POLYMERS Polymers are usually divided into two categories: Addition polymers Condensation polymers ADDITION POLYMERS In addition polymerisation, a large number of molecules of a monomer combine to produce a polymer, but no other product is formed. The polymer has the same empirical formula as the monomer but has a larger molecular mass, which could be as high as 500,000. Polymerisation is initiated by a radical or an ion (this depends on the catalyst system which is used) which adds to a carbon-carbon double bond. For example: . X + CH2=CH2 X . CH2CH2 Further molecules of monomer then add sequentially to the reactive end, and the chain grows in length. The overall reaction for addition polymerisation can be represented as: H n R C ( C H H H R C C H H )n The repeating unit is enclosed within the brackets. n is a large number, which typically lies in the range 100 to 10,000. The end groups constitute such a small fraction of the polymer molecule that they are usually omitted. The backbone of a polyalkene molecule is made up of singly-bonded carbon atoms. The molecule is saturated and is chemically unreactive. These polymers are nonbiodegradable. The attractive forces between polymer chains are weak. This means that, on heating to relatively low temperatures, they soften and become mouldable: these are thermosoftening plastics. With the possible exception of p.v.c., these plastics are flammable. When heated, p.v.c. decomposes releasing HCl; this acts as a self-extinguisher. Examples of addition polymers are: Monomer ethene, CH2=CH2 propene, CH3CH=CH2 phenylethene, CH2=CHC6H5 chloroethene, CH2=CHCl Polymer Use poly(ethene) bags, buckets poly(propene) ropes, containers poly(phenylethene) yoghurt pots poly(chloroethene) window frames, (PVC) guttering, pipes propenenitrile, CH2=CHCN poly(propenenitrile) acrylic fibres tetrafluoroethene, CF2=CF2 poly(tetrafluoroethene) non-stick surface methyl 2-cyanopropenoate,CH2=C(CN)COOCH3 poly(methyl 2-cyanopropenoate) super glue TOPIC 13.10: POLYMERS 1 CONDENSATION POLYMERS Condensation polymers are formed by the reaction between molecules containing two functional groups. The reaction is accompanied by the elimination of a small molecule such as water. POLYESTERS A polyester may be formed by the reaction of a dicarboxylic acid and a diol. The reactants are heated together at temperatures up to 180oC, often in the presence of a titanium-containing catalyst. Water is released during the reaction. If the methyl ester of the dicarboxylic acid is used, there is less likelihood of subliming reactants/products blocking the condenser. In this case, methanol is released during the reaction. The most important polyester is formed from benzene-1,4-dicarboxylic acid and ethane-1,2-diol; it has the trade name Terylene. It is used to make plastic bottles, seat belts, parachute harnesses, magnetic recording tapes and fleece clothing. O O C C HO + OH HOCH2CH2OH loss of water HO O O C C OCH2CH2O H n repeating unit Hydrolysis Like simple esters, polyesters can be hydrolysed into their component monomer units. Polyesters are, therefore, biodegradable. For example: O O C C + OCH2CH2O 2n H2O n O O C n HO TOPIC 13.10: POLYMERS 2 C + OH n HOCH2CH2OH POLYAMIDES A polyamide may be formed by the reaction of a dicarboxylic acid and a diamine. The most important polyamide is nylon-6,6; it is called nylon-6,6 because it is made from a 6 carbon dicarboxylic acid, hexanedioic acid, and a 6 carbon diamine, 1,6diaminohexane. Nylon-6,6 is used to make fishing line, hosiery, casings for power tools, bearings, tyre cords and ropes. 1,6-diaminohexane is a base and reacts initially with hexanedioic acid to form a salt, known as nylon salt. When the salt is heated to about 250oC, water is liberated and the polymer, nylon-6,6 forms. O O C C (CH2)4 HO OH O O -O C C (CH2)4 O- + H2N(CH2)6NH2 + + + H3N(CH2)6NH3 nylon salt loss of water O O HO C (CH2)4 C NH(CH2)6NH H nylon-6,6 n repeating unit The two functional groups (carboxyl group and amine) can be in the same molecule, so when the amino acid, 6-aminohexanoic acid is heated, nylon-6 is formed. + H3N O (CH2)5 C O- O loss of water H NH (CH2)5 C OH n repeating unit nylon-6 TOPIC 13.10: POLYMERS 3 Hydrolysis Like simple amides and proteins, synthetic polyamides can be hydrolysed into their component monomer units. Polyamides are, therefore, biodegradable. For example: O NH (CH2)5 C + n H2O n TOPIC 13.10: POLYMERS 4 + n H3N O (CH2)5 C O-