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Polymers
Polymer: A long chain organic molecule consisting of
many repeating units called monomers or
mers.
Monomer (mer): Smallest repeating unit in a polymer.
Mer term is derived from the Greek word
meros.
Polymerization reaction: The reaction by which the
monomer units become chemically linked
together to form high molecular weight
molecule (polymer).
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I. The origin
Natural Synthetic
Proteins
Polysaccharides
Polyisoperine
DNA - RNA
Bakelite
Polyvinyl chloride
PMMA
Nylon
Classification
According to:
Molecular
shape
Molecular
structure
Molecular
size
Straight
Copolymer
Homopolymer
Isomeric
states
Stereo
isomers
Geometrical
isomers
II. The molecular characteristics
Molecular
chemistry
Atactic
Syndiotactic
Isotactic
Cis
Trans
Alternating
Random
Block
Graft
Bent
Kinked
Twisted
Linear
Branched
Cross linked
Network
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Thermoplasts Thermosets
III. The mechanical response at elevated temperature:
Paste Hard polymer
Cross linked and network polymers.
Hard polymer Soft polymer
Linear polymers with few branches and flexible
chains.

Brittle Elastomers
IV. The stress strain behaviour:
Plastic
Strain
S
t
r
e
s
s
Brittle
Plastic
Elastomers
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Polymer properties:
1- Molecular weight and degree of polymerization:
M.W of a polymer = M.W of mers X No. of mers
Degree of polymerization = Total No. of mers in a polymer
Average D.P. =Total No. of units / Total No. of molecules
M.W. and D.P. strength, stiffness, softening and
melting temperature.
Crystallinity depends on:
a- Complexity of Mol. Chemistry crystallinity
b- Side branches crystallinity
c- Co polymerization crystallinity
d- Network polymer Amorphous
e- Mol. weight crystallinity
Crystalline polymers strength, density, resistance to
dissolution , softening temperature.
2- Polymer crystallinity:
Usually Mesomorphous = Short range crystalline region in
amorphous material.
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Cross linking T
G
rigid and brittle
polymer
Plasticity T
G
3- Melting and glass transition phenomenon (T
g
):
2
ry
bonds in a polymer Breakage of bonds until milting.
Mol. weight amount of 2
ry
bonds melting point.

T
G
Amorphous polymers
(rigid solids)
Softening
(rubber like)
Liquid
Temp
Polymer
(a)
Polymer
(b)
Room
Temp
Still solid (i.e.
just behavior
change of solid
and no state
transformation)
4- Mechanical properties:
Polymers < metals and ceramics due to 2
ry
bonds.
E and tensile, impact and fatigue strengths.
Mol. Weight
Cross linking
Crystallinity
Degree of polymerization
Mechanical properties
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5- Viscoelastic creep:
Polymers are strain rate sensitive materials.
Cross linkage
Crystallinity
Creep
Fine cracks at highly stressed regions tensile stress access.
They are 5 I thickness with interconnected voids.
Causes:
1- Tensile stresses.
2- Thermal stresses.
3- Solvent action.
6- Crazing:
Polymerization reactions
Condensation
(With by product formation)
Addition
(No by product formation)
Characterized by:
1- Exothermic heat.
2- Polymerization shrinkage
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Characterized by:
1- Stepwise reaction.
2- Usually consists of more than one monomer species.
3- Small molecular weight due to by product elimination.
4- Slow reaction and short polymer chains.
5- The functional groups are amide, urethane, ester or sulfide.
a) Condensation Polymerization [step reaction]:
Characterized by:
1- No by - product.
2- Polymer is exact multiplication of the original reactant
monomer.
3- Faster reaction.
b) Addition Polymerization:
Stages:
i- Initiation.
ii- Propagation.
iii- Termination.
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By initiator like benzoyl peroxide to release free radical.
Initiator must be activated to release the free radicals.
Activation is done by:
1- Light: U.V., visible and rays.
2- Heat.
3- Chemicals: Dimethyl-p- toluidine and Louryl mercaptan.
i- Initiation:
Linear growth of molecules.
Shifting of free radical to the end of the growing chain.
Viscosity entrapment of some monomer residual
monomer.
ii- Propagation:
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It is the stoppage of the reaction.
It may occur in one of three ways:
1- Direct coupling.
iii- Termination:
2- Hydrogen atom transfer.
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3- Chain transfer.
Effect Types Nature The additive
Partial neutralization of 2
ry
bonds
flexibility .
ductility
T
G
Low Mol.
Wt.
molecules
1- Plasticizers
Prevent deterioration 0.006 methyl ester of
hydroquinone to MMA
2- Stabilizers
Inhibitors
-Impurities
-Hydroquinone
-Eugenol
- Oxygen
Bridging of linear chains by chemical
bonds strength
. T
G
resistance to solvent
action
3- Cross linking
agents
Usually transparent.
Sometimes opacifiers.
Dyes Dissolve in
monomer
4- Colorants
Pigments Separate
phase
Polymer additives: