Polymers are giant molecules that are made up of many, many smaller molecules.

Building blocks for polymers are called monomers.

Examples: plastics, rubber etc.

Biopolymers: proteins, polysaccharides, nucleic acids

PolymersPolymers

PolymersPolymers

ProteinsBiopolymers:

• Basic building blocks are amino acids• Amino acids linked together into proteins by amide groups

• Peptide bonds formed by condensation reactions between two amino acids.

e.g. Alanine + Glycine:

Gly Ala Gly-Ala

NN

N

O

O

* *

H

H

H

R1 H

H R2

R = any amino acid

Representative structure of a segment of protein

PolymersPolymers

Biopolymers:

PolymersPolymersAmino acids:

PolymersPolymers

Representative segment of cellulose: a tough fibre.

Polysaccharides (Carbohydrates)

• Monosaccharides linked together by ether-bridges

PolymersPolymersNucleic acids

Composed of:

H3PO4 molecule

Organic base

5-C sugar

PolymersPolymers

In order to get a polymer formed we need a bifunctional molecule.

Y Y

X

X X

Y

(-XY)

PolymersPolymersAddition Polymerization

Example: ethylene H2C=CH2, can polymerize by opening the C–C bond to form C–C bonds with adjacent ethylene molecules (with the help of radicals).

The result: polyethylene.

This is called addition polymerization because ethylene molecules are added to each other.

PolymersPolymersStep 1 Initiation: generation of radicals from catalyst

Step 2 radical adds to ethylene and polymerisation starts

PolymersPolymers

Step 3 Propogation: repeated addition of carbon radical to other ethylene molecules

In CH2CH2.

H2C CH2 In CH2CH2CH2CH2.

+

In (CH2CH2)nCH2CH2.Repeat

many times

Step 4 Termination: radicals consumed to stop the reaction

PolymersPolymers

Styrene monomer

Draw a segment of polystyrene that consists of four styrene molecules added together.

Now what is the repeating unit?

PolymersPolymers

This is the repeat unit

PolymersPolymers

Poly(vinyl chloride) has the following structure

Cl Cl Cl n

Simplify the above to show its repeat unit only.

What is the monomer of the above polymer?

PolymersPolymers

repeat unit

PolymersPolymersCondensation Polymerization

Condensation Polymerization: molecules are joined by the elimination of a small molecule (e.g. water):

Example of condensation polymerization: formation of nylon.

N

H

H H O C

O

+ N

H

C

O

H O H+

PolymersPolymers

O

HO

O

OHH2N

NH2

Heat

O

O

NH

HN

n

HO

H2n

+

+

Adipic acid Hexamethylenediamine

Nylon 66

PolymersPolymers

N

OH

H2O

O

HONH2

Caprolactam 6-aminohexanoic acid

Another example of a condensation polymerisation is the formation of nylon 6.

Used for clothing and mountaineering ropes amongst others

PolymersPolymers

O

HONH2

6-aminohexanoic acid

Show the condensation product of this molecule that occurs between itself.

PolymersPolymers

PolymersPolymers

Terylene is a polymer used for the carbonated drinks market as it has a low permeability towards CO2 and prevents the drink from going 'flat'.

O

OH

O

HO

HOCH2CH2OH+

Draw a section of the polymer containing just the repeat unit

PolymersPolymers

PolymersPolymersTypes of Polymers

Plastic Materials that can be formed into shapes by application of heat and pressure.

Thermoplastics:

• Hard at room temp.• Become soft + viscous when heated. can be shaped more than once.• Little or no cross-linking individual chains can slip past each other.• E.g.’s include polyethylene, nylon, polystyrene….

Thermosetting resins:PolymersPolymers

• Become highly cross-linked when heated. solidify into a hard, insoluble mass.• Can only be shaped once, polymerisation irreversible.• Can withstand high temperatures.• For example, Bakelite; used for adhesives, moulded parts and coatings:

Phenol formaldehyde

PolymersPolymersElastomers:• Have the ability to stretch out & spring back to their original shapes.• Have a modest amount of cross-linking.• Polymer chains have irregular shapes.• Most common example is natural rubber

PolymersPolymersStructure and Physical Properties of Polymers

Polymer chains tend to be flexible and easily entangled or folded due to free rotation around the C–C single bonds.

Some regions of the polymer, may however, display a more ordered arrangement of chains than other regions:

PolymersPolymersStructure and Physical Properties of Polymers

The degree of crystallinity is a measure of the extent of such ordering.More ordering in a polymer = denser, harder, less soluble polymers that are more resistant to heat.

e.g. Properties of PE as a Function of Crystallinity.

PolymersPolymers

Structure and Physical Properties of Polymers

Stretching or extruding a polymer can increase crystallinity.

Degree of crystallinity is also determined by average molecular mass:

Low density polyethylene (LDPE) has an average molecular mass of 104 amu (used in plastic wrap);

High density polyethylene (HDPE) has an average molecular mass of 106 amu (used in milk cartons).

PolymersPolymers

Structure and Physical Properties of Polymers

LDPE:• Obtained by polymerization of ethylene at high pressure and high temperature.

• Polymer chains have irregular branches and cannot pack together in an ordered way.

• Result: LDPE is an open polymer of low density and little mechanical strength.

PolymersPolymers

Structure and Physical Properties of Polymers

HDPE:

• Polythene can also be prepared catalytically at lower pressures and temperatures.

• Result: regular non-branched chain polymer which is highly ordered or crystalline.

• HDPE is tough and strong and the ordered structure means that it has higher density.

PolymersPolymers

Structure and Physical Properties of Polymers

Polyethylene is a very versatile material & it’s properties can be “fine tuned” by varying:

PolymersPolymersCross-Linking Polymers

Bonds formed between polymer chains make the polymer stiffer.

Natural rubber is too soft and chemically reactive to make a useful material.

By vulcanizing the rubber (cross-linking the polymer chains) useful materials are made.

Rubber is usually cross-linked with sulfur.

Cross-linked rubber is stiffer, more elastic and less susceptible to chemical reaction.

PolymersPolymers

Cross-Linking Polymers