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Lec7 8

Polymer structure can be described by its configuration and conformation. Configuration refers to the chemical bonding structure which cannot be changed without breaking bonds. Conformation describes the rotational structure which can change with rotation. There are two main polymer configurations - cis and trans, which describe the orientation of substituent groups around a double bond. Stereoregularity refers to the configuration of polymer chains and can be isotactic, syndiotactic, or atactic. Polymers are also classified based on their monomer composition into homopolymers or copolymers including block, graft, alternating, or statistical copolymers.

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142 views

Lec7 8

Polymer structure can be described by its configuration and conformation. Configuration refers to the chemical bonding structure which cannot be changed without breaking bonds. Conformation describes the rotational structure which can change with rotation. There are two main polymer configurations - cis and trans, which describe the orientation of substituent groups around a double bond. Stereoregularity refers to the configuration of polymer chains and can be isotactic, syndiotactic, or atactic. Polymers are also classified based on their monomer composition into homopolymers or copolymers including block, graft, alternating, or statistical copolymers.

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Structure of Polymer

Polymer Structure
terms configuration and conformation are used to
describe the geometric structure of a polymer
Configuration refers to the order that is determined by
chemical bonds it is cannot be altered unless chemical
bonds are broken and reformed
Conformation refers to order that arises from the
rotation of molecules about the single bonds

Polymer
Structure

Conformati
on
Cis
Configurati
on
Trans

Configuration
The two types of polymer configurations are cis and
trans
These structures can not be changed by physical means
(e.g. rotation)
The cis configuration arises when substituent groups are
on the same side of a carbon-carbon double bond
Trans refers to the substituents on opposite sides of the
double bond.

Stereoregularity
used to describe the configuration of polymer chains
Isotactic is an arrangement where all substituents are on
the same side of the polymer chain
A syndiotactic polymer chain is composed of alternating
groups and atactic is a random combination of the groups

Isotactic

Syndiotactic

Tacticity
Tacticity stereoregularity of chain
isotactic all R groups on
same side of chain

syndiotactic R groups
alternate sides

H H H H H H H H
C C C C C C C C
H R H R H R H R
H H H R H H H R
C C C C C C C C
H R H H H R H H

atactic R groups random

H H H H H R H H
C C C C C C C C
H R H R H H H R

Conformation
If two atoms are joined by a single bond then rotation about
that bond is possible since, and it does not require breaking
the bond.

The ability of an atom to rotate this way relative to the


atoms which it joins is known as an adjustment of the
torsional angle.

A separate kind of chain structure arises


when more that one type of monomer is
involved in the synthesis reaction. These
polymers that incorporate more than one
kind of monomer into their chain are called
copolymers.

Classification by Monomer
Composition
Homopolymer

Copolymer

Block

Graft

Alternating

Homopolymer
Consist of only one type of constitutional repeating unit (A)
AAAAAAAAAAAAAAA
Copolymer
Consists of two or more constitutional repeating units (A.B
)

Statistical

Several classes of copolymer are possible


Statistical copolymer (Random)
ABAABABBBAABAABB
two or more different repeating unit
are distributed randomly
Alternating copolymer
ABABABABABABABAB
are made of alternating sequences
of the different monomers
Block copolymer
AAAAAAAAABBBBBBBBB
long sequences of a monomer are
followed by long sequences of
another monomer
Graft copolymer
AAAAAAAAAAAAAAAAAA
B
B
B
B
B
B

(d)

POLYMERIZATION AND
STRUCTURE OF POLYMERS

POLYMERIZATION
chemical process where monomers linked
into polymers in repeating unit to make
longer and larger molecules

Chain
Reaction
Polymerizatio
n

Also called additional


polymerization, with aids
of initiators to form
benzene or paraffin.

Step
Reaction
Polymerizatio
n

Also called condensation


polymerization, dissimilar
monomer joined into short
groups that gradually grow
with by product released.

Additional Polymerization

The straightforward addition of


monomers of the same kind
Homogeneous type : A +A AA-A-A-
or a different kind
Copolymer type
A-B-A-B-

: A +B+A+B

Condensation Polymerization

A condensation polymer is defined as


a polymer that involves loss of small
molecules during its synthesis, or
contains heteroatoms as part of its
backbone chain, or its repeat unit
does not contain all the atoms present
in the hypothetical monomer to which
it can be degraded.
Involves a polymerization reaction between two monomers with the
expulsion of a simple by product.

A+B AB + simple by

Polymerization mechanisms
- Step-growth polymerization

Step-Growth
Polymerization
Stage 1

Consumption
of monomer

Stage 2
Combination
of small fragments

Stage 3
Reaction of
oligomers to give
high molecular
weight polymer

Step-growth polymers
formed by the stepwise reaction between functional
groups of monomers
usually containing heteroatoms such as nitrogen or oxygen
Most step-growth polymers are also classified as
condensation polymers but not all step-growth polymers
release condensates
Step-growth polymers increase in molecular weight at a
very slow rate at lower conversions and reach moderately
high molecular weights only at very high conversion

Polymerization mechanisms
- Chain-growth polymerization

Chain-growth polymerization (or


addition polymerization)
linking together of molecules incorporating double or
triple carbon-carbon bonds
These unsaturated monomers (the identical molecules
that make up the polymers) have extra internal bonds
that are able to break and link up with other monomers
to form a repeating chain, whose backbone typically
contains only carbon atoms
Chain-growth polymerization is involved in the
manufacture of polymers such as polyethylene,
polypropylene, and polyvinyl chloride

Polymer Degradation

Polymer degradation is a change in the properties tensile


strength, colour, shape, etc of a polymer or polymer based
product under the influence of one or more environmental
factors such as heat, light or chemicals.

The term 'biodegradation' is limited to the description of


chemical processes (chemical changes that alter either the
molecular weight or solubility of the polymer)

Degradation:
CHEMICAL DEGRADATION
BIOLOGICAL DEGRADATION
MECHANICAL DEGRADATION
CHLORINE INDUCED CRACKING
THERMAL DEGRADATION
PHOTO DEGRADATION

Biological Degradation
Biodegradable plastics can be biologically
degraded by microorganisms to give lower
molecular weight molecules.

Chlorine induced cracking


Another highly reactive gas is chlorine,
which will attack susceptible polymers such
as acetal resin and polybutylene pipe work.
There have been many examples of such
pipes and acetal fittings failing in
properties in the US as a result of chlorineinduced cracking.

Chemical Degradation:
Polymers can be degraded by solvolysis and
mainly hydrolysis to give lower molecular weight
molecules.
The hydrolysis takes place in the presence of
water containing an acid or base.
Polymers are susceptible to attack by
atmospheric oxygen, especially at elevated
temperatures encountered during processing to
shape.

Thermal degradation
Thermal degradation of polymers is molecular
deterioration as a result of overheating.
At high temperatures the components of the
long chain backbone of thepolymercan begin
to separate (molecularscission) and react with
one another to change the properties of the
polymer.
The chemical reactions involved in thermal
degradation lead to physical and optical
property changes relative to the initially
specified properties.

Photo degradation
One of the disadvantages of using polymers in
high temperature conditions or in outdoor
applications degradation
environment negatively influences the service
life.
This process is called weathering - ageing an
irreversible chemical process,
undesired changes of properties of the polymers,
discoloration and loss of mechanical properties

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