Addition polymerisation

Addition polymerisation = reaction where many small molecules (monomers) join together to make a long chain molecule and nothing else. Addition polymers are usually formed by alkenes undergoing addition reactions with themselves. Some common examples include:
H H C H

ethene

C H

C6H5 C H

phenylethene

C H

CH3 C COOCH3

methyl 2-propenoate

C H

CN C COOCH3

methyl 2-cyanopropenoate

C H

chloroethene

tetrafluoroethene

propene

Catalysts are used for the polymerisation, and the exact mechanism depends on the catalyst and alkene (it is not electrophilic addition it is usually catalytic addition). Polyalkenes are inert (although can burn) this is partly due to the absence of any polar bonds. As they are inert, they are non-biodegradable.

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Condensation polymerisation
Condensation polymerisation = reaction where many small molecules (monomers) join together to make a long chain molecule with a small molecule (often water) also formed. Many natural polymers are condensation polymers, e.g. silk, starch and DNA. The two main types are polyesters and polyamides.

Polyesters
Esters are formed on reaction between carboxylic acids and alcohols. Polyesters are formed when dicarboxylic acids react with diols.

O HO C

O C OH HO OH HO

O C

O C OH HO OH

ethane-1,2-diol strong acid or specific enzyme

Terylene (PET) is a good example of a polyester, made as shown below:

O n HO C O C OH + n HO CH2 CH2 OH

benzene-1,4-dicarboxylic acid

ethane-1,2-diol strong acid or specific enzyme

Polyesters are hydrolysed (in the presence of strong acid or a specific enzyme) into their constituent acid and alcohol, so they are bio-degradable. The ester linkage (which is polar) is broken.

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Polyamides
Amides are formed on reaction between carboxylic acids and amines. Polyamides are formed when dicarboxylic acids react with diamines. Polyamides are hydrolysed (in the presence of strong acid or a specific enzyme), so they are bio-degradable. The amide linkage (which is polar) is broken. e.g. nylon-6,6 is a good example of a polyamide, made as shown below:
O n HO C (CH2) 4 O C OH + n H2N (CH2) 6 NH2

hexanedioic acid

hexane-1,6-diamine

strong acid or specific enzyme

e.g. Kevlar (used in bullet-proof vests) is a another good example of a polyamide, made as shown below:
O n H2N NH2 n HO C O C OH

benzene-1,4-diamine

benzene-1,4-dicarboxylic acid

Polyamides are also formed when amino acids react with each other. Nylon-6 is made from the polymerisation of the amino acid 6-aminohexanoic acid.
O n NH2 (CH2) 5 C OH
strong acid or specific enzyme

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Chemsheets A2 025