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CH2=CH2
Monomer
CH2-CH2 n
repeat unit
linear polymers
branched macromolecules
Linear Polymers
Branched Polymers
Homopolymers
A Polymer
P l
which
hi h contains
t i single
i l type
t
off repeatt units
it is
i referred
f
d
to as a homopolymer.
The repeat unit may contain one or more species of monomer
units.
units
Copolymers
Classification of Polymers
More than one criterion can be used as the basis for classification of polymers.
Eg.
g
Basis of Classification
Polymer Types
g
Origin
Natural, semi-synthetic,
y
synthetic
y
Mode of Formation
Addition, Condensation
Line Structure
Tacticity
Crystallinity
Thermal Response
Thermoplastic, Thermosetting
Origin
Chainreactionpolymers
(Addition polymers)
(Additionpolymers)
Mode of Formation
Stepreactionpolymers
(Condensationpolymers)
Eg Nylon
Eg.
Nylon, Polyester
Linear polymers
( can be represented by lines)
Line structure
Branched polymers
(can be represented b
by lines with
ith short
or long branches of repeat units)
Network polymers
(polymer chains are interconnected as a net)
Tacticity
Vi
Vinyll polymers
l
th
thatt h
have single
i l substituents
b tit
t ((e.g. propylene)
l
) or
two unsymmetrical substituents (e.g. methyl methacrylate) have
pseudoasymmetric carbon atoms in the backbone.
Then there are many possible relative placements of the groups.
The most common three versions are;
Crystallinity
Polymer molecules are very large so that they could not pack together
regularly and form a crystal.
It now is known that regular polymers may form lamellar (plate-like)
crystals with a thickness of 10 to 20 nm in which the parallel chains
are perpendicular to the face of the crystals.
Thermal Response
Plastics: These are usually much stronger than rubbers. They exhibit
tensile strengths ranging between 4,000-15,000psi and elongation at
breaks ranging
g g from 20-200%. eg.
g Polyethylene,
y y
polypropylene,
p
yp py
polystyrene
Fibres:
These are the strongest types of three different types of
polymers. Their tensile strengths are in the range of 20,000-150,00psi.
eg. Cotton, wool, silk, synthetic polyamides and polyester fibres and
acrylic fibres
Polymer
y
Nomenclature
There is no single nomenclature system. Difficulties are
associated with;
Tacticity
Copolymer arrangement
Structure irregularities
Imperfections
Methods
l
Trade names
n
CH3
CH
H2C
styrene
CH
C CH2
CH3
CH3
isobutylene
isoprene
H2C CH
C N
acrylonitrile
H2C
SourceBased(copolymers)
l
Infixes or connectives
n
-alt- (alternating)
-block- Polyacrylonitrile-block-polybutadiene
nonlinear blends
nonlinear,
blends, cross
cross-link,
link and net
network
ork
n
StructureBased(homopolymers)
l
CH3
CH3
CH3
Examples
1. Poly(1-acetoxyethylene) - structure
2. Poly(vinyl acetate) - source
1. Poly(but-1-ene-1,4-diyl)
2. Polybutadiene
y
1. Poly(1-cyanoethylene)
2. Polyacrylonitrile
1. Poly(methylene)
2. Polyethene;
y
p
polyethylene
y y
1. Poly[(2,5-dioxotetrahydrofuran3,4-diyl)(1-phenylethylene)]
2. Poly(maleic anhydride-alt-styrene)
CommonTradeNames
Selected examples
Crystalor
(polymethylpentene, Phillips)
(HDPE, Amoco)
Kevlar
Lexan
(polycarbonate, G.E.)
Lucite
(acrylic DuPont)
(acrylic,
Mylar
Nylon
y
((polyamides,
y
variations))
(polyethylene, Quantum)
Saran
Teflon
(tetrafluoroethylene, DuPont)
CommonAbbreviations
Selected examples
ABS
PC
(polycarbonate)
PET
[poly(ethylene terephthalate)]
PMMA
[poly(methyl methacrylate)]
PS
(polystyrene)
PVC
[poly(vinyl chloride)]
TP
Structure vs Properties
JJustt because
b
a polymer
l
i synthesized
is
th i d from
f
a pure
monomer, where all the molecules are initially identical,
does not mean that the final product consists of chains of
regularly arranged units.
Conformation
Two polymers which differ only by rotation about single bonds are said
to be two different conformations of that polymer.
Configurations
IsotacticSyndiotacticAtactic
Isomerism in polymers
An asymmetric monomer would produce polymers with a
variety of microstructures consisting of various types of
i
isomers.
Th mostt important
The
i
t t types
t
are;
1 Sequence isomers
1.
2. Configurational isomers
3 Structural isomers
3.
Configurational Isomerism
The same atoms are arranged in the same order but with
different orientations in space.
carbon
b
But when there is a carbon carbon double bond the two molecules are
not the same
cis isomer
has a amorphous structure
rubbery material
trans isomer
very
e y regular
egu a sstructure
uc u e
Crystalline
Plastics material
Stereoisomerism
Head to Tail
Head to Head
If the successive
s ccessi e configurations
config rations of the asymmetric
as mmetric carbons are
regular then the polymer is said to be stereo regular
a random arrangement
of ssubstituent
bstit ent groups
gro ps
Polymer
Tg atactic
Tg isotactic Tg syndiotactic
PP
20 C
0 C
8 C
PMMA
100 C
130 C
120 C
Structural isomerism
In structural isomerism, the atoms are arranged in a completely
different order. eg. Butane,C4H10
I.
Activity
Draw the structure of the repeat units of the polymers obtained in the
polymerization of the following monomers;
I.
CH2=CHCOOH
II. CH2=C(CH3)COOCH3
III. CH2=CHOCOCH3
Give the name(sources based) of each polymer produced
Polymer Morphology
Unfold structure
Folded Structure
E t
Entangled
l d St
Structure
t
Amorphous Polymers
Polymer chains with branches or irregular pendant groups can
not pack together regularly enough to form crystals. These
polymers are said to be amorphous.
Amorphous polymers are usually less rigid, weaker and more easily
deformed. They are often transparent and more affected by solvent
penetration.
Semi-crystalline polymers
Highly Crystalline
Highly Amorphous
Polymers
Polymers
Isotactic polypropylene
Poly(methylmethacrylate)
Syndiotactic polypropylene
Atactic polystyrene
Nylon
Polyisoprene
Kevlar
Polybutadiene
Polyketones
Polycarbonate
Polymer
o y e St
Structure;
uctu e;
Crystallization
C
t lli ti is
i favored
f
d by
b the
th stereo
t
regularity
l it off
the polymer chain
Syndiotactic polystyrene
Degree of Polymerization
Intermolecular Forces
The p
presence of p
polar and hydrogen
y g
bonding
g g
groups
p favors crystallinity
y
y
because they make possible dipole-dipole and hydrogen bonding
intermolecular forces.
A polyester,
polyester such as poly(ethylene terephalate),
terephalate) contains polar ester
groups.
Pendant Groups
Regular polymers with small pendant groups crystallize more readily than do
polymers with large, bulky pendant groups.
PVA
PVAc
PVA crystallizes more readily than PVAc because of the bulky acetate groups
in PVAc.