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

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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.

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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

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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

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Examples of Anionic Polymerization
Products
Acrylonitrile (H2C=CHCN), methyl methacrylate
[H2C=C(CH3)CO2CH3], and styrene (H2C=CHC6H5)
react

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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 Nylon 6: made by

the six-carbon adipic acid polymerisation of the six-
and the carbon carbon caprolactam
hexamethylenediamine

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Polycarbonates
Carbonyl group is linked to two OR groups,
[O=C(OR)2]
E.g.: Lexan, unusually high impact strength machinery
housing, bicycle safety helmets and bulletproof glass

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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 (RN=C=O) gives a urethane
Polyurethane prepared from reaction between a diol and
a diisocyanate.

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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, Tg

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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:
amorphous and non-crystalline e.g. poly(methyl methacrylate),
polystyrene
Partially crystalline e.g. poly(ethylene terephthalate)

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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 cross-linking 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 gutta-percha

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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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