (i) the different environments of the carbon atoms present
(ii) the possible structures for the molecule
b) predict the number of peaks in a carbon-13 NMR spectrum for a
given molecule
22.5 Proton (1H) NMR a) analyse and interpret a proton (1H) NMR spectrum of a simple
spectroscopy molecule to deduce:
(i) the different types of proton present using chemical shift values
(ii) the relative numbers of each type of proton present from
relative peak areas
(iii) the number of equivalent protons on the carbon atom adjacent
to the one to which the given proton is attached from the
splitting pattern, using the n + 1 rule
(iv) the possible structures for the molecule
b) predict the chemical shifts and splitting patterns of the protons in a
given molecule
c) describe the use of tetramethylsilane, TMS, as the standard for
chemical shift measurements
d) state the need for deuterated solvents, e.g. CDCl3, when obtaining
an NMR spectrum
e) describe the identification of O–H and N–H protons by proton
exchange using D2O
44 www.cie.org.uk/alevel Back to contents page
Polymerisation Bilal Hameed

9 Condensation polymers (AHL)
29.1 Condensation polymers
1 11
amino acids
Hint H
H O H O
nderstandings
—
—
—
—
—
When an amide linkage is formed
—
Applications and skills
N —A—C + N —C—B—C
between amino acids, it is often
—
—
17. 1 two
Condensation Polymerisation
H OH H H OH
called a peptide link.
Condensation polymers require functional
amide (peptide)
➔ Distinguishing
H O
between addition and 2
linkage
groups onSynoptic
each monomer.
link Condensation polymerisation H involves O a H condensation
H
condensation
O reaction between two
polymers.
—
types of monomer. A small molecule, usually
N — C —H OCor HCl,
+ H Ois eliminated from
—
—
—
—
—
Amino acids are covered in Topic B2—
NH3, HCl, 30.1,
andIntroduction
H2O are possible products of H N —A—C— 2
H Completion
—
andbetween
descriptions of equations to
—
between two monomer molecules. In the
➔process, aOHbond forms the
—
to amino acids.
condensation reactions. two monomers. Each monomer has a reactive group at both ends of its
show how condensation polymers are formed.
a dipeptide
molecule, so a chain can form.

O O O O
Kevlar® isC —aA polyamide with a strong There
and (one a diamine, H N➔X Deduction
is a difference between a polymer like Nylon-6,6 (where there are
—
—
—
—
—
—
—
—
—C —O—B—O—C—A—C two monomers of the structures of polyamides and

NH and one a dicarboxylic 2 2
ordered ▲structure. The

Figure 8 The repeat unit hydrogen
is inThe two mainbonds
types of condensation polymer are polyesters and polyamides.
acid, HOOC Y COOH)) and a polypeptide (where each amino acid
monomer has one –NH group and one –COOH polyesters from their respective monomers.
group, H NCHRCOOH).
2 2
betweenbrackets
O and N can be broken with
There the
are use
20 naturally of
occurring varieties of amino acids.
Condensation polymerisation can sometimes be reversed by hydrolysis. The
Study tip ➔ Explanation of Kevlar’s strength and its
concentrated sulfuric acid. condensation polymerthe
Identifying is heated
repeatforunit
a long
of atime with aqueous
condensation acid or alkali.
polymer
It is important that you can deduce The repeat unit of a condensation polymer solubility in concentrated
is found by starting at any sulfuric acid.
the monomers from which a point in the polymer and stopping when the same pattern of atoms
polymer is formed and deduce begins again (Figure 8).
the repeating unit in each type of
Identifying the monomer(s) of a condensation
Nature of science
polymer.
polymer
The best way to work out the monomer(s) in a condensation polymer
Speculation – we have had
Intermolecular forcesthe Stone Age,
is to try and Bronze
recognise the links formedis
bythe Age
familiar of Polymers,
functional groups as science continues to
Age, and IroninAge. 17. 2 that
Is it possible
condensation Condensation
today’s age Polymerisation
(Table 1).
manipulate matter for desired purposes?
polymers ▼ Table 1 Condensation polymers – the repeat unit is inside the bracket
The intermolecular forces Monomer 1 Monomer 2 Polymer
between condensation polymers
O O
can be quite strong. In nylon, for O O
HO — B — OH
—
—
—
—
—
—
—
—
example, hydrogen bonds can HO — C — A — C — OH

diol — C — A — C — O — B — O —n
form between the C=O and N–H
groups as shown. This allows
the polymer chains to align and
Condensation polymerization
dicarboxylic acid
O O H H O O H H
—
—
—
—
—
—
—
—
Condensation polymers are—formed

C — A — C — Nby aNreaction that joins monomers
—
attract one another thus forming HO — C — A — C — OHH—N—B—N—H —B— —n

strong fibres. dicarboxylic acid diamine
O H O H O
and also produces H
small molecules as a condensation product. The
N N O
=
formation of an ester from an alcohol and a carboxylic acid (sub-topic 10.2)

=
N N N O H H
—
—
—
=
H
=
H O O H
—
—
—
—
O H O
H O HO — C — C — N — H
N
is an example of a condensation—reaction: C—C—N—
as well as the ester, water
=
N N N N
=
H O H O H
—
R
O H O H O
R n
is formedamino as
acidthe condensation product. In condensation polymerization,
=
=
N N N N N
=
H O H O H
many
1 Startmonomers are joined by condensation reactions to form the polymer.
with the repeat unit.
2 Break the linkage (at the C O for a polyester or C N for a
For two monomers to be joined by condensation polymerization they
polyamide).
3 Add back the components of water for each ester or amide link.
must each contain two functional groups, for example, a dicarboxylic
acid and a diol:
464 17. 3 Polyesters
Polyesters contain
O ester linkages
O formed between the alcohol and carboxylic
acid/or acyl chloride functional groups.
HO C R C OH + HO R´́ OH
A polyester has the ester linkage
a dicarboxylic acid –COO– repeatedaover
diol and over again.
O O
C R C O R´́ O
n
a polyester
In the polyester product shown the carboxyl group on the left can react
with a further alcohol molecule and the hydroxyl group on the right can
react with a further carboxylic acid molecule, and so the polymer chain can
continue to grow.
Bilal Hameed Marginalizer

carboxylic acid alcohol ester water Specification referenc
R—C + HO — R′ R—C + H 2O
—
—
CondensationOH
polymers are normally madeO — R′
from two different
monomers, each
carboxylic acid of which
12
alcohol has two functional
2 ester groups. Both functional
water
groups can react, forming long-chain polymers.
Condensation polymers are normally made from two different
Polyesters, polyamides,
monomers, and polypeptides
each of which aregroups.
has two functional all examples of
Both functional
condensation
17. 4 Polyesters
groups canpolymers (Figure
react, forming 1). polymers.
long-chain
Polyesters, polyamides, and polypeptides are all examples of
Polyesters
To make a polyester
condensation diols are
polymers used, which
(Figure 1). have two –OH groups, and
dicarboxylic acids, which have two carboxylic acid, –COOH, groups:
A polyester has the ester linkage –COO– repeated over and over again.
Polyesters
A andaBpolyester
To make represent unspecified
diols are organic
used,groups,
which often –(CH
have 2)n– .–OH
two The functional
groups,
A polyester
groups on thehas the
ends ofester
each linkage
molecule–COO–
react torepeated over
form a chain. and over again. and
dicarboxylic acids, which have two carboxylic acid, –COOH, groups:
To make a polyester diols are used, which have two –OH groups, and
dicarboxylic acids, which have two carboxylic
O acid, –COOH,
O groups:
—
— —
—
HO — A — OH O C — B — CO
—
—
—
— —
—
HO — A — OH
HO C — B — C OH
—
HO OH
diol dicarboxylic acid
diol dicarboxylic acid
A andABand
represent unspecified
B represent unspecifiedorganic groups,often
organic groups, often –(CH
–(CH )n. The
–
)n.2The
2–
functional groups on the ends of each molecule react to form
functional groups on the ends of each molecule react to form a chain. a chain.
For example, diols
For example, and
diols dicarboxylic
and dicarboxylic acids reacttogether
acids react together to give
to give a a
polyester
polyester by eliminating
by eliminating molecules of
molecules of water
water(Figure
(Figure2).2).
17. 5 Polyesters ▲ Figure
▲1Figure
Examples of p
1 Exa
polyamides (nylon)
O O O O polyamides (nyl
O O O O
—
—
——
—
—
—
—
—
—
—
—
—
—
—
HO — A — OH HO — C — B — C — OH HO — A — OH HO — C — B — C — OH
HO — A — diol
OH HO — Cdicarboxylic
— B — C —acidOH HO — A — OH HO — C — B — C — OH
diol
diol dicarboxylic acid diol
H2O H2O H2O
H2O H2O H2O
O O O O
—
—
—
—
—
—
—
—
— O — A — OO
—C—B—OC — O — A — O — C O
— B — C —O
polyester
—
—
—
—
—
—
—
—
—O—A—O—C—B—C—O—A—O—C—B—C—
▲ Figure 2 Making a polyester
polyester
▲ Figure 2 Making a polyester
17. 6 Polyesters: Terylene (PET)

Terylene® (or PET, polyethylene terephthalate) is a common polyester used in
synthetic fibres and in containers for food and beverages. It is one of the most
important raw materials of synthetic fibres.
TeryleneLet
made from
us look atbenzene-1,4-dicarboxylic
a specific example: acid and ethane-1,2-diol.
Marginalizer Bilal Hameed

The polymer chain as a whole can be represented by the unit shown
in brackets in the equation. This is called the repeat unit or repeating
Polymerisation unit of the polymer. The whole polymer chain could be built up by just Bilal Hameed
joining these units together:
−OH groups
● or monomers which have both a carboxylic acid group and an −OH group.
The repeating units in the polyester chains are linked by a series of ester
bonds.
13
The most common polyester is Terylene, used widely in3fabrics. It is usually
referred to simply as ‘polyester’. Terylene is made by condensation reactions
between benzene-1,4-dicarboxylic acid and ethane-1,2-diol (Figure 6.10). The
traditional names for these two compounds are terephthalic acid and ethylene
glycol – hence the commercial name, Terylene. An alternative name for the
17. 7 terephthalate,
polymer is polyethylene Polyesters: whichTerylene (PET)
gives rise to the name PET
when the same polymer is used to make plastic bottles for drinks.
O O O O
C C C C
HO OH HO OH
HO CH2 CH2 OH HO CH2 CH2 OH
O O O O
C C O CH2 CH2 O C C O CH2 CH2 OH
HO
+ H2O + H2O + H2O
The condensation reactions shown in Figure 6.10 can be repeated again and Figure 6.10 !
again to produce a polymer with the repeat unit shown in Figure 6.11. Condensation polymerisation to produce
the polyester Terylene.
O O
HO C C O CH2 CH2 O H
Figure 6.11 "
17. 8 Polyesters:
repeat unitTerylene (PET)
n The repeat unit and structure of Terylene.
Polyesters have high tensile strength and, because of this, they are widely used
as fibres in clothing and as the bonding resin in glass fibre plastics.
Perhaps the most important development in polyester chemistry in recent
years concerns poly(2-hydroxypropanoic acid), commonly called poly(lactic
acid) or PLA. Poly(lactic acid) is possibly the most useful and most versatile
of the new biodegradable plastics. It is already used in such diverse goods as
67
plant pots, disposable nappies and absorbable surgical sutures (stitches).
17. 9 Polyesters: Properties & Uses

Polyesters have high tensile strength, especially when cold-drawn to form
fibres.
Polyester fibre is often used as a substitute for cotton: it is cheaper

than cotton and does not crease so easily.
Polyester is also used as a plastic, for example in PETE plastic bottles.
Some types of polyester form cross-links, which makes them very hard.
The bonding resin in glass fibre reinforced plastic is a cross-linked polyester.

c Cl CH3 Cl CH3
CH CH CH CH
CH2 CH2 CH2 CH2
14 4
Worked example 2
The following are sections of addition polymers. Draw the monomer(s) from which they are
17.formed.
10 Type 2 Polymers
28 Addition and condensation polymers
a pCH2¬CH(CN)¬CH2¬CH(CN)¬CH2p
Starts
b pwith two different
CH2¬C(CN) monomers,
“ CH¬CH(CN)¬CH2¬C(CN) “ CH¬CH(CN)¬CH2
p
Answer
one containing monomers,
two carboxylic acid groups or two acyl chloride groups,
The second strategy, forming type II polymers, starts with two different
a CH2 “ CH(CN) one containing two carboxylic acid groups or two acyl chloride
b CH2 “ C(CN)¬CH “ CH(CN)
groups, and the other containing two alcohol groups or two amine groups (see
and the other containing
Figure 28.8).two alcohol groups.
Figure 28.8 Formation of type II

condensation polymers
Now try this
O O O
nHO
Suggest the monomer(s)
OH nHO C
from which theCO
following
H
–nH2polymers
O have been made.
2 2
C C
1 2
O
a diol a dicarboxylic acid a polyester
NH NH O
–nHCI
NH2 NH2 nCICO COCI
C C
O
a diamine a diacyl chloride a polyamide

17.There
11 areType
twothe 1 Polymers
The two types of polymer differ in the direction of successive functional groups along
strategies
chain. Infor making
type condensation
I polymers, polymers.
the direction Eachorstrategy
of each ester resultsis in
amide linkage thea same
different type (see Figure 28.9a), whereas in type II polymers, the direction of the ester or amide
of polymer.
startsThe
withfirst
a monomer containing
linkagesproducing
strategy, alternates (see two
typeFigure different functional
28.9b). starts
I polymers, groupscontaining
with a monomer that can
condense together to form either
thatester or amide groups.
Table 28.2 lists some common condensation polymers. The different nylons
two
28_08different
Cam/Chem functional
AS&A2 groups can condense together to form either ester or
(polyamides) are named according to the number of carbon atoms contained within
amide groups (see Figure 28.7).
Barking Dog Art each monomer: the first number is the number of carbon atoms in the diamine, and
the second is the number of carbon atoms in the diacid.
Figure 28.7 Formation of type I O
condensation polymers Polymers –nH2O
nHO ester
Figure 28.9 The orientation of adjacent a CO2H O C OO
linkages in a a type I polyester and b a type II
polyester Poly(lactic acid) is O
manufactured
by the Ccondensation
C polymerisation of a
O
single monomer which contains both a carboxylic acid group, −COOH, and
O C
a hydroxy acid an alcohol group, −OH (Figure 6.13).
a polyester O
O C CH3 O CH3 O
O CO O
C lactic acid
–nH2O HO C C + HO C C monomers
nH2N CO2H O HNC O C O
H OH H OH
C C O HN C
CH3 O CH3 O
an amino
b acid a polyamide
Polymers O C C O HO C C O C C + H2O
O O O OH
17. 12 Type 1 Polymers
H H
Poly(lactic acid) is manufactured by the condensation polymerisation
C of aC many more reactions at
28_07 Cam/Chem AS&A2 O C
single monomer which contains both a carboxylic acid Ogroup, −COOH, and each end of the molecule
O O O
474 an alcohol group, −OH (Figure
Barking Dog6.13).
Art
CH3 CH3
C CH3 OC
O O
Figure 6.12 !
lactic acid O
H O C C OH
HO The
C blazer,
C tie,+shirtHO and trousers
C C that this monomers
181333_28_A_Chem_BP_469-494.indd 474 schoolboy is wearing may all contain 09/10/14 2:07 AM
polyester
H OH
(Terylene). The fabrics
H OH
are hard H
n
wearing, washable and relatively cheap.
Figure 6.13 !
The synthesis of poly(lactic acid) by condensation polymerisation.
CH3 O CH3 O
28_09 Cam/Chem AS&A2 Polyamides 475
HO C C O C C + H2O
Polyamides are polymers in which the monomers are linked by an amide
Barking Dog Art
OH bond. This is exactly the same as the amide bond in proteins, in which it is
H H
181333_28_A_Chem_BP_469-494.indd 475
usually called the peptide bond (Figure 6.14). So,09/10/14
proteins and polypeptides
2:07 AM
Omany more reactions at are naturally occurring polyamides.
each end of the molecule Earlier work in Topic 5 showed that polypeptides and proteins are
C N
synthesised in living things by condensation reactions between amino acids.
CH3 O H In these reactions, the amine group, −NH2, of one amino acid reacts with the
Figure 6.12 ! carboxylic acid group, −COOH, of another amino acid to split out water and
H O C peptide
C OH
The blazer, tie, shirt and trousers that this form an amide link (Figure 5.5).
schoolboy is wearing may all contain bond
This process is then repeated time after time to produce a polymer (protein)
polyester (Terylene). The fabrics are hard Figure 6.14 !H
n with tens, hundreds or, in some cases, thousands of units.
wearing, washable and relatively cheap. The amide bond is usually called the The first synthetic and commercially important polyamides were various forms
Figure 6.13 !
peptide bond in proteins.
The synthesis of poly(lactic acid) by condensation polymerisation. of nylon. However, these were not produced from amino acids. Instead, they
were formed by condensation polymerisation between diamines and
Polyamides dicarboxylic acids. One of the commonest forms of nylon is nylon-6,6. This is
Polyamides are polymers in which the monomers are linked by anmade amideby a condensation reaction between 1,6-diaminohexane and
bond. This isMarginalizer
exactly the same as the amide bond in proteins, in which hexanedioic
it is acid (Figure 6.15). The product
BilalisHameed
called nylon-6,6 because both
monomers contain six carbon atoms.
usually called the peptide bond (Figure 6.14). So, proteins and polypeptides
O are naturally occurring polyamides.
Figure 6.15 " O
Earlier work in Topic 5Condensation
showed that polypeptides and proteins are O H H O O H
C N
Polymerisation synthesised in living things by condensation
polymerisation to makereactions between
C (CHamino
2)4 Cacids. N (CH2)6 N C (CH2)Bilal
4 C Hameed N (CH2)6 NH2
H In these reactions, the amine group, −NH2, of one amino acid reacts with the
nylon-6,6.
HO OH H H HO OH H
carboxylic acid group, −COOH, of another amino acid to split out water and
peptide
form an amide link (Figure 5.5).
bond
This process is then repeated time after time to produce a polymer (protein)
5 15
17. 13 Skill Check
39 Draw two repeat units of the polymer formed when the following molecules react:
40 From which monomers could the following polymers be formed?

a
Given a polymer chain, the repeat unit may be generated:
b
17. 14 Generating Repeat Units From Polyesters
Given a polymer chain, the repeat unit may be generated:
An amide may be formed when a carboxylic acid is heated with an amine. This is not a very good method for
As an amine is a base and a carboxylic acid is an acid, the initial reaction making amides, and they are more
is an acid–base reaction to form a salt. Upon strong heating, this is then usually prepared by reacting an acyl
converted slowly to an amide. Overall the general reaction is: chloride or acid anhydride with an
amine.
heat
amine + carboxylic acid amide + water
For example:
To work out the monomers from a polymer chain the following

17. 15procedure
Generating
is followed: Monomers From Polyesters
The amide functional group is:

procedure is followed:
This is a condensation reaction, as water is eliminated when the
two molecules are added together. The reaction is equivalent to the
esterification reaction shown previously. A nitrogen atom is joined directly
to C=O.

procedure is followed:
16 6
17. 16 Generating Monomers From Polyesters
39 Draw two repeat units of the polymer formed when the following molecules react:
17. 17 Skill Check

Draw the structure of the monomer or monomers that would be used to
40 From which monomers could the following polymers
prepare the polymer.
be formed?
a
b units of the polymer formed when the following molecules react:

39 Draw two repeat
17. 18 Skill Check

Draw the structure of the monomer or monomers that would be used to
40 From which monomers could the following polymers be formed?
prepare the polymer.
a An amide may be formed when a carboxylic acid is heated with an amine. This is not
As an amine is a base and a carboxylic acid is an acid, the initial reaction making am
is an acid–base reaction to form a salt. Upon strong heating, this is then usually prep
converted slowly to an amide. Overall the general reaction is: chloride or
b amine.
heat
For example:
An amide may be formed when a carboxylic acid is heated with an amine. This is not a very good method forThe am
As an amine is a base and a carboxylic acid is an acid, the initial reaction making amides, and they are more
is an acid–baseMarginalizer
reaction to form a salt. Upon strong heating, this is then Bilal Hameed
usually prepared by reacting an acyl
converted slowly to an amide. Overall the general reaction is: chloride or acid anhydride with an
Polymerisation amine. Bilal Hameed
heat
This isacid
amine + carboxylic a condensation reaction, as water is eliminated when the
amide + water
For example:
two molecules are added together. The reaction is equivalent to the
7 17H
O N N
40 From which monomers
H could the following polymers be formed? H
Oa N
17. 19 Skill Check
N O
H H
Draw the structure of
O the monomer or monomers
O that would
N be used to N
prepare the polymer. H H
b
O N N O
H
O
Figure 18.2.29 Polymer chains in Kevlar.
Tip
An amideThemay
longer
bethe carbonwhen
formed chainsa carboxylic
in nylons theacid
lessisthe material
heated withabsorbs water. Early
an amine. This is not a very good method for
As an amine is a base and a carboxylic acid is an acid, the initial reaction but they
versions of nylon shirts were very popular as they did not need ironing, left
making amides, and they are more
the wearer
is an acid–base damp and
reaction sweaty
to form as the
a salt. material
Upon strongdidheating,
not absorb
thisperspiration
is then as well as
usually prepared by reacting an acyl
natural
converted fibres.
slowly Modern
to an amide.shirts usingthe
Overall mixtures
general of reaction
different polymers
is: and natural fibres
chloride or acid anhydride with an
have generally solved this problem. amine.
heat
17. 20 Skill Check
Test yourself
For example:
27 a) What type of polymerisation would produce the polymer with a
repeat unit like that below?
O O
C CH2 CH2 C The amide functional group is:
O O
repeat unit
This is a condensation
b) Draw thereaction, as water
structure is eliminated
of the monomerwhen the
or monomers that would be
two molecules areusedadded together.the
to prepare Thepolymer.
reaction is equivalent to the
esterification reaction shown previously. A nitrogen atom is joined directly
28 The compound below can form a polymer.
to C=O.
O
C NH2
HO
17. 21 Polyamides
a) Identify the functional groups involved in forming the polymer.
b) What type of polymerisation will the monomer undergo?
Polyamides
c) What contain
otheramide linkages
product forms formed between the amine and carboxylic
during polymerisation?
acid/ord)acyl chloride functional groups.
Draw a short length of the polymer chain showing two repeat units.
This
29 amide
Statebond is exactly the
two similarities andsame
two as the amidebetween
differences bond in proteins.
the structure of
nylon-6,6 and the structure of a protein.
The first synthetic and commercially important polyamides were various
forms of nylon.
18.2.9 Condensation polymerisation 559
469983_18.2_Chem_Y1-2_541-567.indd 559 13/04/19 10:00 PM

HO C C + HO C C lactic acid
HO
OH C C + HO
OH C C monomers OH OH
H H monomers
H H
H OH H OH
H OH H OH
CH3 O CH3 CH3 O CH3 O

18 O
8 CH3 O
CH3 O
CH3
CH3 O
HO C C O C C + H2O O HO C C O C C +
HO C C O C C + H2O
HO C C OH O C C + H2O H OH
H H H
H H OH
H H at OH
many more reactions many more reaction
A general scheme for the polymerisation reaction showingmolecule
themore reactions at
17. 22 Polyamides
formation of the repeat unit is shown in Figure 10.28.
each end of themany
many more reactions at
each end of the molecule
each end of the mol
each end of the molecule
CH3 O CH3 O
Figure 6.12 ! Figure 6.12 ! CH3 O
CH3 O
The blazer, tie,Figure 6.12
shirt and trousers
! that this The blazer, tie,H shirt O C C thatOH
and trousers this H O C C OH
Figure 6.12 !
The blazer,
schoolboy is wearing may tie, shirt and trousers that this
all contain schoolboy is wearing may allHcontain O C C OH
The blazer, tie, shirt and trousers that this H O C C OH H
schoolboy
polyester (Terylene). is wearing
The fabrics are may
hard all contain H
polyester (Terylene). The fabrics are nhard n
schoolboy is wearing may all contain
polyester
wearing, washable (Terylene).
and relatively The fabrics are hard
cheap. wearing, washable and relatively cheap.H H n 6.13 !
polyester (Terylene). The fabrics are hard
Figure 6.13 ! Figure
n
wearing, washable and relatively cheap.
wearing, washable and relatively Thecheap.
synthesis Figure 6.13 !
of poly(lactic The synthesis of poly(lactic acid) by condensation polymerisation
acid) by condensation polymerisation.
Figure 6.13 !
Polyamides Polyamides
Polyamides
Polyamides are Polyamides
polymers in which the monomers are linked
Polyamides by an are polymers in which the monomers are linke
amide
bond. This isPolyamides
exactly the are
Polyamides same
are polymers
as the amide
polymers in
in which
whichbondthe
theinmonomers
bond. This
proteins,
monomers are
in islinked
arewhich
linked it by
exactly by an
an amide
is the same as the amide bond in protei
amide
usually calledbond. This
This is
the peptide
bond. exactly
isbond
exactly the
(Figure
the same
6.14).
same as
as the
So,
the amide
proteins
amide bond
usually
bond in
andcalled proteins,
polypeptides
in proteins, in
the peptide
in which
bondit
which is
it(Figure
is 6.14). So, proteins
O are naturally usually
occurring called theO peptide bond (Figure 6.14).
polyamides. So,
are naturally proteins and
occurring polypeptides
polyamides.
O
usually called the peptide bond (Figure 6.14). So, proteins and polypeptides
are
areinnaturally
Earlier work Topic 5 occurring
showed polyamides. Earlier work are in Topic 5 showed that polypeptides and pr
C N O naturally occurring
C Nthat polypeptides and proteins
polyamides.
synthesised in Earlier
Earlier work in Topic 55 showed
living work
things in
by Topic
condensation showed that
that polypeptides
reactions synthesised
between amino
polypeptides and
and proteins
in living
acids.things
proteins are
are by condensation reactions betw
C N
C N synthesised in group, −NH2, of one amino a
H In these reactions, the amine
synthesised in livinggroup,
living things
H −NHby
things condensation
2, condensation
by of one amino reactions
In these
acid reacts
reactions between
reactions, withthe
between theamino
amineacids.
amino acids.
H
H
In
carboxylic acid
In these
group,
these reactions,
−COOH,the
reactions, amine
of another
the amine amino−NH
group,
group, −NH ,, of
acidcarboxylic
2to of one
split
one amino
out acid
amino wateracid
group,
acidand −COOH,
reacts
reacts with
with the
of
theanother amino acid to
peptide carboxylic acid peptide−COOH, of another
group, 2
amino acid to split out water
form an amide link (Figure
carboxylic acid 5.5).
group, −COOH, of another form an amide
amino acid link
to split(Figure
out 5.5).and
water and
bond peptide bond
peptide form
This process
form an
is then amide
an6.14 repeated
amide link
linktime(Figure
(Figureafter5.5).
time to produce
5.5). This process (protein)
a polymer is then repeated time after time to produce
bond Figure
Figure 6.14 ! bond with tens, hundredsThis
This process
or, in
process
!some is
is then
cases,
then repeated
thousands
repeated time
time ofafter
units.
after time
with
time to
tens,
to produce
hundreds
produce aa polymer
or, in some
polymer (protein)
cases, thousands of units.
(protein)
Figure
The amide bond 6.14 called
is usually ! the The
with amide
tens, bond
hundreds is usually
or, incalled
some the
cases, thousands
The first of units.
synthetic and commercially important polyamide
Figure 6.14 ! The first synthetic
with and commercially
tens, hundreds or, important
in some polyamides
cases, thousands were
of various forms
units.
The
peptide bond in amide bond is usually called the
proteins. peptide
The bond in proteins.
of nylon.
The amide bond is usually called
An example
peptide bond in proteins.
the The first
of a However,
reaction first synthetic
these were not
synthetic
involving
and commercially
produced
andformation
the commercially important
from amino of nylon.
aimportant
ofproduced acids.
polyamide
polyamides
However,
Instead,
polyamides
is: acids.
were
these
they
were various
various forms
were not
forms produced from amino a
17. 23 Nylon-6,6
peptide bond in proteins. were formed byof
of nylon. However,
condensation
nylon. However, these
polymerisation
these were
were not
notbetween
producedwere from
diamines formed
from amino
andby condensation
amino acids. Instead,
Instead, they
polymerisation
they between diam
were
were formed
dicarboxylic acids. One ofby
formed bythecondensation
commonest forms
condensation polymerisation
of nylon
polymerisation isbetween
dicarboxylic
nylon-6,6.
between diamines
acids.
This
diaminesOne isand
of the commonest forms of nylon i
and
dicarboxylic
made by a condensation
dicarboxylicreactionacids.
acids. One One of
of the
between commonest
commonestmade
the1,6-diaminohexane forms
formsbyof anylon
ofand is
is nylon-6,6.
condensation
nylon nylon-6,6. This
reaction is
Thisbetween
is 1,6-diaminohex
Industrially, Nylon-6,6
hexanedioicis made
made
acid from
by
made(Figure
by 1,6-diaminohexane
aa condensation
6.15).
condensation reaction
The product andnylon-6,6
reactionis between
called
between hexane-1,6-
1,6-diaminohexane
hexanedioic acid (Figure
because
1,6-diaminohexane both and
and 6.15). The product is called
1,6-diaminohexane nylon
can also b
dicarboxylic acid: hexanedioic
monomers contain six carbon
hexanedioic acid (Figure
(Figure 6.15).
acid atoms. 6.15). The
The product
product is
is called
monomers nylon-6,6
calledcontain
nylon-6,6 six because
carbon both
atoms.
called
because hexane-1,6-diamine.
both
monomers contain six carbon atoms.
Figure 6.15 " O O Hmonomers
Figure 6.15contain" H sixOcarbonOatoms. O H O H H O O H
Condensation Figure 6.15 " O Condensation
O H H O O H
Figure 6.15 " (CH2)4O C O 2)6H to HC2)4O(CH ON H
polymerisationCondensation
to make C N (CH
polymerisation N make C (CH C 2)4 C N (CH 2)6
(CH
NH22)6 N C (CH2)4 C
Condensation C (CH ) C N (CH ) N C (CH ) C N (CH2)6 NH2
nylon-6,6. polymerisation to make 2 4nylon-6,6. 2 6 2 4
polymerisation to
HOmake (CH
C OH H )
2 4 C (CH )
N H HO2 6 HO
N (CH )
C OH H2 4OH C H N (CH )
2 6 H NH
HO2 OH H
nylon-6,6.
nylon-6,6. HO OH H H HO OH H
HO OH H H HO OH H
O O O OO O O O
O O O O
C (CH2)4O C N (CHO2)6 N C (CH2)4 OC C N (CH (CH)O) C NHN
2 42 6 2
(CH )
2 6 N C (CH2)4 C N (CH2)6
C (CH2)4 C N (CH2)6 N C (CH2)4 C N (CH2)6 NH2
HO C (CH2)4 C N (CH2)6 N C
HO (CH2)4 C N (CH2)6 NH2
H H H H H H
HO
68 HO + H O 68 H
H
+ H O
H
H + H O +
H
H
H O + H 2O + H2O
68 2 2 2 2
68 + H2O + H 2O + H2O
+ H2O + H 2O + H2O
Nylon-6,6 can be produced more readily in the laboratory using hexanedioyl
dichloride in place of the less reactive hexanedioic acid. A solution of
hexanedioyl
The repeat unitsdichloride in cyclohexane
and monomers is floated
for polyamides on an aqueous
may be worked out in solution of
1,6-diaminohexane.
basically Nylon-6,6
the same way as described forms474
on pages as and
a skin
475atforthe interface and can be
polyesters.
pulled out as fast as it is produced forming a long thread – the ‘nylon rope’
17. 24(Figure
Nylon-6,6
18.2.26).
In can
Nylon-6,6 thisbereaction
producedhydrogen chloride
more readily molecules
in the laboratory arehexanedioyl
using eliminated in the
condensation reaction (Figure 18.2.27).
dichloride in place of the less reactive hexanedioic acid.
O O H H
n Cl C(CH2)4C Cl + nH N(CH2)6N H
Figure 18.2.26 The nylon rope trick. O O H H
C(CH2)4C N(CH2)6N + 2nHCl

n
Figure 18.2.27 The reaction used to make nylon-6,6 in the laboratory.
Although nylon is similar in structure to wool and silk, it does not have the
softness of the natural fibres. It is, however, much harder wearing and one
of its earliest uses was as a substitute for silk in the manufacture of ladies’
stockings (Figure 18.2.28).
Apart from their obvious use in stockings and tights, nylon fibres are used in
Marginalizer
various forms of clothing. In fact, about 75% of the UK nylonBilal Hameed
consumption
goes on clothing, but its uses are many and varied. Nylon is used to make
nylon ropes that don’t rot, machine bearings that don’t wear out, and it is
Polymerisation mixed with wool to make durable carpets. Bilal Hameed
Nylon is the collective name for polymers with aliphatic hydrocarbon
sections linked by amide bonds. They are aliphatic polyamides in which the
made by a condensation reaction between 1,6-diaminohexane and
41 Copy and complete the table:
hexanedioic acid (Figure 6.15). The product is called nylon-6,6 because both
monomers contain six carbon atoms. Polymerisatio
Figure 6.15 " 9 19
O O H H O O H
Condensation
polymerisation to make C (CH2)4 C N (CH2)6 N C (CH2)4 C N (CH2)6 NH2
nylon-6,6.
Nylon
HO OH H Nylon-6,6 is H
Industrially, HO from 1,6-diaminohexane
made OH H and
17. 25 Nylon-6,6
hexane-1,6-dicarboxylic acid:
H H H H H
O O OH O O H H H H O
—
—
—
—
—
C (CH2)4 HC2N —NC — C(CH
— C) — C — C — C — NH2
2 6 N C (CH2)4 C NC —(CH
C — )C — C — C — C
2 6 NH2
—
—
—
—
—
HO H H H H H H HO H H H H OH
H H H
8 1,6-diaminohexane
+ H2O +H O 2 + H2hexane-1,6-dicarboxylic
O acid
O
H
= N
41 Copy and complete the table: N
=
H
O n
Nylon-6,6
In the
42 Name laboratory,
the following the reaction goes faster if a diacid chloride is used
amides:
rather than the dicarboxylic acid, and in this case hydrogen chloride
is eliminated. Nylon-6,10 is made from 1,6-diaminohexane and
decane-1,10-dicarboxylic acid. Many other nylons are made each
with slightly different properties.
17. 26 SkillKevlar
Check ▲ Figure 5 When 1-6-di
and hexane-1,6-dioyldich
Kevlar is made from benzene-1,4-diamine and
Draw two43repeat units
Write an for the polymer
equation for themade from the
formation afollowing monomers: Nylon-6,6 is formed at th
benzene-1,4-dicarboxylic acidof(Figure
polymer6).from the monomers shown.
demonstration was first p
Stephanie Kwolek who de
H H O O H H
—
—
—
—
—
—
—
N— —N + C— —C + N— —N
—
—
—
—
—
—
H H HO OH H H
44 Give the structures of the monomers that could be used to produce the polymer shown:
benzene-1,4-diamine benzene-1,4-dicarboxylic acid
42 Name the following amides:
H H O O H H
—
—
—
—
—
—
—
—N— —N—C— —C—N— —N—
Kevlar
43 Write an equation for 6theKevlar
▲ Figure formation of a polymer
is a polyamide. from the
Because monomers
the shown.
amide groups are linking rigid
benzene rings, Kevlar has very different properties to nylon ▲ Figure 7 Formula 1 dr
17. 27 Skill Check need to be lightweight as
Kevlar’s strength is due to the rigid chains and the ability of the flat it adds to a driver’s head,
Draw the structure of the monomer
aromatic rings toorpack
monomers
togetherthatheld
wouldbybestrong
used tointermolecular forces. the risk of whiplash injuri
prepare the polymer. the extreme G-forces exp
The polymer,
44 Give the structures developed
of the monomers in the
that could 1960s
be used by Stephanie
to produce Kwolek
the polymer shown:of the
accelerating and braking
DuPont company, is credited with saving some 3000 lives because
by racing drivers contain
of its use in bullet proof vests and anti-stab clothing as worn by the
is five times stronger tha
police. You may have Kevlar oven gloves at home.
for weight
Polypeptides and proteins

Hint
Polypeptides are also polyamides. They may be made from a single
amino acid monomer, or many different ones. Once a dipeptide is for
In a polypeptide, each amino acid has both an amine group and a tetra, and polypeptide
carboxylic acid group. So the amine group of one amino acid can by further reaction at
react with the carboxylic acid group of another. A molecule of water is the molecule.
eliminated and a condensation polymer can begin to form:

▲ Figure 8 The repeat unit is in monomer has one –NH2 group
O
brackets O
There are 20 naturally occurrin
C CH2 CH2 C
20 10
Study tip
O O
Identifying the repeat u
repeat unit
It is important that you can deduce The repeat unit of a condensa
b) Draw the structure of the monomer or monomers that would be
17. 28
used Skill Check
the monomers from which a
to prepare the polymer. point in the polymer and stop
polymer is formed and deduce
28 The compound below can form a polymer. begins again (Figure 8).
the repeating unit in each type of
O
polymer. Identifying the monom
C NH2
HO polymer
The best way to work out the
Intermolecular forces
a) Identify the functional groups involved in forming the polymer.
is to try and recognise the link
b) What type of polymerisation will the monomer undergo? (Table 1).
c) What other productinforms
condensation
during polymerisation?
d) polymers
Draw a short length of the polymer chain showing two repeat
▼units.
Table 1 Condensation polymers –
29 State two similarities and two differences between the structure of
Thestructure
nylon-6,6 and the intermolecular forces
of a protein. Monomer 1 M
between condensation polymers
O O
can be quite strong. In nylon, for HO
—
—
—
—
example, hydrogen bonds can HO —18.2.9
C — ACondensation
— C — OH polymerisat
17. 29 Intermolecular form betweenForces in Condensation
the C=O and N–H Polymers
dicarboxylic acid
There are hydrogengroups as shown.
bonds between This allows
the chains of polymers in polyamides due
O O H
to the presence
469983_18.2_Chem_Y1-2_541-567.indd 559of C=O bonds and N–H bonds.
the polymer chains to align and
—
—
—
—
attract one another thus forming
Polyesters have permanent dipole–dipole attractions between the polymer
HO — C — A — C — OH H—N
strong fibres.
chains due to the presence of the polar C=O bonds. dicarboxylic acid
O H O H O H
N N O
=
=
N N N
—
—
—
=
H
=
H O O H
O H O
H O HO — C — C — N — H
N
=
—
N N N N
=
H O H O H
O O O
R
H H
amino acid
=
=
N N N N N
=
H O H O H
Start with the repeat unit. 1

Break the linkage (at the C 2
polyamide).
17. 30 Intermolecular Forces in Condensation Polymers
3 Add back the components
There are greater forces of attraction between the polymer chains in
polyamides and polyesters compared to addition polymers, so polyamides
like nylon and Kevlar and polyesters like Terylene can be used to create
clothing. 464
The stronger forces of attraction between the polymer chains mean that the
fibres can be woven together or knit together.
Most addition polymers cannot be used to create clothing as there are only
weak van der Waals’ forces of attraction between the polymer chains.

condensation reactions.
Kevlar 21
11 is a para-aramid polymer (‘aramid’ is short for ‘aromatic amide’)
created by the reaction between 1,4-diaminobenzene and terephthaloyl
chloride (the diacyl chloride of benzene-1,4-dioic acid) (Figure C22).
The polymer chains align themselves in such a way that allows for An acyl
17. 31 Kevlar the formation of comparatively strong intermolecular hydrogen bonds structur
between amide groups (C=O to H–N) along the whole chain (Figure except
Kevlar is created by the reaction between 1,4-diaminobenzene
C23). Additional and the
intermolecular diacyl
interactions arise in the form of extensive replaced
chloride of benzene-1,4-dioic acid.van der Waals’ forces. These hold the polymer chains together very tightly in the f
and contribute to Kevlar’s high tensile strength. rather t
Kevlar
ture of aofpolymer
ructure a polymer clothin
sties
– e.g. atactic
– e.g. vs vs
atactic
As explored in Section C3 on page 12, the structure of a polymer synthet
yany
polymers
polymersformed by by
formed
has a significant impact on its physical properties – e.g. atactic vs equipm
isotactic polypropene. The same is true for many polymers formed by
condensation reactions.
t for for
hort ‘aromatic
‘aromaticamide’)
amide’) To crea
nzene
benzene andandterephthaloyl
terephthaloyl levels o
Kevlar is a para-aramid polymer (‘aramid’ is short for ‘aromatic amide’)
oic acid)
dioic (Figure
acid) C22).
(Figure C22). methan
a way
ch a waythatthat
allows for for
allows AnAn acylacyl created
chloride
chloride byhas
has athe reaction between 1,4-diaminobenzene and terephthaloyl
similar
a similar the mo
ecular hydrogen
molecular hydrogen bonds
bonds structure
structure chloride
to atocarboxylic (the
a carboxylic diacyl
acid,chloride of benzene-1,4-dioic acid) (Figure C22).
acid,
The polymer chains align themselves in such a way that allows for An acyl chloride has a similar is less th
17. 32 Kevlar
gethe
whole
whole chain (Figure
chain (Figure except
exceptthatthatthe OH
the OHgroup
grouphas been
has been
se in the
arise form
in the formof extensive
of extensive replaced
replaced the
with withaformation
Cl. This
a Cl. This ofmeans
means comparatively
thatthat strong intermolecular hydrogen bonds structure to a carboxylic acid, form. H
ains together very tightly in the between
formation
in the formation amide
of Kevlar, groups
HCl,
of Kevlar, HCl, (C=O In
to Kevlar,
H–N) intermolecular
along the whole forces
chain hold
(Figure the polymer
exceptchains together.
that the OH group As we
has been ratio ris
chains together very tightly
The
rather polymer
than
rather C23).
water,
than
chains
Additional
water,
align
is eliminated. themselves
intermolecular
is eliminated.
ininsuch
sawinteractionsa way
Figure C19,
arisethat
in inallows
the formfor
of the
phenol–methanal
extensive plasticsreplaced
there are
withcovalent
a Cl. Thisbonds,
means that inciden
th.
formation vanof dercomparatively
Waals’ forces. These strong intermolecular
called
hold hydrogen
cross-links,
the polymer chains bonds
between
together verybetween
chains. As covalentinbonds
tightly are much
the formation stronger
of Kevlar, HCl, higher
amide groups and contribute(C=O to toH–N)
Kevlar’s along the
highthan whole
tensile chain.
strength. rather than water,
intermolecular forces, cross-linked phenol–methanal is eliminated.
plastics are far mor
Kevlar
Kevlaris used
is used in protective
in protective
clothing, including armour,
harder and more rigid than Kevlar; hence their use in making items such resistan
clothing, including armour,
synthetic
synthetic ropesropes andandsporting
sporting as pool balls. Kevlar is used in protective
equipment.
equipment. clothing, including armour,
synthetic ropes and sporting
equipment.
To To create
createa polymer
a polymer with diffdiff
with eringering
levels of cross-linking,
levels of cross-linking, thethe
methanal
methanal : phenol
: phenol ratio is varied.
ratio is varied.If If To create a polymer with differing
thethemolar
molar ratio of methanal
ratio of methanal :phenol
:phenol levels of cross-linking, the
is less than
is less thanone, one,fewfewcross-links
cross-links methanal : phenol ratio is varied. If
form. However,
form. However, whenwhen thethe
molar
molar the molar ratio of methanal :phenol
er chains
ymer together.
chains As As
together. we we ratio rises
ratio to about
rises to about 1.5,1.5,
thethe is less than one, few cross-links
there areare
cs there covalent
covalentbonds,
bonds, incidence
incidence of cross-linking
of cross-linking is much
is much form. However, when the molar
bonds
nt bondsareare
much
muchstronger
stronger higher
higherandand theKevlar,
plastic
the produced
plastic produced is is forces hold the polymer chains together. As we
In intermolecular ratio rises to about 1.5, the
methanal plastics
ol–methanal areare
plastics far far
moremorerigid, thermostable
rigid, thermostable andinand
17. 33 Kevlar
saw in Figure C19, phenol–methanal plastics there are covalent bonds, incidence of cross-linking is much
use in making
ir use items
in making such
items such resistant tocalled
resistant chemicals.
to chemicals.
cross-links, between chains. As covalent bonds are much stronger higher and the plastic produced is
than intermolecular forces, cross-linked phenol–methanal H
plastics are far more rigid, thermostable and
harder and more rigid than Kevlar; hence their use in making items such resistant to chemicals.
O N N
as pool balls.
H H
O N N O
H H
O O N N
H H
O N N O
H
O
Figure 18.2.29 Polymer chains in Kevlar.
Tip
The longer the carbon chains in nylons the less the material absorbs water. Early
versions of nylon shirts were very popular as they did not need ironing, but they left
the wearer damp and sweaty as the material did not absorb perspiration as well as
natural fibres. Modern shirts using mixtures of different polymers and natural fibres
have generally solved this problem.
Test yourself
27 a) What type of polymerisation would produce the polymer with a
repeat unit like that below?
ers
2 Draw two repeat units of the polymer that could be formed from each
of the following monomers.
a) O b) CHCH2 c) O
22C Cl 12
C NH2
HO
17. 34 Kevlar
The flat, rigid benzene rings
OHmake the polymer chains in Kevlar very rigid.
The benzene rings also lead to extensive, strong van der Waals’ forces.
3 A section of a polymer is shown below:
Because of this, it is a very strong O
material; weight for weight
O five times
stronger than steel. C CH CH C2 2
O Kevlar is used O
in ropes, tyres, sports
O equipment and bullet-proof
O vests.
C CH2 CH2 C
O O
a) What type of polymerisation will produce the polymer above.

b) Identify the repeat unit in the polymer.
c) Identify the two monomers used to produce the polymer.
Polymers 17. 35 Hydrolysis

Hydrolysis
The ester link in of condensation
a polyester and the amide link polymers
in a polyamide are both polar
6.5
Theand
ester
The hydrolysis of polyesters and polyamides
arelink
subject
in atopolyester
acid-catalysed
and and
the base-catalysed
amide link in ahydrolysis.
polyamide are both
polarEsters
and are subject to
and polyesters acid-catalysed and base-catalysed hydrolysis.
In Topic 3, we found that an ester can be hydrolysed to form an acid and an
alcohol. Ester δ– Amide δ–
O O
link link
Figure 6.22 ! O δO+ δ–
The hydrolysis of a simple ester, ethyl C δ+ H C N
CH3 C +δ– H2O CH3 C + CH3CH2OH
ethanoate. +
O δ
O CH2CH3 OH H
Acid hydrolysis of a polyester results in theethanoic

ethyl ethanoate acid
formation of aethanol
diol and a dioic
acid:Both acids and alkalis can catalyse the hydrolysis. Hydrolysis catalysed by acid
is the reverse of the reaction
+
used to synthesise esters from carboxylic acids
Polyester + H2O H
and alcohols.
(aq) catalyst
→ Diol + Dioic acid
Base catalysis is generally more efficient because it is not reversible. This is
because the acid reacts with the base as soon as it is produced to form its
carboxylate salt, which does not react with the alcohol.
17.CH36 Hydrolysis− of Polyesters−
3COOH(aq) + OH (aq) → CH3COO (aq) + H2O(l)
ethanoic acid ethanoate
Polyesters can be hydrolysed in a similar way to simple esters forming 219
Polyesters can be hydrolysed in a similar way to simple esters forming products
products with carboxylic
with carboxylic acid and
acid and alcohol alcohol
groups groups.
(Figure 6.23).
Figure 6.23 !
CH3 O CH3 O
The hydrolysis of poly(lactic) acid.
H O C C + (n – 1)H2O nH O C C
H OH H OH
n
lactic acid
(2-hydroxypropanoic acid)
If the reaction is catalysed by an acid, the product is lactic acid

(2-hydroxypropanoic acid). If the reaction is catalysed by a base, the lactic
acid produced reacts with the base to form a salt.
HO−CH(CH3)−COOH(aq) + NaOH(aq)
→ HO−CH(CH3)−COONa(aq) + H2O(l)
Polyamides
In Topic 5, we found that peptides and proteins could by hydrolysed to form
amino acids, and that the hydrolysis was catalysed by both acids and bases.
However, when the reaction is catalysed by acid, H+ ions from the acid react
with −NH2 groups in the amino acids produced to form cations containing the
Marginalizer
−NH3+ group. Bilal Hameed
But, when the reaction is catalysed by base, ions such as OH− from the base
react with −COOH groups in the amino acids produced to form carboxylate
Polymerisation anions containing the −COO− group. Bilal Hameed
Polyamides which contain the amide group, C N , like proteins, are
hydrolysed in the same way.
The products are compounds containing O H
13 23
17. 37 Hydrolysis of Terylene

Polyester (terylene)
O O
C C + H 2O
O O CH2 CH2
H+(aq) catalyst
HO O
C C HO CH2 CH2 OH
O OH
Benzene-1,4-dioic acid Ethane-1,2-diol
Base hydrolysis of a polyester also forms a diol, but the dioic acid formed
then reacts with the base catalyst to form the dioate salt. The products of
refluxing Terylene® with an aqueous solution of NaOH(aq) are:
Na+ O– O
17. 38 Hydrolysis
C
of Polyamides
C and HO CH2 CH2 OH
– Na+
O O
Polyamides are hydrolysed in the same way. The products are compounds
Polyamides can also be hydrolysed:
containing carboxylic acid groups, −CO2H, and amine groups, −NH2.
● Acid-catalysed hydrolysis results in the formation of the dioic acid and
If the hydrolysis
the di-saltisof
catalysed by acid, the −NH2 groups are converted to
the diamine.
−NH●3 ;Base-catalysed
+ and if the reaction is catalysed
hydrolysis results by base,
in the the −COof2Hthe
formation groups areand
diamine
convertedthe to −COO
di-salt of −the dioic acid.
Hydrolysis of polyamides is summarised in the reaction scheme below.
O O
+ +
H3N (CH2)6 NH3 and HO C (CH2)4 C OH
Acid catalyst forms a
salt with the diamine
Acid hydrolysis
H H O O H H O O
N (CH2)6 N C (CH2)4 C N (CH2)6 N C (CH2)4 CH
17. 39 HydrolysisBase
Nylon-6,6
ofhydrolysis
Polyamides The development
O of degradable
O polymers
H2N (CH2)6 ONH2 andO –O C (CH2)4 C O–
N ( CH2 )6 N C ( CH2 )4 C Base catalyst forms a

salt with the dioic acid
H H n
Polyamides, such as nylon, and polyesters containing aromatic groups are
O + 2nH+ + 2nH2O + 2nOH–
fairly resistant+acid
2nH
tohydrolysis
2hydrolysis (Figure 11.7), unless the reaction is catalysed
base hydrolysis
by acid or base. But polyesters made from purely aliphatic monomers
H
hydrolyseH
slowly at pH 7 without acid or base catalysts. This has led to the
O O H H O O
+ use of poly(glycolic)
+ acid for stitching internal wounds. Once the stitches
nH N ((sutures)
CH2 )6 N N + n C ( CH2 )4 C
have been inserted and the surgical incision ( CH2 )6 Nthe+stitches
n N closed, n C ( CH2 )4 C
H dissolve H slowly in HO the patient’s OH tissue fluid. H H

–
O O–
+ 2nH2O
Figure 6.24 !
The hydrolysis of nylon-6,6 by acid and base.
Test yourself
10 A bottle made of poly(phenylethene) can be used to store dilute potassium
hydroxide, but holes gradually appear in a polyester lab coat which has soaked
up splashes of the same reagent. Account for the difference in the behaviour of
the two polymers.
11 Suggest a reason why many polyesters and polyamides are degradable while
poly(alkenes) are not.
12 a) Which type of plastic makes up most of the plastic waste from households –
condensation or addition polymers?
b) What are the implications of this when it comes to disposing of the waste?
13 Explain the difference between a co-polymer and a composite.
Bilal Hameed
14 Nylon-6 contains the repeat unit shown below. Marginalizer
H
N ( CH2 )5 C
O
Draw the structures of the products formed when it is hydrolysed by refluxing

with:
a) dilute hydrochloric acid
important polymers are made from monomers in which some o
atoms in ethene have been replaced by other atoms or groups.
their
24 uses, are
14 listed in Table 28.1.
Table 28.1 Structures and uses of some Monomer Polymer Use

addition polymers
17. 40 Addition Polymerisation
Addition
chloroethene
CH “ CHCl
polymerisation poly(chloroethene)
(polyvinylchloride,
of
PVC)
other et
gutt
win
Addition polymerisation involves adding together many alkene monomers to
2
form a long polymerderivatives
chain.
tetrafluoroethene poly(tetrafluoroethene) non
There is no loss of small
Most CF “ CF2when monomers
molecules
2compounds join, and (Tefl
containing the on,>CPTFE)
resulting
the bea
“ C< group will undergo
polymer contains repeating units 2-methylpropenoate
methyl joined by carbon–carbon single bonds, e.g.2-methylpropenoate) prot
poly(methyl
poly(ethene). Addition polymerisation of other ethe
important
CH2 “
polymers are made from monomers in which som
atoms inC(CH 3)COhave
ethene (Perspex) by other atoms or grou
2CH3 been replaced ligh
derivatives
methyl
their 2-cyanopropenoate
uses, are listed in Tablepoly(methyl
28.1. 2-cyanopropenoate) inst
CH2 “
Most C(CN)CO2CHcontaining
compounds 3 the >C “ C< group will undergo p
(cyanoacrylate)
Table 28.1 Structures and uses of some important polymers are made
cyanoethene from monomers in which some
poly(cyanoethene) co-po
Monomer Polymer U
addition polymers CH2 “in
atoms ethene have been replaced
CH¬CN (acrylic) by other atoms or groups.
com
chloroethene poly(chloroethene)
their uses, are listed in Table 28.1. g
fibre
CH2 “ CHCl (polyvinylchloride, PVC) w
Table 28.1 Structures and uses of some Worked
tetrafl
Monomer example 1
uoroethene poly(tetrafluoroethene)
Polymer Usen
addition polymers
17. 41 Skill Check
CF 2 “ CF
Draw two (Teflon, PTFE)
2 repeat units of the poly(chloroethene)
chloroethene polymer folb
formed from each of thegutt
Draw two repeat unitsmethyl
pair
CH
of “2-methylpropenoate
the2of monomers. poly(methyl
CHClformed from the following
polymer 2-methylpropenoate)
(polyvinylchloride,
monomer PVC) winp
CH 2 “ C(CH
atetrafl 3)CO2CH3
uoroethene (Perspex) uoroethene)
poly(tetrafl nonli
CH 2 “ CH¬OCOCH3
bCFCH2“
methyl2“
CFCCl¬CH
2-cyanopropenoate
2 “ CH2 (Tefl on, PTFE) 2-cyanopropenoate) beain
poly(methyl
c methyl
CH CH “2-methylpropenoate
2 “2C(CN)CO
CHCl and 3 2 “ CH¬CH
2CHCH (cyanoacrylate)
poly(methyl
3 2-methylpropenoate) prot
CH2 “ C(CH3)CO2CH3
cyanoethene (Perspex)
poly(cyanoethene) lighc
Answer
CHmethyl 2-cyanopropenoate
2 “ CH¬CN poly(methyl
(acrylic) 2-cyanopropenoate) instc
aCH “ CHC(CN)CO
2 CH2CH (cyanoacrylate)
2 2 3 fi
CH
cyanoethene CH poly(cyanoethene) co-p
Worked example
CH2 “ CH¬CN
OCOCH 1
3 OCOCH3
(acrylic) com
fibre
Draw two repeat units of the polymer formed from each of the
b Worked
pair Cl exampleCl1
of monomers.
17. 42 Skill Check CH2 “
a Draw twoCH¬OCOCH
C repeat
CHunits
2 CHpolymer
C3 of the 2 formed from each of the fol
b of
Draw two repeat units CH
pair “
the2of
CH CCl¬CH
monomers.
polymer “
CHCH
CH from
2 formed the CH
2 2following monomer
c CH2 “ CHCl and CH2 “ CH¬CH3
a CH2 “ CH¬OCOCH3
bc CH2 “Cl
Answer CH3“ CH
CCl¬CH Cl 2 CH3
a CH2 CH CHCH
2 CH CH
Answer
CH CH2 CH CH2
1333_28_A_Chem_BP_469-494.indd 473 CH
2 CH2
a CH2 CH2
OCOCH
CH 3 OCOCH
CH 3
OCOCH3 OCOCH3
b Cl Cl
b CCl CH2 CCl CH2

CH2 CH CH CH
C CH2 2C CH2
CH2 CH CH2 CH
c Cl CH3 Cl CH3
Polymerisation c Cl
CH CH3
CH Cl
CH CH
CH3 Bilal Hameed
CH2 CHCH2 CHCH2CH CH2CH
8_A_Chem_BP_469-494.indd 473
CH CH CH CH
CH2 CH CH2 CH
a CH2 CH2
c CH
Cl CH
CH 3
Cl CH3
15 25
CH
OCOCH CH CH CH
3 OCOCH3
CH2 CH2 CH2 CH2
C CHEMISTRY b Cl Cl
a CH2 CH2
17. 43C Skill

CH2Check
CH CH
C CH2 OCOCH3 OCOCH3
TheWorked example 2an addition polymer. Draw the monomer(s) from

CH CH CH CH
following is a section of
2 2 ORGANIC CHEMISTRY
b Cl Cl
which it is formed. C CH C CH 2 2
cThe following
Cl CHare
3 Clsections
CH3 of addition polymers. Draw the monomer(s) CH from
CH which
CH CH they are 2 2
formed.
CH CH CH CH c Cl CH3 Cl CH3
a pCH CH2 CH2 CH2 2¬CH(CN)¬CH2p

CH2 2¬CH(CN)¬CH CH CH CH CH
p
b CH2¬C(CN) “ CH¬CH(CN)¬CH2¬C(CN) “ CH¬CH(CN)¬CH2p
CH CH CH CH 2 2 2 2
Answer Worked example 2

Worked example 2 The following are sections of addition polymers. Draw the monomer(s) from which they are
a CH “ CH(CN)
2
The following 2
are sections of addition
b CH “ C(CN)¬CH “ CH(CN)
polymers. Draw the monomer(s) from which they are
formed.
a pCH2¬CH(CN)¬CH2¬CH(CN)¬CH2p
formed. b pCH ¬C(CN) “ CH¬CH(CN)¬CH ¬C(CN) “ CH¬CH(CN)¬CH p 2 2 2
a pCH2¬CH(CN)¬CH2¬CH(CN)¬CH2p Answer
b pCH2¬C(CN) “ CH¬CH(CN)¬CH2¬C(CN) “ CH¬CH(CN)¬CH2p a CH2 “ CH(CN) b CH2 “ C(CN)¬CH “ CH(CN)
Now try this
Answer
a Suggest the monomer(s) from which the following polymers have Now
beentry made.
this
CH “ CH(CN)
2 b CH “ C(CN)¬CH “ CH(CN) 2
Suggest the monomer(s) from which the following polymers have been made.
1 2
17. 44 Skill Check
1 2
Now try this

Suggest the monomer(s) from which the following polymer have been made.
1 2

There are two strategies for making condensation polymers. Each strategy results in a
different type of polymer.
The first strategy, producing type I polymers, starts with a monomer containing
two different functional groups that can condense together to form either ester or
28.2 Condensation polymers Figure 28.7 Formation of type I

condensation polymers
–nH2O
O
nHO CO2H O C O
O C
a hydroxy acid a polyester
The
There arefitwo
rst strategy, producing
strategies for type I polymers,
making condensation polymers.starts with a results
Each strategy monomer in a containing O
two different functional
different type of polymer. groups that can condense together to form either ester–nHorO 2
nH N CO H HN 2 2 C O
The fi rst strategy, producing type I polymers, starts with a monomer containing
HN C
mation of type I 17. 45 Dienes
amide groups (see Figure 28.7). Oan amino acid a polyamide
ymers
.7 Formation of type I –nH O O
on polymers When
nHOa diene undergoesCO
addition
2H polymerisation,
2
a double
O bond is still C O
present
nHO in the product.
CO2H
–nH2O
O C
28_07 Cam/Chem AS&A2
O
474 Barking Dog Art
O C
O C
a hydroxy acid 181333_28_A_Chem_BP_469-494.indd 474

a polyester 0
O O
–nH2O O
–nH2HN
nH2NN CO2HCO C
nH 2H HN C
2
O O
HN C
HN C
an amino acid a polyamide

Barking Dog Art

Bilal Hameed
Barking Dog Art Marginalizer
469-494.indd 474 09/10/14 2:07 AM

indd 474 09/10/14 2:07 AM
bubbled
Barkingthrough Rubber
Dog Artthe phenylethene as it–isnatural and synthetic
being polymerised, co-polymers
the familiar white, very
light, solid known as expanded polystyrene
The rubber is formed. This
tree is indigenous is used
to South as a protective
America, but large plantations have
packaging, and for sound and established in India and Malaysia. When its bark is stripped, it oozes a whit
heat insulation.
26 called 16
sticky liquid latex, which is an emulsion of rubber in water. Purificati
of this produces rubber. In its natural state, rubber is not particularly useful
has a low melting point, is sticky and has a low tensile strength. In 1839, Ch
Rubber – natural
17. 46 Rubber
and
Goodyear synthetic
discoveredco-polymers
the process of vulcanisation, which involves heating
The rubber tree is indigenousnaturaltorubber
Southwith sulfur.but
America, Thislarge
produces a substance
plantations with a higher melting
have been
Rubber is an addition polymer of 2-methylbutadiene.
established in India and Malaysia. When its bark is stripped, it oozes a white of 2-methylbutadien
and of greater strength. Rubber is an addition polymer
sticky liquid called latex,(isoprene)
which is an (seeemulsion
Figure 28.3).
of rubber in water. Purification
Figure 28.3 Isopreneof undergoes
polymerisation to form rubber.
addition
this produces rubber. InCH
Addition polymerisation of other ethe
H
its3 natural state,
has a low melting point, is sticky and
rubber is not particularly useful. It
has a low tensile strength. In 1839, Charles
C
derivatives
C or
Goodyear discovered the process of vulcanisation, which involves heating
natural rubber with sulfur. CH
This produces CH2a substance with a higher melting point
2
Most compounds containing the >C “ C< group will undergo p
isoprene
and of greater strength. Rubber important polymers are of
is an addition polymer 2-methylbutadiene
made from monomers in which some o
(2-methylbutadiene)
(isoprene) (see Figure 28.3).
atoms in ethene have been replaced by other atoms or groups.
e undergoes addition CH3 H
their uses, are listed in Table 28.1.
rm rubber.
C C or
Table 28.1 Structures and uses of some Monomer Polymer Use
addition polymers CH2 CH2
isoprene chloroethene poly(chloroethene) gutt
17. 47
(2-methylbutadiene) Rubber CH2 “ CHCl (polyvinylchloride, PVC) win
tetrafluoroethene poly(tetrafluoroethene) non
CF2 “ CF2 (Teflon,
rubber PTFE) bea
methyl 2-methylpropenoate poly(methyl 2-methylpropenoate) prot
Note that when a diene undergoes addition polymerisation, a double bond is st
CH2 “ C(CH3)CO2CH3 (Perspex) ligh
present in the product. This double bond may be cis or trans. In natural rubber
methyl
long chain is cis2-cyanopropenoate poly(methyl
across all the double bonds. 2-cyanopropenoate)
From different trees, a naturallyinsta
oc
28_03 CH
Cam/Chem 2 “ C(CN)CO
AS&A2 CH (cyanoacrylate)
substance called gutta percha can be obtained; this is an isomer of rubber in wh
2 3
Figure 28.4 A rubber tree being tapped. The
double
white latex is converted to rubber suitable for Barking bonds
Dog Art are trans. Gutta percha ispoly(cyanoethene)
cyanoethene harder than rubber, and in the 19thco-pcen
tyres by the process of vulcanisation. was usedCHas2 “
arubber
coating
CH¬CNfor golf balls. (acrylic) com
fibre
Note that when a diene undergoes addition polymerisation, a double bond is still
present in the product. This double Worked
bond may example
be cis or 1
trans. In natural rubber, the
long chain is cis across all the double bonds. From different trees, a naturally occurring
28_03 Cam/Chem AS&A2 Draw two repeat units of the polymer formed from each of the fol
er tree being tapped. The
81333_28_A_Chem_BP_469-494.indd
substance
471 17.gutta
called 48 percha
Skill Check
can be obtained; this is an isomer of rubber in which all
pair of monomers.
double
ted to rubber suitable for Barking Dogbonds
Art are trans. Gutta percha is harder than rubber, and in the 19th century
of vulcanisation. was used as a Draw two repeat
coating units
for golf of
a the
CHpolymer
balls. formed from the following monomer
2 “ CH¬OCOCH3
b CH2 “ CCl¬CH “ CH2
c CH2 “ CHCl and CH2 “ CH¬CH3 471
Answer
a CH2 CH2
471
CH CH 09/10/14 2:07 AM
OCOCH3 OCOCH3
b Cl Cl
C CH2 C CH2
CH2 CH CH2 CH

c Cl CH3 Cl CH3
Polymerisation CH CH CH CH Bilal Hameed
CH2 CH2 CH2 CH2

1333_28_A_Chem_BP_469-494.indd 473
a CH2 “ CH¬OCOCH3
CH2 “ CH¬CN (acrylic) components of ‘ac
fibres, ABS
17 27
Worked example 1
Answer
a Draw
CH2two CH
repeat
2 units of the polymer formed from each of the following monom
17. 49 2 Skill Check
a CH 2 CH
CH
pair ofCH
monomers.
CH
CH
Draw two repeat units of
a the
CHpolymer formed from the following monomer
“ CH¬OCOCH
OCOCH3 OCOCH32 OCOCH 3
3 OCOCH3
EMISTRY b Cl
Cl
b Cl Cl
C CH2 Answer
C CH2
CH2 CH CHa2 CHC
CH CH
CH
2 C CH2
2 2
CH2 CH
CH CH2CH CH
c Cl CH3 Cl CH3
a CH2 CH2 CH CH CH CH OCOCH3 OCOCH3

c Cl CH3 Cl CH3
CH CH CH CH2 CH2 CH2
2
OCOCH3 OCOCH3 CH CH CH CH
b Cl Cl
CH2 CH2 CH2 CH2
469-494.indd 473 b C CH2 C CH2
Cl
Worked
Cl
example 2
17. 50 Skill
CH2 Check
a CH2 CH2
C CH2 C
CHaddition
The following are sections of 2 CHpolymers.
CH2 Draw
CH the monomer(s) from which they are CH CH
CH2 CH CH2 CH OCOCH3 OCOCH3
The following is a section ORGANIC

formed. of an addition polymer. Draw the monomer(s) from
CHEMISTRY
which it is formed.
b Cl Cl
c Cl a 3 pCH
CH Cl 2¬CH(CN)¬CH
CH3 c 2 ¬CH(CN)¬CH
Cl
p
CH3 Cl CH CHCHCH3 C CH CH
2 C CH 2 2
b CHp ¬C(CN) “ CH¬CH(CN)¬CH2¬C(CN) “ CH¬CH(CN)¬CH2p 2 2
CH CH CH 2 CH
CH2 CH2 Answer
CH2 CH2 CH CH CH
c Cl
CH
CH 3 Cl CH3
CH CH CH CH
a CH2 “ CH(CN)
CH CH2 “
b CH2 “ 2C(CN)¬CH
CH 2 CH
CH
CH(CN)
CH
2
2 2 CH2 CH2
_BP_469-494.indd 473
Worked example 2 Worked example 2

formed.
formed. a pCH2¬CH(CN)¬CH2¬CH(CN)¬CH2p
Now try this b pCH2¬C(CN) “ CH¬CH(CN)¬CH2¬C(CN) “ CH¬CH(CN)¬CH2p
a pCH2¬CH(CN)¬CH2¬CH(CN)¬CH2p Answer
b pCH2¬C(CN) “
Suggest the monomer(s)
CH¬CH(CN)¬CH from
2¬C(CN) “ CH¬CH(CN)¬CH 2
p
which the following
a CH2 polymers
“ CH(CN) have
b CH been“ CH(CN)
2 “ C(CN)¬CH made.
Answer 1 2
Now try this
a CH2 “ CH(CN) b CH2 “ C(CN)¬CH “ CH(CN) Suggest the monomer(s) from which the following polymers have been made.
1 2
17. 51 Skill Check

Now try this
Q. Suggest the monomer(s) from which the following polymer has been
made.
1 2

Figure 28.7 Formation of type I O

There are two strategies for making
condensation polymers condensation polymers. Each –nH O
strategy results in a 2
nHO CO H O C 2 O
O C
two different functional groups that can condense together to form either ester Oor
amide groups (see Figure 28.7). nH N CO H
–nH O
HN C 2
There are two strategies for making condensation polymers. Each strategy results in a 2 2 O
different type of polymer. HN C
mation of type I The first strategy, producing type I polymers, starts with a monomer containing O
mers two different functional groups that can condense together
–nH2O to form either ester or
amide groups (see nHOFigure 28.7). CO2H O C O
pe I 474 O Barking Dog Art O C
–nH2O
nHO Bilal Hameed
CO2H O C O Marginalizer
a hydroxy acid
181333_28_A_Chem_BP_469-494.indd 474 a polyester 09/10/14 2:07 AM
O C
Bilal Hameed O Polymerisation
–nH2O
nH2N CO2H HN C O
O
ORGANIC CHEMISTRY
S
S
28 18
The presence of the double bond in rubber allows further addition reactions
S to take place. If liquid rubber is heated with sulfur, sulfur atoms add across some
S
17. 52 Co-Polymers
of the double bonds in different chains, cross-linking the rubber molecules (see
Figure 28.5). This is what happens during the vulcanisation process. It stops the
A co-polymer
chains from moving is formed when
past each twoand
other, or more
givesdifferent alkenes
the material arerigidity.
more polymerised
together.
S
S
S Even if the ratio of monomers is 50:50, there
S is no guarantee that the
monomer fragments will alternate along the chain. The order is fairly random
28.5 Vulcanisation of rubber (in contrast to condensation co-polymerisation).
05 Cam/Chem AS&A2 S Not all double bonds have sulfur added to them. That would make the substance too
S
hard. About 5% sulfur by mass is adequate to give the desired properties. Many millions
king Dog Art
of tonnes of vulcanised rubber are made each year for the manufacture of car tyres.
Synthetic rubber-like polymers were S
developed when rubber was in short supply
S during the Second World War. The one most commonly used today is a co-polymer
Figure 28.5 Vulcanisation of rubber
of phenylethene and butadiene, called SBR (styrene–butadiene rubber).
28_05 Cam/Chem AS&A2 NotAallco-polymer
double bonds have sulfur added
is formed whento them.
twoThat would make
or more the substance
different alkenestooare polymerised
hard. About 5% sulfur by mass is adequate to give the desired properties. Many millions
Barking Dog Art together. Even if the ratio of monomers is 50 : 50, there is no guarantee that the
of tonnes of vulcanised rubber are made each year for the manufacture of car tyres.
monomer fragments
Synthetic rubber-like will alternate
polymers alongwhen
were developed the chain. Theinorder
rubber was is fairly random (in
short supply
17.the53
contrast
during to Co-Polymers
condensation
Second World War. Theco-polymerisation
one most commonly–usedsee today
sections 28.2 and 28.3).
is a co-polymer
of phenylethene and butadiene, called SBR (styrene–butadiene rubber).
A co-polymer is formed when two or more different alkenes are polymerised
together. Even if the ratio of monomers is 50 : 50, there is no guarantee that the
monomer fragments will alternate along the chain. The order is fairly random (in
contrast to condensation co-polymerisation – see sections 28.2 and 28.3).
styrene butadiene SBR
n
The product
styrene SBR still contains a double SBR
butadiene bond, and so can be vulcanised just like
natural rubber.
TheAnother
product SBR still containsinvolving
co-polymer a double bond, and so can beand
phenylethene vulcanised just like
butadiene as reagents, along with
natural rubber.
acrylonitrile, is the tough, rigid plastic ABS, or acrylonitrile–butadiene–styrene:
Another co-polymer involving phenylethene and butadiene as reagents, along with
17. 54 Co-Polymers
acrylonitrile, is the tough, rigid plastic ABS, or acrylonitrile–butadiene–styrene:
CN
CN CN
CN
n n
phenylethene butadiene acrylonitrile ABS
phenylethene butadiene acrylonitrile ABS
Once again, the monomers join together in a fairly random manner, so the drawing
Once
of again,‘repeat
a particular the monomers
unit’ does notjoin together
imply a regular in a fairly
order. ABS israndom manner, so
the drawing
used for suitcases,
telephones and other objects that need to be strong and hard,
of a particular ‘repeat unit’ does not imply a regular order. but not too ABS
brittle.is used
for suitcases,
telephones and other objects that need to be strong and hard, but not too brittle.
472
_AS_Chem_BP_469-494.indd 472 Marginalizer Bilal Hameed

07/11/14 3:03 PM

BP_469-494.indd 472 07/11/1
2
their uses, are listed in Table 28.1. fibres, ABS
1 Structures and uses of some Worked

Monomer example
19 1 29 Polymer Uses
olymers
Draw two repeat units of the poly(chloroethene)
chloroethene polymer formed from each of theguttering,
followingwater pipes,
monomers
pair “monomers.
CH2of CHCl (polyvinylchloride, PVC) windows, floor covering
17. 55 Skill Check
atetrafl
CH2 “ uoroethene
CH¬OCOCH3 poly(tetrafluoroethene) non-stick cookware, bri
Draw two repeatbunits
CF
CH2 of
“the polymer
CFCCl¬CH
“ 2 formed
“ CHfrom the following
(Teflon,monomers
PTFE) bearings
2 2
CH2 “2-methylpropenoate
c methyl CHCl and CH2 “ CH¬CH
poly(methyl
3 2-methylpropenoate) protective ‘glass’, car re
CH2 “ C(CH3)CO2CH3 (Perspex) lights, shop signs
Answer
methyl 2-cyanopropenoate poly(methyl 2-cyanopropenoate) instant ‘superglue’
aCH “ CHC(CN)CO
2 CH2CH (cyanoacrylate)
2 2 3
CH
cyanoethene CH poly(cyanoethene) co-polymerised with
a 2 “ CH¬CN
CH CH2 CH2 (acrylic) components of ‘acrylic’
OCOCH3 OCOCH3
CH CH fibres, ABS
b Worked
Cl example 1
OCOCH3 Cl
OCOCH3
Draw two C repeat

CHunits CHpolymer
C of the formed from each of the following monomers
C CHEMISTRY pair
b ofCHmonomers.
Cl
2
Cl
2
CH CH2 CH
17. 56 Skill Check
2
a CH2 “ CH¬OCOCH
C CH2 3 C CH2
Draw two repeatbunits
CHof the polymer formed
“ CCl¬CH “ CHfrom the following monomers
c 2 Cl
CH2 CH CH3 CHCl 2 CH
CH3
2
CH CH CH CH
Answer
CH
69-494.indd 473 c 2 ClCH2 CH
CH2
3
CH2
Cl CH3
a CH2 CH2
CH CH CH CH
CH CH
CH2 CH2 CH2 CH2
OCOCH3 OCOCH3
b Cl Cl
Worked example 2
C 2 CH C CH
The following are sections of2 addition polymers. Draw the monomer(s) from wh
CH2 CH CH2 CH
17. 57 Polymer formed.
Properties
a inpproperties
Polymers vary widely CH2¬CH(CN)¬CH 2¬CH(CN)¬CH
such as tensile strength, flexibility and 2
p
c p Cl CH3 Cl CH3
b CH2¬C(CN) “ CH¬CH(CN)¬CH2¬C(CN) “ CH¬CH(CN)¬CH2p
softening temperature.
Some, such as polyester

Answer andCH CHstrongCH
nylon, are and notCH
easily stretched, and
are therefore suitable forCH
use2 as fibres.
CH2 CH2 CH2
69-494.indd 473
a CH “ CH(CN)
Others, such as polythene2and PVC, are more easily shaped
b CH “ C(CN)¬CH “ CH(CN)
2 and are classified
as plastics.
Now try this

1 2

30 20
17. 58 Thermoplastic Polymers

Many polymers soften when heated and harden on cooling.
The long, flexible chains slide over one another when the temperature is high,
but they bond to one another when the polymer cools.
Polymers that behave in this way are called thermoplastics.
They are flexible, yet strong, and can be moulded into whatever shape you
need.
Polythene and PVC are thermoplastics.
17. 59 Thermosetting Polymers

Some polymers set into a rigid solid as soon as they are made, and cannot be
moulded.
They are called thermosetting polymers.
The hard melamine resin used to make kitchen worktops is a thermosetting

ploymer.
17. 60 Polymer Properties

Different polymers have different characteristics, depending on the properties
of the molecular chains. The five most important properties are listed here:
Chain length: The tensile strength of a polymer increases with chain length.
Intermolecular forces attract the chains to each other all along their length,
and the longer the chain, the more intermolecular forces there are.
Chain flexibility: Poly(ethene) contains alkane chains which are very flexible.
Some polymer chains, such as those in Kevlar are much more rigid, and this
results in a strong, tough rigid polymer.

21 31
17. 61 Polymer Properties: Side Groups

Different polymers have different side-groups on their chains. For example,
poly(chloroethene), commonly called PVC, has Cl atoms as side groups.
Polar side groups, such as Cl, increase the intermolecular forces between the
chains, so they attract each other more strongly than in polythene.
As a result, PVC is stronger and harder to melt.
28.2 Polymer prop

17. 62 Polymer Properties: Side Groups
28.2 Polymer prope
28.2 Polymer properties
H H H H H H H H
− −− −
−−
−−
−
− −− −
− −− −
−−
−−
H HH H HH HH H H H HH HH poly(ethene)
−C−C−C−C−C−C−C−C−
−
−
−
−
−−−−
−−−−
−−−−
−−−−
−−−−
no side groups
poly(ethene)
poly(ethene)
− C −−CC−
−CC−
−CC−−C C−−
C−C C−−CC−
−CC −
− no side groups
no side groups
−
−
−
H HH H H HH H H H HH HH H H
H H H H H H H H
H HH H H HH H H H HH HH H H poly(chloroethene)
poly(chloroethene)
−
−
−
−
−
−
−
−
− −− −
− −−− −
− −−− −
− −−− −
− −− −
− −− −
− −−− −
− −−− −
H −HC − H C − C
H− C
H− C
H
− C − HC − HC −
polar Cl side
polar groups
Cl side makemake
groups
poly(chloroethene)
− C − C − C − C − C − C − C − C δ+ −
δ+ the polymer chains attract
the polymer chains attract
polar Cl side groups make
−
−
−
one another more strongly

− C − CH− Cl C −HC − Cl C − − CH− C
H C Cl −δ−
Clδ+
δ− onepolymer
the another chains
more strongly
attract
H Cl H Cl H Cl H Cl one another more strongly
H Cl H Cl H Cl H Cl δ− (PVC)
Fig 28.3 Poly(ethene) (polythene) and poly(chloroethene)
Fig 28.3 Poly(ethene) (polythene) and poly(chloroethene) (PVC)
Fig 28.34Poly(ethene)
Branching(polythene) and poly(chloroethene)
Highly branched polymer chains(PVC)
cannot pack together as tightly
and neatly
4 Branching as unbranched
Highly branchedchains.
polymer Highly
chains branchedcannotpolymers
pack therefore
togethertend as tightly
to haveHighly
4 Branching lower tensile strength
branched and to melt
polymer chains more easily than
cannot pack unbranched
together as tightly
and neatly as unbranched chains. Highly branched polymers therefore tend
polymers (Figure 28.4(a)) and (b)). This is the reason for the different
and neatly
to have as unbranched
lower
properties tensile chains.
strength
of low-density andand
Highly
to meltbranched
high-density more
polythene
polymers
easily therefore
than 15.6).
(Section unbranched
In most
tend
to have
polymers lower
(Figure
polymers, tensile
there strength
28.4(a))
are andin
regions and
(b)).toThis
which melt
theis more
the reason
chains easily
are neatly than
for theunbranched
and different
regularly
17. 63
polymers
properties
packed.
Polymer
(Figure
of low-density
These
Properties: Branching
28.4(a))
are called and
and (b)). regions,
This is the
high-density
crystalline reason
polythene
and they make for the
(Section
the different
15.6). In most
polymer
properties
polymers, of
stronger low-density
therethan in regions
are and inhigh-density
the non-crystalline,
which the polythene
or amorphous
chains regions.
are (Section
neatly and15.6).
Stretching In most
or cold-
regularly
drawing a polymer makes thewhich
polymer chains linethey
up to form more crystalline
Highly
polymers,
packed. branched
there
These
regions
are
(Figurepolymer
are regions
called chains
in
thiscannot
crystalline
28.6), and is used pack
the
regions,
to turn together
chains
and are
polymers aslike
tightly andinto
neatly
make and
the neatly
regularly
polymer as
packed. These
unbranched arethe
called crystalline regions, and they makenylon the polymertough
fibres. chains.
stronger than in non-crystalline, or amorphous regions. Stretching or cold-
stronger
drawing athan in themakes
polymer non-crystalline,
the polymer orchains
amorphous line upregions.
to form Stretching or cold-
more crystalline
Highly (Figure
drawing
regions abranched
polymer polymers
makes
28.6), therefore
andthethispolymer tendto
is used to(a)turn
chains have lower
line
Polymer
uptensile
polymers
with few
to strength
form
like
branched chains, and to
moreinto
nylon crystalline
tough
melt more easily than unbranched polymers.
regions
fibres. (Figure 28.6), and this is used to turn
e.g. polymers
high-density like
polythene. nylon into tough
fibres. Chains regularly packed, with extensive
crystalline regions. High tensile strength,
This is the reason for the different properties high
(a) ofPolymer
low-density
melting point.
with few and high-density
branched chains,
polythene. e.g. high-density polythene.
(a) Polymer with few branched chains,
Chains
e.g. regularly packed,
high-density with extensive
polythene.
crystalline
Chains regions.
regularly High tensile
packed, strength,
with extensive
high melting
crystalline point.High tensile strength,
regions.
high melting point.
(b) Polymer with many branched chains, Fig 28.5 Spiders’ webs and silkworm silk are
e.g. low-density polythene. made from a strong protein called fibroin.
Chains irregularly packed: largely Strong intermolecular forces between the side
amorphous with few crystalline regions. groups make fibroin stronger than steel with
Lower tensile strength, lower melting the same diameter
point.
(b) Polymer with many branched chains, Fig 28.5 Spiders’ webs and silkworm silk
e.g.Polymer
(b) low-density
withpolythene.
many branched chains, made
Fig from
28.5 a strong
Spiders’ protein
webs and called fibroin.
silkworm silk
Chains
e.g. irregularly
low-density packed: largely
polythene. Strongfrom
made intermolecular forcescalled
a strong protein between the
fibroin.
amorphous with few crystalline
largelyregions. groups intermolecular
make fibroin stronger than steel w
Bilal Hameed Chains irregularly packed: Marginalizer Strong
the same diameter
forces between the
Lower tensile
amorphous strength,
with lower melting
few crystalline regions. groups make fibroin stronger than steel w
point. tensile strength, lower melting
Lower the same diameter
point.
Bilal Hameed (c) Polymer with much cross-linking, Polymerisation
e.g. epoxy resin.
Rigid and hard, fairly brittle
to have lower tensile strength and to melt more easily than unbranched
properties H H H H and
of low-density H high-density
H H H polythene (Section 15.6). In most
poly(chloroethene)
32 22
−
−
−
−
−
−
−
−
polymers, there are regions in which the chains polar
are Cl side groups
neatly andmake
regularly
− C − C − C − C − C − C − C − C δ+ − the polymer chains attract
packed. These are called crystalline regions, and they make the polymer
−
−
−
−
−
−
−
−
δ− one another more strongly
H in
stronger than Cl theH non-crystalline,
Cl H Cl H orClamorphous regions. Stretching or cold-
drawing a polymer makes the polymer chains line up to form more crystalline
17. 64 Polymer Properties:
this is usedBranching
Fig 28.3 Poly(ethene) (polythene) and poly(chloroethene) (PVC)
regions (Figure 28.6), and to turn polymers like nylon into tough
4fibres.
Branching Highly branched polymer chains cannot pack together as tightly
to have lower tensile strength and to melt more easily
(a) Polymer than
with few unbranched
branched chains,
polymers (Figure 28.4(a)) and (b)). Thise.g.is high-density
the reasonpolythene.
for the different
properties of low-density and high-densityChains regularly packed,
polythene with15.6).
(Section extensive
In most
crystalline regions. High tensile
polymers, there are regions in which the chains are neatly and regularly strength,
high melting point.
stronger than in the non-crystalline, or amorphous regions. Stretching or cold-
regions (Figure 28.6), and this is used to turn polymers like nylon into tough
fibres.
(a) Polymer with few branched chains,

e.g. high-density polythene.
(b) Polymer
Chains withpacked,
regularly many branched chains,
with extensive Fig 28.5 Spiders’
e.g. low-density
crystalline polythene.
regions. High tensile strength, made from a stron
Chains irregularly
high melting point.packed: largely Strong intermolecu
amorphous with few crystalline regions. groups make fibroi
17. 65 Polymer Properties: Branching

Lower tensile strength, lower melting the same diameter
point.
(b) Polymer with many branched chains, Fig 28.5 Spiders’ web
e.g. low-density polythene. made from a strong p
Chains irregularly packed: largely Strong intermolecular
amorphous with few crystalline regions. groups make fibroin s
Lower
(c) tensilewith
Polymer strength,
muchlower melting
cross-linking, the same diameter
point.
e.g. epoxy resin.
Fig 28.4 Unbranched, branched and cross-linked polymers
(c) Polymer with much cross-linking,
17. 66 Polymer Properties: Cross Linking

e.g. epoxy resin.
Thermosetting polymers have extensive cross-linking between chains. This

forms a rigid network, making a hard polymer. The more cross-linking, the
Fig more rigid the polymer.
28.4 Unbranched, branched and cross-linked polymers
When an epoxy resin glue sets, the monomers in the liquid glue form a strong
cross-linked network to one another, giving a hard, rigid join between the
surfaces that are being glued together.

properties of low-density and high-density polythene (Section 15.6). In most
polymers, there are regions in which the chains are neatly and regularly
33
23non-crystalline,
stronger than in the or amorphous regions. Stretching or cold-
regions (Figure 28.6), and this is used to turn polymers like nylon into tough
fibres.
A cross-link is a bond that links one polymer chain to another. They can be with few branched chains,
(a) Polymer
e.g. high-density polythene.
covalent bonds or ionic bonds. Chains regularly packed, with extensive
crystalline regions. High tensile strength,
The cross-linking of the chains of the rubber molecules makes the rubber
high melting point.
harder, stronger, less flexible and less ‘sticky’.
(b) Polymer with many branched chains, Fig 28.5 Spide

e.g. low-density polythene. made from a st
Chains irregularly packed: largely Strong intermo
amorphous with few crystalline regions. groups make fi
Lower tensile strength, lower melting the same diam
point.

Representation of a polymer with much cross-linking, e.g. epoxy resin. They
are rigid and hard, fairly brittle.
(c) Polymer with much cross-linking,

e.g. epoxy resin.
Fig 28.4 Unbranched, branched and cross-linked polymers
Chapter 28: Polymerisation
17. 69 Cross-Linked Polymers
S cross-linking
between polymer chains
S
CH2 CH CH CH2 CH2 CH CH CH2 CH2
S
S
CH2 CH CH CH2 CH CH CH2 CH2 CH CH CH2
S
S
CH2 CH CH CH2 CH CH CH2 CH2 CH CH
S
S
Figure 28.22 The sulfur bridges between polymer chains make rubber more resilient.
Non-solvent-based
Bilal Hameed adhesives OCH3 Marginalizer 423
Traditional adhesives (glues) use an organic solvent to Si
dissolve a polymer that will stick two surfaces together.
OCH3
Bilal Hameed
After applying the adhesive, the solvent evaporates off and H2O+
OCH3
Polymerisation
the solid polymer is left behind and acts as the glue. The
solvent used is often the ester, ethyl ethanoate, as it has a Si
low toxicity and is volatile. However, it is flammable and
34 24
28 Addition and condensation polymers

Polymers
17. 70 Cross-Linked Polymers
Figure 28.16 Cross-linking in Fibre before cold-drawing Fibre after OH
HO
condensation polymers cold-drawingO
2 HO OH + 4 C C + 1 HO OH
O OH
OH
–6 H2O
chain
O O O
chain
C C
O O O
O O
C C
O O O O
C C
O O
O chain
Amorphous Crystalline
C C
KEY POINT region chain region O

O
The characteristics of polymers Fig 28.6 Cold-drawing increases the crystallinity of a fibre
are determined by the properties
PTFE28_16 Cam/Chem
5 Cross-linking Thermosetting polymers have extensive cross-linking
of their molecules. Their key AS&A2
between chains
The opposite (Figure
Barkingeffect
Dog 28.4(c)).
is noticed
Art This uoroethene,
with polytetrafl forms a rigid network,
PTFE (see Topic 14).making
Here, a hard
properties are: all of the hydrogen
polymer. The more atoms in the polymerthe
cross-linking, havemore
been replaced by flpolymer.
rigid the uorine atoms.When an
Polymers Fluorine is the most electronegative element in the Periodic Table, and strongly
• chain length, epoxyattracts
resintheglue sets, the monomers in the liquid glue form a strong cross-
electrons in covalent bonds attached to it. This means that the electrons
• chain flexibility, linked
arenetwork
held firmly to
andone another,
are not giving
easily polarised. a results
This hard,inrigid joinvan
very weak between
der Waals’the surfaces
• side groups, 17. 71 Conducting

that are
forcesbeing
Fibre
betweenglued
before Polymers
together.
cold-drawing
PTFE Fibre and,
molecules and each other aftermore importantly, between PTFE
cold-drawing forces that cause molecules to
molecules and other molecules. It is the intermolecular
• chain branching, Most polymers areand
stick together, insulators. Indeed,
so PTFE is used the insulation
as a non-stick on electric
surface on cookware, wires
and also for and
• cross-linking.
Most polymers
cables isthe
often are insulators.
poly(ethene)
bearings The
or reason
that might most
poly(chloroethene)
at the ends of bridges polymers
expand and (PVC).
contract arechanges
with insulators
in is that
their electrons are held in covalent bonds inis the
thatpolymer chain. are
They cannot
the environment’s temperature.
The reason most polymers are insulators their electrons held in
move, and‘Ecopolymers’
covalent cannot conduct
bonds in electricity.
the polymer chain. They cannot move, and cannot conduct
electricity.
Until recently, the raw materials for most polymers came from the products of the
However, some
Also,
polymer
polymer
the disposal
chains
chainscontain
of polymeric contain
materials
delocalised
delocalised
after
electrons
electrons
their useful life
which
refining of crude oil, which is a finite, non-renewable and diminishing resource.
However, some has causedwhich
canmove
can
problems
move and conduct
and conduct
of pollution, electricity.
electricity. The
since many areThe
simplestsimplest
example
non-biodegradable. example
Bothis of is poly(ethyne),
poly(ethyne),
these commonly
problems have been called
commonlyofcalled
polyacetylene
polyacetylene.
(Figure by 28.7).
partially overcome an increase in the recycling of polymers: thermal cracking
polyethene can convert it into its monomer, ethene, which can then be reused;
the polyethylene-terephthalate (PET) from plastic bottles can be converted into a
H fleeces H
wool-like material for and other H
clothing. H H H
−
−
AnAmorphous Crystalline
alternative solution is to use renewable plant material to make polymers that
KEY POINT are alsoregion
−− = C
biodegradable. region
The− C
=most commonly
= C
− used C − C = C acid)
=is poly(2-hydroxypropanoic
= − − −−
(poly(lactic C PLA). C
acid), C C C C
The characteristics of polymers Fig 28.6 Cold-drawing increases the crystallinity of a fibre
−
are determined by the properties H O H H H O H CH 3 H n

5 Cross-linking Thermosetting polymers have O
extensive cross-linking
of their molecules. Their key
Figbetween chains
28.7 Polyacetylene
HO (Figure
contains
C 28.4(c)).
long chains This forms C a rigid
withOalternating CH network,
double andO singleCmaking a hard
properties are: bonds betweenThe the carbon 2H O
polymer. CH atoms
more cross-linking, the more
CH rigid O the C polymer.CH When an
2
OH
• chain length, epoxy resin glue sets, the monomers in the liquid glue form a strong cross-
CH 3 CH 3 O CH 3
• chain flexibility, Compare this hydroxypropanoic
linked network structure
to one with the alternating doublePLAand
acid another, giving a hard, rigid
single
join bondsthe
between in surfaces
thethat
benzene
are beingring glued
(Section 26.2). In benzene, the π electrons in the double
together.
• side groups, bonds are delocalised acid around the whole ring. A similar
Hydroxypropanoic is a naturally occurring compound, which thing
is made happens
industrially in
17.cables
72 Conducting Polymers
• chain branching, Most polymers
polyacetylene: are πinsulators.
the
by the fermentation electrons Indeed,sugar.the
PLAinsulation
areordelocalised
of corn starch along
is easily on whole
the electric
hydrolysed, wires and
either polymer chain.
They areischemically
often
free to poly(ethene)
or by esterase
move along or
thepoly(chloroethene)
enzymes, to re-form
chain, carrying (PVC).
hydroxypropanoic
electric acid, which isand this is why
charge,
• cross-linking. readily metabolised by all living matter into CO2 and water.
the polymer conducts electricity.
They
The
contain long chains
reason most polymers
with alternating double and single bonds481between
are insulators is that their electrons are held in
covalent bonds in the polymer chain. They cannot move, and cannot conduct
theelectricity.
carbon atoms.
Polyacetylene is just one of many conducting polymers that scientists have
made. There are hopes that conducting polymers will have practical uses,
such as organic solar cells and organic light-emitting diodes (LEDs). But
181333_28_A_Chem_BP_469-494.indd 481 TheHowever,
! bonds
the polymerson made
adjacent alkene
so far units overlap,
aresimplest
difficult to shapeand the ! electrons become
some polymer chains contain delocalised electrons which 09/10/14can move
2:07 AM
and conduct electricity. The example isand fabricate,
poly(ethyne), socommonly
large-scalecalled
delocalised throughout
applications
polyacetyleneare yet tothe
(Figure whole length of the polymer chain.
come.
28.7).
H H H H H H
−
−− =C − =C − =C − =C − =C − =C −−
C C C C C C
−
522 H H H H H H n
Fig 28.7 Polyacetylene contains long chains with alternating double and single
bonds between the carbon atoms
Compare this structure with the alternating double and single bonds in
the benzene ring (Section 26.2). In benzene, the π electrons in the double
bonds are delocalised around the whole ring. A similar thing happens in
polyacetylene: the π electrons are delocalised along the whole polymer chain.
They are free to move along the chain, carrying electric charge, and this is why
the polymer conducts electricity.
Polyacetylene is just one of many conducting polymers that scientists have
made. There are hopes that conducting polymers will have practical uses,
such as organic solar cells and organic light-emitting diodes (LEDs). ButBilal
Marginalizer Hameed
the polymers made so far are difficult to shape and fabricate, so large-scale
applications are yet to come.
hydrolysis of this to
monomer.
keep bones in place whilst they heal (see Figure 28.17).
O
O O
Figure 28.17 A biodegradable screw
O 25 35
made of PLA
Draw the structures of the products of the
Figure 28.17 A
hydrolysis of this monomer. biodegradable screw
made of PLA
17. 73 Conducting Polymers Conducting polymers
Figure 28.17 A biodegradable screwR R R R Conducting
Graphitepolymers
is a conductor of electricity be
made of PLA
R R R Graphite is
R
atoms
a conductorthereofare delocalised
electricity becauseelectrons
within eachco of
onducting polymers C C C atoms there C
when a potential
are delocalised difference
electrons coveringisevery
applied
atom a w
raphite is a conductor of electricity because within each of C C of
its layers CC
Conducting
C carbon CC polymers C when a potential difference is applied at opposite ends of th
oms there are delocalised electrons covering every atomR within
C C
Graphite
R the layer. Thus, is aC conductorCof electricity because withinelectrons
each of its layerswill flow from one end to the
of carbon
R R electrons will flow from one end to the other.
hen a potential difference is applied at opposite R R
atoms R
there are delocalised R
electrons
Some polymer long-chain
covering every atom within the layer. Thus,
polymer molecules
C C ends of C the layer,
C R the delocalised
R
when R
a potential R is applied at opposite
difference Some long-chain
ends of the layer, molecules
the delocalised act as ‘molecular wir
ectrons will flow from one end to the other.C C C C
electrons will flow from one end to theconjugated
other. conjugated
double bonds, double
which meansbonds, thatwhich mea
the π bonds
Some long-chain polymer molecules act as R‘molecular R wires’.
R They
R contain Some long-chain polymer molecules act as ‘molecular wires’. They contain
onjugated double bonds, which means that the π bonds on adjacent alkene units double bonds, which means
conjugated overlap,
that theand theonπadjacent
πoverlap,
bonds electrons
andalkenethe π electrons
become
units delocalised throughout
become de
verlap, and the π electrons become delocalised throughout the whole length overlap,
of the polymerthroughout
and the π electrons become delocalised chain (see Figure
the whole 28.18).
length of the
Figure 28.18 Thepolymer structurechain of(see
a Figure 28.18).
polymer chain (see Figure 28.18).
olymer chain (see Figure 28.18). Just as with the three-dimensional delocalised electrons in me
st as with the three-dimensional delocalised electrons Figure
Figure 28.18 The structure of a
in ‘molecular
metals, or 28.18 two-The
wire’
the
Just structure of a
as with the three-dimensional delocalised electrons
Just as with electrons
in metals, or the two-
theone-three-dimensional deloca
‘molecular wire’ dimensional delocalised electrons in thedimensional
sheets of graphite delocalised
or graphene, these in the sheets of graphite or
mensional delocalised electrons in the sheets of
‘molecular
graphite or graphene,
wire’
these one- dimensional
dimensional delocalised electrons can conduct a currentdimensional
delocalised
when delocalised
a potentialelectrons
difference electrons
can conduct in
a current the
when s
mensional delocalised electrons canBarking Dog aArt
conduct currentBarking
when aDog potential
Art difference
is applied to the ends of the polymer. An eventual aim is to construct micro-miniature
28_18 is applied to the
dimensionalends of the polymer.
in the heart delocalised
An eventual aim is
electrons can co to co
applied to the ends of the polymer. An eventual aim is to Cam/Chem AS&A2
circuits that can lead electrical signals to ‘molecular microchips’
construct micro-miniature of computing
rcuits that can lead electrical signals to ‘molecular Barking
microchips’Dog in theArt
heart of devices
circuits
that will be thousands of times smaller that
than cansilicon-based
today’s lead electrical
units. signals to ‘molecular microchips
computing
Three main classes of conducting polymersdevices arethat
theispolyacetylenes,
applied to
will be thousands the the of ends of the polymer. An
times smaller than today’s sil
evices that will be thousands of times smaller than today’s silicon-based units.polyphenylene vinylenes and the polythiophenes
Three main circuits that
(see Figure 28.19).
classes of can lead electrical
conducting polymers aresignals to ‘
the polyac
17. 7428.19 Conducting Polymers: Examples
Three main classes of conducting polymers are the polyacetylenes, the
Figure
olyphenylene vinylenes and the polythiophenes
polymer
(see types
Three Figure 28.19).
of conducting polyphenylene
S devices
S that
vinylenes
S will
and thebe polythiophenes
thousands of (see times sm
Figur
S S Figure 28.19
S Three types of conducting
Three main classes of conducting pol
S S
polymer Rpolyphenylene vinylenes and the polyth
n
R R n
polyacetylene (polyethyne) a substituted polythiophene (PT)
n
R R Figure
R 28.19 n Three typesOR
of conducting
n
polyacetylene (polyethyne) polymer (PT)
a substituted polythiophene OR R R
polyacetylene
OR (polyethyne) a substituted polythiop
OR
OR RO
OR
n
OR RO
OR R
RO
a disubstituted polyphenylene vinylene (PPV)

n
polyacetylene (polyethyne) OR
RO
RO 28_19 Cam/Chem AS&A2
482 Barking Dog Art
RO RO OR
n
RO
a disubstituted polyphenylene vinylene (PPV) OR
181333_28_AS_Chem_BP_469-494.indd 482 07/11/14 3:03 PM
RO
28_19 Cam/Chem AS&A2 A 17. M75 Properties of Polymers: Summary
AT E R I A L S n
Barking Dog Art a disubstituted polyphenylene vinylene (PPV)
Structural property Physical property Example

Chain length 482 The longer the chain, the stronger the Longer polymer chains have higher
point, increasedBarking Dog RO
Art
polymer. 07/11/14 3:03 melting
PM strength, and
increased impact resistance due to
increased van der Waals’ forces. RO
Branching and packing structures
Straight unbranched chains can pack HDPE with no branching is more rigid
more closely. A higher degree of than the more branched LDPE. Use
branching keeps482
181333_28_AS_Chem_BP_469-494.indd strands apart and of plasticizers in PVC to soften the
weakens intermolecular forces. polymer.
Side groups on monomers Hydrogen bonding can increase Polystyrene a disubstituted polyphenylene vin
strength, eg Kevlar. Atactic and
isotactic placement can influence
strength, eg polystyrene.
482
Cross-linking Extensive covalently bonded cross-
linkage increases polymer strength.
Vulcanized rubber, Bakelite
Barking Dog Art
▲ Table 1 Summary of polymer properties
Breaking down condensation polymers

Condensation polymers are formed from two monomers, releasing a
181333_28_AS_Chem_BP_469-494.indd 482 These polymers can be broken down by
small molecule in the process.
the reverse reaction. Proteins, for example, are hydrolysed (a reaction
that adds water) to amino acids during digestion. Polyamides with
strong hydrogen bonding such as Kevlar can dissolve in sulfuric acid:
the acid donates a proton to the oxygen and nitrogen atoms involved
in hydrogen bonding. This breaks hydrogen bonds between chains of
Kevlar fibres and the substance dissolves.
O
H O N
O N N O H
Bilal Hameed H H
Polymerisation
O
H O N N
O N N O H
H
36 26
17. 76 Addition vs Condensation Polymers

Table 11.2 A comparison of addition and condensation polymerisation.
Differences Addition polymers Condensation polymers

The type of reaction Addition reaction only Addition reaction followed by elimination reaction,
resulting in the condensation of a small molecule such
as H2O or HCl
Type of links along the C-C single bonds only, which are Short aliphatic or aryl sections linked by either ester
central chain non-polar groups or amide groups, which are polar
The type of monomer All monomers have C=C double bond The monomers have molecules with at least two
involved functional groups, which may be the same or different
Hydrolysis Resistant to hydrolysis Undergo hydrolysis
Conditions for preparation Require an initiator, together with high Do not require initiators and usually occur at much
temperature and high pressure, unless lower temperatures and atmospheric pressure
a catalyst is involved
Polymer properties Non-polar and resistant to attack Polar and subject to hydrolysis
As polymer science has grown, chemists and material scientists have learnt
how to develop new materials with particular properties. Some of the ways
of modifying the properties of polymers include:
● altering the average length of polymer chains
● changing the structure of the monomer to one with different side groups
and different intermolecular forces, thereby varying the extent of cross-
linking between chains
17. 77 Biodegradability
● selecting a monomer which produces a polymer that is biodegradable or
photodegradable
● adding fillers and pigments.
A biodegradable polymer is one that can be broken down in the environment
The development of degradable polymers
by the action of micro-organisms.
As it becomes more and more expensive to dump waste in landfill sites,
plastics are seen as an increasing problem. The major problem with most
Polyalkenes are chemicallyplastic
inertwaste
and isnon-biodegradable because
that it is non-biodegradable. This meansthey areonly
that the
saturated and have no bond polarity.
choices for dealing with plastic waste are recycling and energy recovery.
Although some progress has been made, the separation, sorting and
recycling of different plastics is difficult to mechanise and automate.
Condensation polymers can be hydrolysed
Modern andburn
incinerators, which soplastic
are now
wastebeing
in order used more
to recover the
than addition polymers. This means
energy that
from its they are
combustion, biodegradable
have in the standards.
to meet tough environmental
Despite these higher standards, many people remain suspicious of the
environment. Many drink bottles (especially
emissions water
from incinerators bottles)
and worry areare
that they now made
a health risk. from
PET. These concerns over incineration and the difficulties in recycling have led
chemists to look for other ways of minimising the waste from plastics.
The most promising approach involves the development of biodegradable
Chapter 11 Polymers
polymers, such as poly(lactic acid), see page 215.

Another important approach is the development and use of condensation
polymers that are either:
● photodegradable, in which the C=O bonds in condensation
polymers absorb radiation that has sufficient energy to facilitate the
decomposition of the polymer
● readily degraded by hydrolysis, such as poly(glycolic acid), see page 223.
222 17. 78 Disposal of Polyalkenes

Poly(ethene) and poly(propene) are not biodegradable because they are
basically long-chain alkane molecules.
Alkanes are unreactive because they have only strong, non-polar C—H and C
—C bonds. There is nothing in the natural environment that will easily break
them down and they persist for many years.
They are usually disposed of in landfill sites, along with other rubbish, or by
incineration. Some may be melted down and remoulded.

For example:
Synoptic link
O O 27 O 37 O
You will need to know bond
—
—
—
—
—
—
—
—
C—A—C—O—B—O—C—A—C
polarity studied in Topic 3.6,
Electronegativity – bond polarity in
17. 79 Disposal of Polyalkenes
+H O
2
covalent bonds
O
As it becomes more and more expensive
O to dump waste in landfill sites,
—
—
—
—
plastics are seen as anCincreasing
— A — C problem.
and HO — B — OH
—
HO OH
The major problem with most plastic waste is that it is non-biodegradable.
monomers
This means that the only choices for dealing with plastic waste are recycling
andisenergy
This recovery.
exactly the same process that occurs when condensation
polymers are hydrolysed.
Disposal of polymers
Poly(ethene) and poly(propene) are not biodegradable because they ▲ Figure 9 Undecomposed poly(ethene)
are basically long-chain alkane molecules. Alkanes are unreactive and poly(propene) cause problems for
because they have only strong, non-polar C H and C C bonds. There wildlife
is nothing in the natural environment that will easily break them
down and they persist for many years. They are usually disposed of in
landfill sites, along with other rubbish, or by incineration. Some may Recycling plastics
be melted down and remoulded.
17. 80 Disposal of Polyalkenes Many polyester materials are
Poly(alkenes) can be burnt to carbon dioxide and water to produce now recycled. They are being
Poly(alkenes)
energy, can be
although burnt to carbon
poisonous carbondioxide and water
monoxide mayto produce energy,
be released into collected, sorted, and then melted
although poisonous carbon monoxide may be released into the
the atmosphere if combustion is incomplete (when there is a shortage atmosphere if and reformed. Fleece garments
combustion
of oxygen). is incomplete (when there is a shortage of oxygen). may well be made from recycled
soft drink bottles. With all
Burning poly(alkenes)
Burning poly(alkenes) does addadd
does to the
toproblem of increasing
the problem the level ofthe level
of increasing recycling, the costs and benefits
of carbon
carbondioxide in the
dioxide inatmosphere
the atmosphere: have to be balanced. Melting
1 and reforming of plastics can
–[CH2–]n + 1 nO2 ➝ nCO2 + nH2O
2 only be done a limited number
Other addition polymers, such as polystyrene, may release toxic of times, as during the process
products on burning. Complete combustion of polystyrene (a the polymer chains tend to break
hydrocarbon) would produce carbon dioxide and water only. and shorten, thus degrading the
However, under certain conditions the polymer may depolymerise properties of the polymer.
to produce toxic styrene vapour. Incomplete combustion produces
carbon monoxide and unburnt carbon particles – black smoke. Advantages of recycling
Condensation polymers like polyesters and polyamides can be broken Almost all plastics are derived
from crude oil. Recycling
17. 81 Disposal of Polyalkenes
down by hydrolysis and are potentially biodegradable by the reverse of
saves this expensive and ever
the polymerisation reaction by which they were formed.
Other addition polymers, such as polystyrene, may release toxic products on diminishing resource, as well as
The reaction below shows the hydrolysis of a polyamide such as nylon.
burning. the energy used in refining it.
However, this reaction is so slow under everyday conditions that you do
not need to worry
Incomplete about
combustion your nylon
produces umbrella
carbon monoxidedepolymerising in the rain.
and unburnt carbon If plastics are not recycled they
particles –Hblack smoke. mostly end up in landfill sites.
H O O
Disadvantages of recycling
—
—
—
—
—
—N—R—N—C—R—C— + n H2O
n
The plastics need to be collected,
Throughout the polymer,
transported, and sorted, which
the N—C bond is broken.
uses energy and manpower and
H H O O
is therefore expensive.
—
—
—
—
—
n —N—R—N—H + H—O—C—R —C—
465

Fluorine is the most electronegative element in the Periodic Table, and strongly
attracts the electrons in covalent bonds attached to it. This means that the electrons
are held firmly and are not easily polarised. This results in very weak van der Waals’
forces between PTFE molecules and each other and, more importantly, between PTFE
molecules and other molecules. It is the intermolecular forces that cause molecules to
stick together, and so 38 28 surface on cookware, and also for
PTFE is used as a non-stick
the bearings at the ends of bridges that might expand and contract with changes in
the environment’s temperature.
‘Ecopolymers’
17. 82Until
Disposal ofmaterials
recently, the raw Condensation Polymers
for most polymers came from the products of the
refining of crude oil, which is a finite, non-renewable and diminishing resource.
Also, the disposal of polymeric materials after their useful life has caused problems
Condensation polymers
of pollution, likearepolyesters
since many and polyamides
non-biodegradable. Both of these can be broken
problems have beendown
by hydrolysis
partiallyand are potentially
overcome biodegradable
by an increase in the recycling ofby the reverse
polymers: thermalof the
cracking
of polyethene can convert it into its monomer, ethene, which can then be reused;
polymerisation reaction by which(PET)
the polyethylene-terephthalate they were
from formed.
plastic bottles can be converted into a
wool-like material for fleeces and other clothing.
The most Ancommonly used degradable
alternative solution polymer
is to use renewable is poly(2-hydroxypropanoic
plant material to make polymers that
acid) (poly(lactic acid), PLA).

are also biodegradable. The most commonly used is poly(2-hydroxypropanoic acid)
(poly(lactic acid), PLA).
O O CH 3 O
HO C O C CH O C
2H2O
CH OH CH O C CH
CH 3 CH 3 O CH 3
hydroxypropanoic acid PLA
Hydroxypropanoic acid is a naturally occurring compound, which is made industrially

by the fermentation of corn starch or sugar. PLA is easily hydrolysed, either
chemically or by esterase enzymes, to re-form hydroxypropanoic acid, which is
readily metabolised by all living matter into CO2 and water.
481
17. 83 PLA
PLA is easily hydrolysed, either chemically or by esterase enzymes, to re-form
181333_28_A_Chem_BP_469-494.indd 481 09/10/14 2:07 AM
hydroxypropanoic acid, which is readily metabolised by all living matter into

CO2 and water.
The uses of PLA include replacing conventional plastics in the manufacture of

bottles, disposable cups and textiles, but it is also used in applications where
its slow biodegradability is an advantage.
17. 84 Photodegradable Polymers

Chemists are now developing degradable plastics that break down when they
are discarded: biodegradable plastics and photodegradable plastics.
Polymer chains also have been designed that incorporate carbonyl groups
(C=O) at intervals down their length. These carbonyl groups absorb uv
radiation which causes the bonds in the region of the carbonyl group to
weaken and break down.
As the polymer breaks into smaller fragments, the plastic will biodegrade
much more quickly if it is not chemically inert.

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9

suggest the identity of molecules formed by simple fragmentation in a given mass

Bilal Hameed Polymerisation

44 www.cie.org.uk/alevel Back to contents page

Polymerisation Bilal Hameed

molecule, so a chain can form.

—C —O—B—O—C—A—C two monomers of the structures of polyamides and

ordered ▲structure. The

example, hydrogen bonds can HO — C — A — C — OH

Condensation polymers are—formed

attract one another thus forming HO — C — A — C — OHH—N—B—N—H —B— —n

formation of an ester from an alcohol and a carboxylic acid (sub-topic 10.2)

Bilal Hameed Marginalizer

Bilal Hameed Polymerisation

17. 6 Polyesters: Terylene (PET)

Marginalizer Bilal Hameed

C C O CH2 CH2 O C C O CH2 CH2 OH

17. 9 Polyesters: Properties & Uses

Polyester fibre is often used as a substitute for cotton: it is cheaper

Polyester is also used as a plastic, for example in PETE plastic bottles.

The bonding resin in glass fibre reinforced plastic is a cross-linked polyester.

Bilal Hameed Marginalizer

Bilal Hameed Polymerisation

Figure 28.8 Formation of type II

28.2 Condensation polymers

17. 13 Skill Check

40 From which monomers could the following polymers be formed?

Given a polymer chain, the repeat unit may be generated:

To work out the monomers from a polymer chain the following

The amide functional group is:

To work out the monomers from a polymer chain the following

Bilal Hameed Marginalizer

Bilal Hameed Polymerisation

17. 16 Generating Monomers From Polyesters

17. 17 Skill Check

b units of the polymer formed when the following molecules react:

17. 18 Skill Check

Figure 18.2.29 Polymer chains in Kevlar.

469983_18.2_Chem_Y1-2_541-567.indd 559 13/04/19 10:00 PM

Bilal Hameed Marginalizer

Bilal Hameed Polymerisation

CH3 O CH3 CH3 O CH3 O

Figure 18.2.26 The nylon rope trick. O O H H

C(CH2)4C N(CH2)6N + 2nHCl

—N— —N—C— —C—N— —N—

Polypeptides and proteins

Bilal Hameed Marginalizer

Bilal Hameed Polymerisation

Start with the repeat unit. 1

Marginalizer Bilal Hameed

Polymerisation Bilal Hameed

Figure 18.2.29 Polymer chains in Kevlar.

a) What type of polymerisation will produce the polymer above.

Polymers 17. 35 Hydrolysis

Acid hydrolysis of a polyester results in theethanoic

If the reaction is catalysed by an acid, the product is lactic acid

17. 37 Hydrolysis of Terylene

N (CH2)6 N C (CH2)4 C N (CH2)6 N C (CH2)4 CH

H2N (CH2)6 ONH2 andO –O C (CH2)4 C O–

N ( CH2 )6 N C ( CH2 )4 C Base catalyst forms a

H dissolve H slowly in HO the patient’s OH tissue fluid. H H

Draw the structures of the products formed when it is hydrolysed by refluxing

Table 28.1 Structures and uses of some Monomer Polymer Use