CHAPTER 7

Synthetic Polymers

Polymers

Large molecules built up by repetitive bonding

together of monomers
Indicate repeating unit in parentheses
Synthetic polymers are classified by the
synthesis method:

Chain-growth
Step-growth

Chain-Growth Polymers

Produced by chain-reaction polymerization

Initiator (radical, acid or anion) adds to a
carboncarbon double bond of an unsaturated
substrate (a vinyl monomer) to yield a
reactive intermediate that reacts with a
second molecule of monomer and so on.
Common method is radical polymerisation
carried out with practically any vinyl
monomer.

Cationic polymerisation (acid catalysed)

Effective only with vinyl monomers containing

an electron-donating group (EDG) that
capable to stabilise the chain-carrying
carbocation intermediate.
E.g. :Isobutylene polymerisation

Anionic Polymerization (basic catalysed)

Vinyl monomers with electron-withdrawing

substituents (EWG) can be polymerized by
anionic catalysts
Chain-carrying step is conjugate nucleophilic
addition of an anion to the unsaturated
monomer

Examples of Anionic Polymerization

Products

Acrylonitrile (H2C=CHCN), methyl

methacrylate [H2C=C(CH3)CO2CH3], and
styrene (H2C=CHC6H5) react

Step-Growth Polymers
Produced by reactions in which each bond in the
polymer is formed independently, typically by
reaction between two different functional reactants

Nylon 66: reaction

between the sixcarbon adipic acid
and the carbon
hexamethylenediamin
e

Nylon 6: made by
polymerisation of the
six-carbon
caprolactam

Polycarbonates

Carbonyl group is linked to two

[O=C(OR)2]

E.g.: Lexan, unusually high impact strength

machinery housing, bicycle safety helmets
and bulletproof glass

OR groups,

Polyurethanes

Urethane - carbonyl carbon is bonded to both an

OR group and an NR2 group

Prepared by nucleophilic addition of an alcohol to

an isocyanate (R N=C=O) gives a urethane
Polyurethane prepared from reaction between a
diol and a diisocyanate.

Polymer Structure and Physical Properties

Polymers experience
substantially larger
van der Waals forces
than do small
molecules, producing
regions that are
crystallites.
Crystallites highly
ordered portions in
which the zigzag
polymer chains are
held together by van
der Waals forces.
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Heat Transitions

Heating at the melt transition temperature,

Tm, gives an amorphous material

Heating noncrystalline, amorphous polymers

makes the hard amorphous material soft and
flexible at the glass transition temperature, T g

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Thermoplastics

Have a high Tg and are hard at room

temperature
When heated, become soft and viscous can
be molded
The individual can slip past one another in the
melt because it has little or no cross-linking.
Some are:

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amorphous and non-crystalline e.g. poly(methyl

methacrylate), polystyrene
Partially crystalline e.g. poly(ethylene
terephthalate)

Plasticizers

Small organic molecules that act as lubricants

between chains
Added to thermoplastics to keep them from
becoming brittle at room temperature
Dialkyl phthalates are commonly used for this
purpose

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Fibers

Thin threads produced by extruding a molten

polymer through small holes in a die, or spinneret
then cooled and drawn out orients the
crystallite regions along the axis of the fiber and
adds considerable tensile strength
E.g.: nylon, dacron

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Elastomers

Amorphous polymers that have the ability to

stretch out and spring back to their original
shapes.
Have low Tg values and small amount of crosslinking to prevent the chains from slipping over
one another
When stretched, the randomly coiled chains
straighten out and orient along the direction of
the pull

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Natural Rubber and Gutta-Percha

The upper structure is rubber, a natural

elastomer
The lower structure is the nonelastic guttapercha

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Thermosetting resins

Polymers that become highly cross-linked and

solidify into a hard, insoluble mass when heated
Bakelite is from reaction of phenol and
formaldehyde, widely used for molded parts,
adhesives, coatings

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