Topic 4.

9
POLYMERS
Formation of addition polymers
Properties and uses of addition polymers
Formation of condensation polymers
Properties and uses of condensation polymers
Disposal and recyclin
ADDITION POLYMERS
i) Formation of addition polymers
Addition polymers are formed from alkenes.
Alkenes can be made to join together in the presence of high pressure and a suitable
catalyst. The -bond breaks and the molecules join together. No other product is formed,
and so this is known as addition polymerisation. Since the polymers are made from
alkenes they are also known as polyalkenes.

C
C
H
H
H
H
n C C
H H
H
H
n

ethene polyethene
The product of this addition process is a ery long hydrocarbon chain.
Addition polymers can be made from any alkene!
"g propene poly#propene$
C
C
H
H
H
n C C
H H
H
n

CH
3
CH
3
"g but-%-ene poly#but-%-ene$
C
C
H
H
C C
H
H
n

n
CH
3
CH
3
CH
3
CH
3
&any useful polymers are addition polymers made by this process!
polyethene is used in plastic bags and in crates
polypropene is used in plastic tubing
polychloroethene #polyinylchloride$ is used in waterproof clothing and records
H
H
C
C
H
H
C C
H
H
n

n
Cl
Cl
polyphenylethene #polystyrene$ is used in packaging
H
H
C
C
H
H
C C
H
H
n

n
The most faourable conditions for the polymerisation of alkenes can be deduced from
'e (hatelier)s principle, if two points are noted!
- the reaction inoles breaking -bonds only, and many -bonds are made. The
reaction is thus e*othermic.
- The reaction inoles a reduction in the total number of moles!
Since the reaction is e*othermic, the best yield is obtained at low temperature. Since the
number of gas moles decreases, the best yield is obtained at high pressure.
Addition polymerisation reactions are carried out at i! press"re in the presence of a
s"ita#le $atalyst.
ii) Properties of addition polymers
Addition polymers #polyalkenes$ are long chain hydrocarbons which are saturated and
non-polar. Their structure results in their haing a number of characteristic properties!
a$ Since the hydrocarbon chains are often ery long, the +an der ,aal)s forces between
the chains are often ery strong and the polymers hae relatiely high melting and
boiling points. Since the chain length is ariable, most polymers contain chains of a
ariety of different lengths. Thus the +an der ,aal)s forces are of ariable strength
and these polymers tend to melt gradually oer a range of temperatures rather than
sharply at a fi*ed temperature. As the chains are not rigidly held in place by each
other, polymers tend to be reasonably soft.
b$ Since the chains are non-polar, addition polymers are insoluble in water. Since the
intermolecular forces between the molecules are strong and the chains are often
tangled, they are generally insoluble in non-polar solents as well. -n fact the long
saturated hydrocarbon chains result in polyalkenes being ery unreactie generally, as
they cannot react with electrophiles, nucleophiles or undergo addition reactions.
This results in their widespread use as inert materials - they are ery useful as
insulators, as packaging and in making containers.
.oweer their low reactiity means that they are not easily decomposed in nature and
as a result hae a ery long lifetime. Such substances are said to be non%
#iode!rada#le, and constitute an enironmental ha/ard as they are ery persistent in
nature and thus difficult to dispose of.
c$ The density and strength of addition polymers aries widely. They depend to a certain
e*tent on the length of the hydrocarbon chain, but depend much more strongly on the
nature and e*tent of the branching on the chain.
0olymers which hae ery few branches are ery compact and the chains can thus
pack together ery efficiently!
These polymers tend to hae a ery high density. Since the chains are closely packed,
the +an der ,aal)s forces between the chains are strong and these polymers tend to be
stronger and harder as well.
0olymers which are highly branched cannot pack together as well, and there tend to
be large spaces in the structure!
These polymers hae a much lower density. Since the chains are not closely packed,
the an der ,aal)s forces between the chains are weaker and these polymers tend to
be weaker and softer.
&ONDENSATION POLYMERS
i) Polyesters
-t has been shown that if a carbo*ylic acid or acyl chloride is reacted with an alcohol,
then an ester is formed and a small molecule is lost.
"g ethanoyl chloride 1 ethanol ethyl ethanoate 1 .(l
C
O
C
H
H
H
CH
3
C
O
O
CH
2
CH
3
CH
2
CH
3
CH
2
OH
+
+
HCl
Cl
"g ben/oic acid 1 methanol methyl ben/oate 1 .%2
OH
C
O
+
+ H
2
O
CH
3
OH C
O
O
CH
3
These are e*amples of condensation reactions 3 combination of two or more molecules
followed by the elimination of a small molecule.
-t follows that if a dicarbo*ylic acid is reacted with a diol, then the -(22. group at each
end of the dicarbo*ylic acid should join to an -2. group, and the -2. group at each end
of the diol should join to a -(22. group. -t should therefore be possible for all the
molecules to link together and form a polymer.
"g ben/ene-4,5-dicarbo*ylic acid and ethan-4,%-diol
C
O
O H
C
O
O H
C C
H
O
H
H
O
H
H H
ben/ene-4,5-dicarbo*ylic acid ethan-4,%-diol
These two compounds can link together to form a polymer, and water is gien off!
C
O
O H
C
O
O H
C C
H
O
H
H
O
H
H H
C C
H
O
H
H
O
H
H H
C
O
C
O
C C
H
O
H
H
O
H
H C C
H
O
H
H
O
H
H
C
O
O H
C
O
O H
This polymer can be represented by the following repeating unit!
C C
O
C C
H
O
H
H
O
H
O
n

The oerall e6uation can be represented as!
C C
O
C C
H
O
H
H
O
H
O
n

H
H O
C
O
O H
C
O
O H
C C
H
O
H
H
O
H
H H
+
n n
(2n-1) H
2
O
+
The monomer units are linked together by the ester group!
C
O
C O
0olymers containing this type of linkage are therefore known as polyesters.
The aboe polymer is known as terylene. -t is used in fire-resistant clothing #eg racing
driers$
The same polyester can also be formed by the combination of a diacyl chloride and a
diol!
"g ben/ene-4,5-diacyl chloride and ethan-4,%-diol
C C
H
O
H
H
O
H
H H
C
O
C
O
Cl Cl
These two monomer units link together to form the same polymer. The only difference is
that .(l instead of .%2 is gien off.
The oerall e6uation can be represented as!
C
O
C
O
C C
O
C C
H
O
H
H
O
H
O
n

H
C C
H
O
H
H
O
H
H H
+
n n
(2n-1) HCl
+
Cl
Cl Cl
The polymerisation reaction with diacyl chlorides produces a much better yield than the
corresponding polymerisation reaction with dicarbo*ylic acids. This is because acyl
chlorides are more reactie than carbo*ylic acids and also because the .(l produced is
gaseous and thus escapes, making the reaction more difficult to reerse.
Thus dicarbo*ylic acids are generally conerted to diacyl chlorides #by addition of 0(l7$
before a polymerisation is carried out.
Another e*ample of polyester formation is!
"thanediacyl chloride and propan-4,%-diol
C C O
H
H
O
H
O
n

C C
O
O
C
O
H
C C O
H
H
O
H
H H
+
n n
(2n-1) HCl
+
Cl
Cl
Cl
C
CH
3
CH
3
ii) Polyamides
-t has been shown that if a carbo*ylic acid or acyl chloride is reacted with a primary
amine, an N-substituted amide is formed!
"g propanoic acid 1 ethylamine 88 N-ethylpropanamide 1 .%2
C
O
C
H
C
H
H
H
H
OH
+
CH
2
CH
3
H
N
H
C
O
CH
2
C
H
H
N
H
CH
3
C
H
H
H
+ H
2
O
"g ethanoyl chloride 1 4-aminopropane N-propylethanamide 1 .(l
C
O
C
H
H
OH
H
+
+ H
2
O
H
CH
2
CH
3
H
N
H
CH
2
C
O
C
H
H
N
H
C
H
H
CH
3
C
H
H
-t follows that if a dicarbo*ylic acid is reacted with a diamine, the -(22. group at each
end of the dicarbo*ylic acid with join to an -N.% group, and the -N.% group at each end
of the diamine will join to a -(22. group. -t should therefore be possible for each of the
molecules to join together and form a polymer.
"g he*anedioic acid 1 4,9-diaminohe*ane
(CH
2
)
4
C C
O
O
HO
OH
(CH
2
)
6
N
N
H
H
H
H
These two compounds can link together to form a polymer, and water is gien off.
(CH
2
)
6
N
N
H
H
H
H
(CH
2
)
4
C C
O
O
HO
OH
(CH
2
)
4
C C
O
O
HO
OH
(CH
2
)
4
C C
O
O
HO N
H
(CH
2
)
6
N
H
H
(CH
2
)
6
N N
H
H
H
H
The polymer can be represented by the following repeating unit!
(CH
2
)
4
C C
O
O
N
H
N
H
n

HO
(CH
2
)
6
H
The oerall e6uation can be represented as!
(CH
2
)
4
C C
O
O
N
H
N
H
n

HO
(CH
2
)
6
H
(CH
2
)
6
N N
H
H
H
H
(CH
2
)
4
C C
O
O
HO
OH
n
+
+
(2n-1) H
2
O
The monomers are linked together by the amide, or peptide link!
C
O
N
H
0olymers containing this type of linkage are therefore known as polyamides.
The aboe polymer is known as nylon ''. -t is a man-made fibre used in clothing
The same polyamide can be formed by the combination of the diacyl chloride and the
diamine!
(CH
2
)
6
N
N
H
H
H
H
(CH
2
)
4
C C
O
O
Cl Cl
These two monomer units link together to form the same polyamide. The only difference
is that .(l is gien off instead of water.
The oerall e6uation can be represented as!
(CH
2
)
6
N N
H
H
H
H
(CH
2
)
4
C C
O
O
Cl Cl
n
+
n
(CH
2
)
4
C C
O
O
N
H
N
H
n

Cl
(CH
2
)
6
H
+
(2n-1) HCl
The polymerisation reaction with diacyl chlorides gies a much better yield than with the
corresponding dicarbo*ylic acid for the same reasons as with the polyesterification
reaction. :icarbo*ylic acids are therefore conerted to the corresponding diacyl chloride
#by addition of 0(l7$ before the polymerisation is carried out.
Another e*ample of polyamide formation is!
;utanedioyl chloride and 4,% diaminopropane
+ +(2n-1) HCl n CH
2
N N
H
H
H
H
C
CH
3
H
n
(CH
2
)
2
C C
O
O
Cl
Cl
N N C C
O
O
H
H
H
C
n

CH
2
H (CH
2
)
2
Cl
CH
3

0olyesters and polyamides are collectiely known as $ondensation polymers because
they are the product of condensation reactions.
iii) Properties and "ses of $ondensation polymers
(ondensation polymers tend to consist largely of straight chains with few branches. This
is because they are formed by reactions with heterolytic mechanisms, which are much
less random than homolytic mechanisms. Addition polymers are formed by free radical
addition mechanisms which always lead to a ariety of products and conse6uently much
more branching.
Since there are few branches in condensation polymers, they are usually linear and can
thus pack closely tegether. (ondensation polymers are therefore more rigid than addition
polymers and hae a higher tensile strength.
The strength of the intermolecular forces between the different chains in polyamides is
further enhanced by the presence of hydrogen bonding.
C
O
N
H
N
H
C
O . . .
. . .
C
O
N
H
N
H
C
O
0olyamides are therefore generally ery strong. -n some natural polyamides, such as
proteins, intramolecular hydrogen bonding is possible and the molecule curls up to form a
helical structure!
...
.....
.....
hydrogen bonding
0olyamides and polyesters are both used largely in high-strength synthetic fibres.
0olyesters are used as wool and cotton substitutes in clothing #esp jumpers, T-shirts,
shirts etc$ and also in carpets and rugs. ;ullet-proof ests and some flame-retardant
clothing are made from polyesters.
0olyamides are more elastic and used in underwear, fishing nets and other synthetic
fibres.
0erhaps the most important difference between condensation polymers and addition
polymers is that condensation polymers are made up of chains containing polar bonds<
i.e. (-N and (-2 bonds which link eery polymer unit. These polar carbon atoms can be
readily attacked by nucleophiles and as a result the polymers can be broken up and the
constituent monomers reformed. (ondensation polymers are hence #iode!rada#le, and
so clearly constitute a smaller enironmental ha/ard than addition polymers, whose
chains are made up entirely of non-polar (-( bonds and which are hence non-
biodegradable.
The break-up of these polymers is carried out in a6ueous solution and can be classed as
ydrolysis reactions!
0olyesters are best hydrolysed in strongly alkaline conditions, in which they undergo
saponification!
+
n n
+
C C
H
O
H
H
O
H
H H
O
C
O
C
O
O Na Na + +
- -
C
O
C
O
O C C
H
H
H
O
H
n

H
HO
2n NaOH + H
2
O
0olyamides are best hydrolysed in strongly acidic conditions!
(CH
2
)
4
C C
O
O
HO
OH
(CH
2
)
4
C C
O O
N
H
N
H
n

HO
(CH
2
)
6
H n
+ (2n-1) H
2
O + 2n HCl
+
H
Cl (CH
2
)
6
N
N
H
H
H
H
H
Cl
+ -
+ -
n
The biodegradability of condensation polymers may compromise their effectieness,
since physical and chemical durability is one of the reasons for their widespread use. A
balance must be struck between practical durability and long-term biodegradability.
DISPOSAL AND RE&Y&LIN( OF POLYMERS
The disposal of non-biodegradable polymers is a significant problem. There are three
options!
- #"ryin! in landfill sites
This is widespread in all deeloped countries but is a completely unsustainable
practice, as each landfill site will eentually fill up. 'andfill sites are also unsightly
and unhygienic.
- #"rnin!
This is also common, but burning polymers releases greenhouses gases such as
carbon dio*ide and can also release to*ic gases, depending on e*actly what polymer
is being burned
- re$y$lin!
This is enironmentally preferable to burying or burning, but it is not easy. :ifferent
plastics need to be collected, separated and cleaned. They then need to be melted
down before being recast into the new item. 2ften this process can cost more than it
costs to manufacture the plastic from crude oil.
Some plastics cannot be melted 3 they burn or harden instead of melting. -t is een
more difficult to recycle these plastics as they can only be used in the same shape in
which they were originally cast.
The aboe problems mean that the continued manufacture of non-biodegradable
polymers is a cause for enironmental concern.
;iodegradable polymers decompose naturally, so burying them is slightly less
enironmentally unsustainable as they will eentually break down.
They can be recycled, broken down into their original components and reused, but they
still need to be collected, separated and cleaned.
S)MMARY OF POLYMER FORMATION AND *YDROLYSIS REA&TIONS
Type of rea$tion Me$anism
4. Addition polymerisation +alkenes polyalkenes)
conditions! high temperature, =iegle-Natte catalyst
e6uation!

C C C C
n

n
%. &ondensation polymerisation
a$ polyesters
dicarbo*ylic acid 1 diol polyester
conditions! .%S25, heat under reflu*
e6uation!
C C
O O
HO OH
R
1
O O R
2
H H
O
H O O
O
n

R
2
R
1
C C
HO
n +
n
+
(2n-1) H
2
O
or
diacyl chloride 1 diol polyester
conditions! room temperature
e6uation!
C C
O O
R
1
Cl Cl
O
H
Cl
O O
O
n

R
2
R
1
C C
O O R
2
H H
n
+
n
+
(2n-1) HCl
b$ polyamides
dicarbo*ylic acid 1 diamine polyamide
conditions! warm, reflu*
e6uation!
C C
O O
N
H
N
H
n

HO
H
R
1
R
2
C C
O O
HO OH
R
1 n +
n +
(2n-1) H
2
O N N
H
H
H
H
R
2
or
diacyl chloride 1 diamine polyamide
conditions! room temperature
e6uation!
>ree radical
addition
#not
re6uired$
Nucleophilic
addition-
elimination
#not
re6uired$
C C
O O
N
H
N
H
n

H
R
1
R
2
Cl
C C
O O
R
1
Cl Cl
n +
N N
H
H
H
H
R
2
n
(2n-1) HCl
+
?. *ydrolysis of $ondensation polymers
a$ polyesters
reagents! Na2.#a6$
conditions! heat
e6uation!
O O R
2
H H
O
H O O
O
n

R
2
R
1
C C
HO
n
+ n + 2n NaOH C C
O O
R
1
O
O
- - +
Na +
Na
+
H
2
O
b$ polyamides
reagents! .(l#a6$
conditions! heat
e6uation!
C C
O O
N
H
N
H
n

HO
H
R
1
R
2 C C
O O
HO OH
R
1
n +
n
+
(2n-1) H
2
O + 2n HCl Cl
N
N
H
H
H
H
H
Cl
+ -
+ -
H
R
2
n@a
n@a