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 carbon–carbon
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 (RN=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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