11.

1 TYPES O F POLYMERISATION
Objectives
By the end of the subtopic the learner should be able to:
 Describe the characteristics of addition polymers as exemplified by polythene and PVC.
 Explain condensation polymerisation as in polyesters and polyamides.
 Predict the type of polymerisation reaction for a given monomer or pair of monomers.
 Deduce the repeat unit of a polymer obtained from a given monomer or pair of
monomers.
 Identify the monomer(s) present in a given section of a polymer molecule.
 Recognise the uses of polymers.

Introduction
 Polymers are large molecules made by linking together smaller molecules called monomers
e.g. polyethene, polyvinyl chloride, nylon, Kevlar, etc.
 A monomer is any molecule that is capable of reacting with a similar molecule repeatedly or
a different molecule and produces a repeated sequence.
 The process of combining monomers into polymers is called polymerisation.
 Polymers exist as homopolymers or copolymers.
 A homopolymer is a polymer made by joining similar monomer units into long chains e.g.
polyethylene, polyvinyl chloride, etc.
 A copolymer is made by joining two or more different monomers together into one long
chain e.g. nylon 6, 6, Kevlar, etc.
 There are two types of polymerisation
1. Addition polymerisation.
2. Condensation polymerisation

1. Addition polymerisation
 An addition polymer is formed when two monomers are added together and nothing else is
formed or eliminated.
 Alkenes or substituted alkenes are the monomers of addition polymerisation.
 The alkenes add to themselves in a heated and pressurized vessel in the present of a
catalyst.
 As the reaction proceeds, long molecular chains are formed (polymers).

Addition polymerization of polyethylene

 Monomer: Ethylene (C2H4)

 Conditions:
o 200oC temperature
o 2000atm pressure
o Oxygen as an initiator
 General reaction :( CH2=CH2) + (CH2=CH2) +……. [-CH2-CH2-] n
 The polymerization of ethylene to polyethylene takes place in three stages which are
o Chain initiation
o Chain growth (propagation)
o Chain termination

Chain initiation
 It is a two stage process where an oxygen peroxide breaks into two reactive free radicals,
the second stage involves the free radical initiator attacking and attaching itself to the
monomer.
 The peroxide breaks down according to the following equation:

.
ROOR ( peroxide ) h eat energy 2 RO (free radical initiator )
→

 The free radical then attacks and attaches itself to the monomer to form an activate
monomer according to the equation:

.
RO +CH 2=CH 2 → RO−CH 2−CH 2 ∙

 After activating the monomer, it needs to grow in a process called propagation

Chain growth (propagation)

 During chain propagation, the activated monomer attacks and attaches itself to the double
bond of another monomer molecule according to the following equation:

RO−CH 2−CH 2 ∙+n ( CH 2=CH 2 ) → RO−¿

 The “n” stands for any number of molecules usually above 1000.

 When the molecule grows to the desired size, the process has to be stopped.

Chain termination

 The chain cannot grow forever; it has to be terminated at some point.

 The second radical is used to terminate the process according to the following equation

RO−CH 2−¿

 ¿ is known as the repeating unit of the formed polymer.

 All addition polymers are synthesized by the same procedure with different conditions of
temperature, pressure and catalyst used.

General characteristics of addition polymers

 They are long chain unsaturated polymers which are non-polar.

 Since they are long, the Van-der-waals forces that hold them together are relatively strong
resulting in addition polymers having high melting and boiling points.
 Insoluble in water due to non-polarity.
 Insoluble in non-polar solvents as well due to the strong intermolecular forces holding them
together.
 Straight chain addition polymers have high densities because the can pack easily.
 Branched addition polymers have low densities as they cannot pack easily.
2. Condensation polymerization

 Condensation polymerization occurs when:

o The monomer is bi-functional
o A molecule is eliminated e.g. H 2 O, HCl .
 Condensation reactions are a combination of both addition and elimination reactions.
 The most important polymers produced by condensation polymerization are esters e.g.
Terylene and amides (peptides) e.g. nylon 6, 6.

Condensation polymerization of polyesters

 Polyesters are generally formed from either of the two pairs:
o A di-carboxylic acid and a diol OR
o A di-acyl chloride and a diol

Example: Terylene

 Monomers: benzene-1,4-dicarboxylic acid and ethane-1,2-diol.

Figure 11.1.1: Condensation polymerisation of a polyester

 Reaction conditions: H2SO4, heat under reflux

 Reaction type: esterification
 By-product eliminated: water
 Main product formed: Polythylene terephthalate (Terylene)
 Repeat unit:

Figure 11.1.2: Structure of Terylene

 The polymer is linked by the following ester group:

Figure 11.1.3: The ester linkage

 The linking group is called an ester hence all polymers that have this repeating unit are
called polyetsrs
 The same product can be formed if benzene-1,4-diacyl chloride is used instead of benzene-
1,4-dicarboxylic acid.
 The use of a diacyl chloride eliminates hydrochloric acid, HCl instead of water, H 2 O.

Figure 11.1.4: Condensation polymerisation using an acyl chloride

 The same repeat unit is achieved and the difference is that HCl is eliminated.
 Polymerisation using di-acyl chlorides produces better yields compared to that of di-
carboxylic acids because:
o Di-acyl chlorides are more reactive than di-carboxylic acids.
o The reaction produces HCl as a gas which escapes thus making the reaction very difficult
to reverse.
 To improve yield dicarboxylic acids are converted to di acyl chlorides by addition of PCl 5.

Condensation polymerisation of polyamides

 If a carboxylic acid or acyl chloride is reacted with a primary amine, an amide is formed.
Example is Nylon 6, 6
 Monomers: Hexanedioic acid and hexane-1,6-diamine.

Figure 11.1.4: Amide link formation from a carboxylic acid and amine

 Reaction conditions: warm, reflux

 Reaction type: Addition-elimination
 By product eliminated: Water
 Main product formed: Nylon 6, 6.
 Repeat unit:

Figure 11.1.5: Structure of nylon 6, 6

 The monomers are linked together by the amide, or peptide link:

 Figure 11.1.6: Amide linkage

 Polymers containing this type of linkage are therefore known as polyamides.

Predicting type of polymerisation

 The type of polymerisation can be predicted from either the monomer or polymer given.

Predicting addition polymerisation from monomer

 If the monomer contains a double carbon-carbon bond C=C , the monomer will undergo
addition polymerisation.
 Addition polymers are usually homopolymers although copolymers are possible.
 If the repeating unit’s main chain contains only carbon atoms, the polymer must be have
been produced by addition polymerisation.

Example
Predicting condensation polymerisation
 If the monomer does not contain a double carbon-carbon bond then it is condensation
polymerisation.
 For polyesters the monomers contain these pair of functional groups: −COOH ∧−OH or
– COCl ∧−OH .
 For polyamides the monomers contain these pairs of functional groups−COOH ∧−NH 2 or
COCl∧NH 2 .
 If the repeat unit`s main chain contains either nitrogen or oxygen, the polymer must have
been produced by condensation polymerisation.
Deducing repeat unit for addition polymers
 Consider the simplest alkene as an example:

 It is very easy to deduce the repeating unit of an addition polymer.

 Draw at least three monomers of the alkene side by side as shown below:

 The ethene monomers add together by opening up of the carbon-carbon bond of the first
monomer, which then attacks the next and the next until the process is terminated.

 The monomers then join up together to form a long chain which contains the repeating
units as shown below.

Identifying monomers in addition polymers

 For easy understanding, we will use the polyacrylonitrile repeat as an example.
 Look for the repeating unit i.e. the part where the molecule starts to repeat itself.
 The repeat unit must have at least two carbon atoms in the main chain.
 Now put a double bond on the carbon-carbon bond on the main chain.

Deducing repeat unit for condensation polymers

 For easy understanding consider part of the polymer nylon 6, 6

 To deduce the repeat unit of a polymer there are just two steps needed:
1. Identify a distinctive group and open a square bracket in it as shown in the example below:

2. Follow through the chain until just before the same functional group is about to repeat
itself and close the bracket:

Determination of condensation polymers monomer units

 From part of the nylon 6, 6 to determine the monomer units using the following steps:
1. Determine what the linkage is in the polymer and circle it as follows:
2. Determine the monomer units on either side of the linkage.
 If there is no nitrogen, the polymer is an ester and the monomer must have been
−COOH ∧−OH or – COCl ∧−OH .
 If there is nitrogen, the polymer is an amide and the monomers must have been
−COOH ∧−NH 2 or COCl∧NH 2 .
 In the nylon 6, 6 the link is an amide because of the presence of nitrogen therefore the
monomers are:

OR

Uses of polymers
 New packaging materials.
 Waterproof coatings for fabrics (such as for outdoor clothing).
 Fillings for teeth.
 Dressings for cuts.
 Hydrogels (for example for soft contact lenses and disposable nappy liners).
 Smart materials (for example shape memory polymers for shrink-wrap packaging).
General advantages of polymers
 Resistance to corrosion and chemicals.
 Low electrical and thermal conductivity.
 Low density, high strength-to-weight ratio.
 Wide choice of colours and transparencies.
 Ease of manufacturing and complexity of design possibilities.
 Relatively low cost.

Disadvantages of polymers
 Comparatively low strength and low dimensional stability.
They have low heat resistance.
 More susceptible to deformation under load.
 They are brittle at low temperatures and are flammable.

Table 11.1.1: Specific uses of polymers

Polymer Properties Uses
Low density polyethylene  Low density  Wrapping materials
(LDPE)  Low melting point  Carry bags
 Flexible  Milk bottles
 Soft  Squeeze bottles
High density polyethylene  High density  Kitchen utensils
(HDPE)  High melting point  Toys
 Hard  Grocery bags
Polyvinyl chloride  Water resistant  Electrical insulation
 Flame resistant  Sewage and drain
pipes
 Garden dose pipes
Polystyrene  Transparent  Tool handles
 Low density  Foam packing
 Good insulator  CD cases