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II two or more molecules oI the same compound join the product is known as polymer.
Examples oI naturally occurring macromolecules are proteins and starch. Some times a
molecule Iormed by two smaller ones are called a dimer, by three a trimer.
Polymers are long chains oI repeating structural units, called monomers.
Polymerisation is the process whereby these small units are joined together to Iorm the
polymer.
There are two types of polymerisation--addition polymerisation and condensation
polymerisation.
ADDITION POLYMERIZATION
These are based on addition reactions such as those undergone by ethene. A common
Iactor in these reactions is the removal oI the double bond. Addition polymerisation
involves a series oI addition reactions such as those in polyethene, (trade name
polythene), under high P and T and in the presence oI catalyst, (E
A
Ior polymerisation is
high), ethene molecules join together.
The number oI repeating ethene unit-(-CH
2
CH
2
-)- in the complete molecule is 'n' plus the
two end groups. The value oI 'n' is usually greater than 100 and oIten exceeds 1000.
Generally some hundreds or even thousands, oI units are joined together in a single
molecule oI the polymer. Polymers are generally used as "plastic".
A monomer that contains a double bond oIten reacts in a process called an addition
reaction.
Special catalysts start the reaction by Iorming Iree radicals, and more Iree radicals are
then produced in a chain reaction. The net result is that the double bond opens (a - bond),
and then reIorms with two adjacent molecules. This kind oI chain reaction depends on the
presence oI an initiator which is nucleophilic. A peroxide such as dibenzoylperoxide
splits up into Iree radicals. II the Iree radical is represented by R, then the Iollowing steps
in the reaction occur.
R CH
2
CH
2
R - CH
2
- CH
2
R - CH
2
- CH
2
CH
2
CH
2
R - CH
2
- CH
2
- CH
2
- CH
2
R -CH
2
-CH
2
-CH
2
-CH
2
CH
2
CH
2
R - CH
2
- CH
2
- CH
2
- CH
2
- CH
2
- CH
2
The reaction may be terminated when (i) two chains add to each other (ii) another Iree
radical adds to chain, or (iii) two Iree radical, R, recombine.
The length oI the chains and the degree to which the chain is branched can be controlled
by varying the conditions oI the polymerisation and using diIIerent catalysts. Thus
polyethenes with a variety oI diIIerent properties can be obtained- they may be viscous
liquids or solids oI varying degree oI hardness. Addition polymers oI this type have a
wide range oI uses.
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Some Iamiliar polymers and the monomers Irom which they are made are listed below.
Name Monomer Typical Uses
Polyethylene CH
2
CH
2
Bottles, plastic gloves, Iood
wrap bags, garment bags
Polypropylene CH
2
CHCH
3
Indoor /outdoor carpeting
Polyvinyl chloride "(PVC) CH
2
CHCl (chloroethene) Credit cards, pipes, records
Polystyrene CH
2
CHC
6
H
5
Eoamed beads, packaging
blocks, ceiling tiles
TeIlon (PTEE) CE
2
CE
2
(tertaIluoroethene)
Non stick surIaces
As can be seen Irom the above table, one oI the hydrogen atoms oI ethene molecule may
be replaced by any oI a number oI other atoms or groups oI atoms - on polymerisation a
correspondingly modiIied product will be obtained.
Polyethene can be manuIactured in two Iorms by the use oI diIIerent catalyst and diIIerent
reaction conditions.
i) Low Density polyethene
This is cheap to produce and is oIten used Ior materials where great strength is not
necessary, have more branched chains.
ii) High Density polyethene
This is more expensive to produce but, in this Iorm, the polyethene is much stronger. The
linear chains are more tightly packed (hence higher density). This Iorm is used Ior making
milk crates, bleach bottles etc.
The importance oI these addition polymers oIten depends upon their lack oI chemical
reactivity. Where the alkene monomer is oI the Iorm CH
2
CHX ( where X is CH
3
-,
C
2
H
5-,
Cl-, etc) when polymerisation occurs, the X can be situated:
i) on the same side oI the chain, called isotactic
ii) on the alternate side oI the chain, syndiotactic
iii) randomly, atactic.
The type oI polymer determines the properties. In isotactic polymers the chains can
approach more closely. This increases the crystallinity oI the polymer.
Polymers can also be classiIied as thermosetting and thermoplastic.
All oI the addition polvmers are thermoplastic. This means that on heating they will
soIten and melt. As a result they can be remoulded or reIormed, hence recycled easily.
Thermosetting polvmers (i.e. condensation polvmers) do not melt on heating; they are
permanently hardened when Iormed. When heated the decompose and, thereIore, cannot
be worked in the same way.
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CONDENSATION POLYMERIZATION
A condensation reaction is a reaction in which two molecules join together to Iorm a
larger molecule with the loss oI a smaller molecules such as H
2
O, HCl, NH
3.
This process is based on nucleophilic attack on a carbonyl group and the subsequent
breaking oI the a -bond oI CO to join molecules together. Some condensation
polymerisations require two diIIerent molecules; reactions that Iorm esters and peptide
bonds are examples.
An example oI a condensation reaction that you have encountered beIore is esteriIication.
Conc. H
2
SO
4
CH
3
COOH CH
3
CH
2
OH CH
3
COOCH
2
CH
3
H
2
O
Also the reaction oI an alkanoic acid with an amine amide, has been encountered
previously. Another example is .
Each monomer may contain an acid and a basic Iunctional group, as shown above, in
which case there is only one reactant.
Another method oI producing a condensation polymer involves using one monomer that
contains two acid groups and another monomer that contains two basic groups. An equal
molar mixture oI these two monomers is used to Iorm the polymer.
Starch and cellulose are both condensation polymers oI glucose. The diIIerent physical
and chemical properties are due to the diIIerent arrangements oI the bonds in these two
polymers. Some common condensation polymers and their uses are listed below.
Name Monomer(s) Typical Uses
Terylene Ethanel, 2-dio
dimethylbenzene -1, 4-
dicarboxylate
Eibres, Iabric
Nylon 1, 6-hexanedicarboxylic
acid 1, 6-diaminohexane
Eibres, Iabric
proteins Amino acids Biological reactants, Iood
starch
Condensation polymerisation oIten results in cross-linking, under suitable conditions,
thus making the product thermosetting. These polymers are Iusible at some stage oI their
production but become permanently hard under the inIluence oI heat and pressure.
Crosslinking alters the physical properties oI the polymers. It increases the eIIective
molecular mass oI the polymer and aIIects its solubility. It also prevents the movement oI
the chain relative to nearby chains. Cross-linking oI some kind is essential iI the polymer
is to act as a Iibre.
Natural rubber is a natural addition polymer. It is unsuitable Ior use in making rubber
tyres unless it is treated with sulphur. Treatment with 30 sulphur hardens the rubber by
Iorming cross-links between chains. This process is called vulcanisation.
Polyamide chains are cross linked by hydrogen bonding.
In terylene, chains are linked by weaker dipole-dipole attractions. This takes place
because carbonyl groups are polarized.
In chains oI addition polymers such as polyethene, the only crosslinking is by van-der-
Waals' Iorces.
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POLYMER PROPERTIES
Polymers with polar, hydrogen-bonding Iunctional groups may be soluble in water
despite their tremendous size. This Iact explains the solubility oI proteins and polyvinyl
alcohols. Most other polymers, however, are insoluble. The length oI these polymers
allows them to align with each other, thereby generating substantial London Iorces oI
attraction.
Although addition polymers are prepared Irom monomers with double bonds, the Iinished
polymer has no double bonds. As a result, these polymers are Iairly inert. The most inert
is TeIlon, in which the very strong C-E bond ca not be broken easily.
Polymers have distinct properties which depend on the method used to manuIacture the
polymer. Branched chain polymers have diIIerent properties than linear polymers.
AMINO ACIDS AND PROTEINS
Amino acids are obtained by hydrolysis oI proteins. The amino acids can be represented
by.
H O
R C C
NH
2
OH
The simplest amino acids are :
i) aminoethanoic acid (glycine)
ii) 2-aminopropanaoic acid (alanine)
All amino acids except aminoethanoic acid contain an asymmetric carbon atom and
exhibit optical isomerism.
Amino acids are linked together by peptide linkages .
O H
- C - N -
Amino acid polymers are called polypeptides (molar mass 1000) , those with larger
molecular masses are called proteins ( test: CuSO
4 (aq)
NaOH
(aq),
, using ninhydrin
produces pink/purple spots on a chromatogram iI amino acids are present).