Polymers F324 1

POLYMERISATION

General A process in which small molecules called monomers join together into large
molecules consisting of repeating units.

There are two basic types ADDITION & CONDENSATION

ADDITION
POLYMERS • all the atoms in the monomer are used to form the polymer
• occurs with alkenes
• mechanism can be free radical or ionic

Formula of monomer Formula of polymer Use(s)

Examples

poly(ethene) n CH2=CH2 —> — (CH2 — CH2)n —

poly(phenylethene)

poly(chloroethene)

poly(tetrafluoroethene)

poly(ethenyl ethanoate)
‘PVA’

Preparation Many are prepared by a free radical process involving high pressure, high
temperature and a catalyst. The catalyst is usually a substance (organic peroxide)
which readily breaks up to form radicals which, in turn, initiate a chain reaction.

Another famous type of catalyst is a Ziegler-Natta catalyst (named after the

scientists who developed it). Such catalysts are based on the compound TiCl4.

Properties
Physical Can be varied by changing the reaction conditions (pressure, temperature etc).

Chemical Are based on the functional groups within their structure.

eg poly(ethene) is typical; it is fairly inert as it is basically a very large alkane.

This means it is resistant to chemical attack and non-biodegradable.
2 F324 Polymers

CONDENSATION
POLYMERS • monomers join up the with expulsion of small molecules
• not all the original atoms are present in the polymer
• examples include polyamides nylon
polyesters terylene
peptides
starch

• reactions between diprotic carboxylic acids and diols

diprotic carboxylic acids and diamines
amino acids

POLYESTERS
COOH
Terylene Reagents terephthalic acid HOOC-C6H4-COOH
H H
ethane-1,2-diol HOCH2CH2OH

H H
Reaction Esterification COOH
Eliminated water

Product poly(ethylene terephthalate) ‘Terylene’, ‘Dacron’

Equation n HOCH2CH2OH + n HOOC-C6H4-COOH —>

− [-OCH2CH2OOC(C6H4)CO-] n − + n H2O

Repeat unit — [-OCH2CH2OOC(C6H4)CO-] n —

Structure

O CH 2 CH 2 CH 2 CH 2 CH2 CH2 O

Properties • contain an ester link δ−

• can be broken down by hydrolysis O
• the C-O bond breaks δ+ δ−
• behaves as an ester C O
• biodegradable

Uses •

•
Polymers F324 3

Poly(lactic
H
acid) Reagent 2-hydroxypropanoic acid (lactic acid)
HO C COOH
Reaction Esterification
CH3
Eliminated water

Equation n CH3CH(OH)COOH —> −[-OCH(CH3)CO-]n − + n H2O

Product poly(lactic acid)

Repeat unit — [-OCH(CH3)CO-] —

Structure
H H H O
O C C C C
CH 3 CH3 CH 3

Properties • contain an ester link

• can be broken down by hydrolysis
• the C-O bond breaks
• behaves as an ester (hydrolysed at the ester link)
• biodegradable
• photobiodegradable (C=O absorbs radiation)

Uses • waste sacks and packaging

• disposable eating utensils
• internal stitches

Q.1 Draw structures for the organic product(s) formed when poly(lactic acid) is treated
with the following reagents. [Hint: see page 5 of these notes]

• HCl(aq)

• NaOH(aq)

What name is given to this type of reaction?

4 F324 Polymers

POLYAMIDES
Nylon-6,6 Reagents hexanedioic acid HOOC(CH2)4COOH
hexane-1,6-diamine H2N(CH2)6NH2

Mechanism Addition-elimination

Eliminated water

Product Nylon-6,6 two repeating units, each with 6 carbon atoms

Equation n HOOC(CH2)4COOH + n H2N(CH2)6NH2 —>

− [-NH(CH2)6NHOC(CH2)4CO-]n− + n H2O

Repeat unit − [-NH(CH2)6NHOC(CH2)4CO-]n —

Structure O
C ( CH 2 )4 ( CH 2 )6 CH 2 )4

Properties • contain a peptide (or amide) link δ−

O
• can be broken down by hydrolysis
δ+ δ−
• the C-N bond breaks C N
• behave as amides
H
• biodegradable
• can be spun into fibres for strength

Uses •
•

NH 2 COOH
Kevlar Reagents benzene-1,4-diamine H H H H

benzene-1,4-dicarboxylic acid H H H H
NH 2 COOH
Product Kevlar

Structure

Use body armour

Polymers F324 5

Peptides • formed by joining amino acids together

• are examples of polyamides
• amino acids have two main functional groups -COOH carboxylic acid
-NH2 amine

• amino acids can join together using a peptide link δ−

O
δ+ δ−
• dipeptide two amino acids joined together
C N
tripeptide three amino acids joined H
polypeptide many amino acids joined together

• a protein is a polypeptide with a large relative molecular mass (>10000)

• peptides/proteins are broken down into the original amino acids by hydrolysis

Hydrolysis
H O CH3
HOO C C N C C NH 2 + H2O ——> HOOCCH2NH2
H H H +
HOOCCH(CH3)NH2

The acid and amine groups remain as they are

Acid
Hydrolysis H O CH3
HOO C C N C C NH 2 + 2HCl ——> HOOCCH2NH3+Cl¯
+
H H H
HOOCCH(CH3)NH3+Cl¯

The amine groups are protonated and the acid groups remain as they are

Base (alkaline)
Hydrolysis
H O CH3
HOO C C N C C NH 2 + 2NaOH ——> Na+ ¯OOCCH2NH2
H H H +
Na+ ¯OOCCH(CH3)NH2

The acid groups become sodium salts and the amine groups remain as they are
6 F324 Polymers

Q.2 Look up the structures of alanine and glycine. Draw the structure of the dipeptide
formed when they react together.

O O
Q.3 Look at the structure of H2N CH2 C N CH2 C OH
the following dipeptide. H

How many different amino acids formed the dipeptide? Draw their structure(s).

Give the formulae of the organic products formed when the dipeptide is
hydrolysed using...

a) NaOH(aq)

b) HCl(aq)