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origin
structure
methods of formation
response to heat
synthetic polymers
Natural polymers are those which are obtained naturally
e.g., Cellulose, Silk, Starch, RNA, DNA, Proteins etc.,
Synthetic polymers are those which are made by man
e.g., polyethylene, polystyrene, PVC, polyester, etc.,
semi-synthetic polymers which are chemically modified
natural polymers
polymers can be classified as
e.g., cellulose acetate, cellulose nitrate, halogenated
rubbers etc.,
Based on the molecular structure
polymers can be classified as
Linear
Branched
Cross-linked
the monomeric units combine linearly with each other
In linear polymers,
secondary bonding
Branch polymers
Cross linked polymers
Based on the method of formation
Addition polymers
Condensation polymers
Addition polymers are formed by self-addition of monomers
The molecular mass of a polymer is an integral multiple of
the molecular mass of a monomer
Condensation polymers are formed by condensation reaction
i.e., reaction between two or more monomer molecules
with the elimination of simple molecules like water,
ammonia, HCl etc.,
Based on the response to heat
Thermo softening
Thermosetting
soften on heating and can be converted into any shape
and can retain its shape on cooling
thermosoftening or thermoplastics
under go chemical change on heating and convert
themselves into an infusible mass
thermosetting polymers
Based on the properties or applications
q
Plastics
q
Elastomers
q
Fibers
qResins
Plastics
The polymers, which are soft enough at some temperature
to be moulded into a desired shape and hardened on cooling
so that they can retain that shape.
e.g., polystyrene, polyvinylchloride, polymethylmethacrylate etc.,
Elastomers
The polymers in which the structural units are either zig zag or
in helical chains.
They undergo elastic changes when subjected to an external force
but readily regain their original shape when the force is withdrawn
e.g., natural rubber, synthetic rubbers, silicone rubbers etc.,
Fibers
In these polymers, the molecular chains are arranged parallel to
each other in a spiral or helical pattern and
the molecular length is at least 100 times its diameter
e.g., nylons, terylene, etc.,
Resins
These polymers have a glossy appearance
These constitutes the major essential part of the plastics
These suffers the polymerization reactions and impart
different properties to plastics
e.g., polysulphide sealants, epoxy adhesives, etc.,
Functionality
the number of reactive sites or bonding sites
Alcohols
Methyl alcohol
Ethers Dimethyl Ether
Acids
Acetic acid
Some mono functional hydrocarbons
Aldehydes
Formaldehyde
Aromatic
hydrocarbons
Phenol
Some bi functional hydrocarbons
adipic acid (hexanedioic acid)
1,6-hexanediamine
Terephthalic acid
ethylene glycol
Stereo regular polymers (or) Tacticity of Polymers
Isotactic
On one side
Syndiotactic
Alternating sides
Atactic
Randomly placed
- Conversion from one stereoisomerism to another is not possible by simple
rotation about single chain bond; bonds must be severed first, then reformed!
Types of Polymerisation
Polymerisation occurs basically in two different modes.
addition (chain growth) polymerization
condensation (step growth) polymerization
Addition
monomers react through stages of initiation,
propagation, and termination
initiators such as free radicals, cations, anions opens
the double bond of the monomer
monomer becomes active and bonds with other such
monomers
rapid chain reaction propagates
reaction is terminated by another free radical or
another polymer
-two monomers react to establish a covalent bond
-
a small molecule, such as water, HCl, methanol or CO
2
is
released.
-the reaction continues until one type of reactant is used up
condensation
DISTINGUISHING FEATURES OF
ADDITION AND CONDENSATION POLYMERISATION
ADDITION CONDENSATION
Monomers undergo self addition to
each other without loss of by products
Monomers undergo intermolecular
condensation with continuous elimination
of by products such as H
2
O, NH
3
, HCl, etc.,
It follows chain mechanism It follows step mechanism
Unsaturated vinyl compounds undergo
addition polymeristion
Monomers containing the functional
groups (-OH, -COOH, -NH
2
, .) undergo
this polymerization
Monomers are linked together
through C C covalent linkages
Covalent linkages are through
their functional groups
High polymers are formed fast The reaction is slow and the polymer
molecular weight increases steadily
throughout the reaction
Linear polymers are produced
with or without branching
Linear or cross linked polymers
are produced
e.g., polystryrene, plexiglass,
PVC, etc.,
e.g., nylons, terylene, PF resins, etc.,
Random, Alternating, Blocked, and Grafted
CoPolymers
Synthetic rubbers are often copolymers.
e.g., automobile tires (SBR)
Styrene-Butadiene Rubber random polymer
Addition polymerization can be explained on the basis of
free radical mechanism
It involves three stages
viz., (i) Initiation
(ii) Propagation
(iii) termination
or
u.v.light
I
(Initiator)
R*
(Free radical)
Initiation
C C
H
X H
H
+
R*
(Free radical)
Vinyl monomer
C C *
H
H X
H
R
(new free radical)
The new free radicals attack monomer molecules further in quick
succession leading to chain propagation
Vinyl monomer
C
C
H
X
H
H
C*
+
C
H
H X
H
R
(Free radical)
C
C
H
H X
H
R C C*
H
H
X
H
(new free radical)
Propagation
Vinyl monomer
C
C
H
X
H
H
+
(new free radical)
C
C
H
H X
H
R C C*
H
H
X
H
(another new free radical)
C* C
H
H X
H
C
C
H
H X
H
R C C
H
H
X
H
at m th stage,
C
C
H
X
H
H
+ C
H
H
R C
X
H
C
H
H
C
X
H
m-2
C* C
H
H X
H
C
H
H
R C
X
H
C
H
H
C
X
H
m-1
C* C
H
H X
H
At some stage this chain propagation is terminated when the
free radicals combine either by coupling (combining) of the two radicals
or by disproportionation
R
C
H
H
C
X
H
m-1
C* C
H
H X
H
R C
H
H
C
X
H
m-1
C*
X
H
C
H
H
+
R C
H
H
C
X
H
m-1
C C
H
H X
H
R
C
H
H
C
X
H
m-1
C
H
H
C
X
H
saturated highpolymer (dead polymer)
coupling
R
C
H
H
C
X
H
m-1
C* C
H
H X
H
+
R C
H
H
C
X
H
m-1
C*
X
H
C
H
H
+ R
C
H
H
C
X
H
m-1
C C
H X
H
H R C
H
H
C
X
H
m-1
C
H
H
C
X
H
saturated oligomer
unsaturated oligomer
(dead polymer) (dead polymer)
disproportionation
TECHNIQUES OF POLYMERISATION
Addition polymerization is brought about using four different
techniques
Bulk or Mass polymerization
Solution polymerization
Suspension polymerization
Emulsion polymerization
Bulk or Mass Polymerization
only the monomer and the initiator are involved
monomer is taken in the liquid state
the initiator should dissolve in the monomer
Initiation can be done either by heating or by exposing
to radiation
the reaction is exothermic
As the reaction proceeds, the reaction mixture becomes
viscous
the polymer molecules with wide range of molecular
masses will be obtained
Disadvantages:
as the reaction proceeds stirring become difficult as the
product becomes more and more viscous
Uncontrolled temperature rise may lead to
discoloration
thermal degradation
branching
cross linking
and some times explosion also
Advantages:
The method is simple
It needs simple equipments
The percentage of conversion is high
Product obtained is pure with high optical clarity
Solution Polymerization
the medium chosen is an inert solvent
the monomer, the initiator and a chain transfer agent
should dissolve in an inert solvent
The solution is heated with constant agitation
After the reaction is over,
the polymer formed may dissolve in the solvent
along with the monomer or may be precipitated
Advantages:
Solvent will reduce the viscosity of the reactant mixture
heat transfer will be better
Disadvantages:
the polymer will not be pure and has to be isolated
by chemical techniques
high molecular mass polymers will not be obtained
Suspension Polymerization
the monomer is suspended in water as droplets of
colloidal size
Water is used as a solvent
Initiators used are soluble in monomer droplets
protective colloids are added to suppress the coagulation
of the monomer molecules
The reaction mixture is heated or exposed to radiation
with constant stirring.
Polymerisation takes place inside the droplet
the polymer formed being insoluble in water, produce
spherical pearls or beads
Advantages:
Disadvantages:
Process is cheap since it uses water as a solvent
instead of costly solvents
Viscosity increase is negligible
Agitation and thermal control are easy
Product isolation is easy since the product is
insoluble in water
Product formed is pure
the method can be used only for water insoluble monomers
it is difficult to control polymer size
Emulsion Polymerisation
This method is used for water insoluble monomers
Emulsion is the colloidal dispersion of a liquid in
another immiscible liquid
Emulsion of water and the monomer is allowed to form
To maintain the system stable, a small amount of an
emulsifier will be added
Soaps and detergents are examples for emulsifiers
Emulsifier contains
a hydrophilic (water loving) polar end group (head) and
a hydrophobic (water hating) non polar end group (tail)
At very low concentration, the soap or detergent (emulsifier)
dissolves completely in water
at slightly higher concentrations, the emulsifier molecules
form aggregates, called miscelles
The monomer molecules dissolve in the hydrocarbon centre
of the miscelles
water soluble initiator will be added and the system is kept
agitated at the required temperature.
The initiator molecules diffuse into the centre of miscelles
through its polar head
Reaction takes place at the centre of the miscelles
The polymer is formed and the miscelles begins to swell
The monomer consumed inside the miscelles is replenished
by diffusion from aqueous phase
This continues till the size of the polymer is big enough
to come out of the miscelles
Advantages:
Disadvantages:
Rate of polymerization is high
polymers with higher molar masses are formed
thermal control is easy
control over the polymer molar mass is possible
no viscosity build up and hence agitation is easy
the polymer formed may contain impurities such as
the emulsifiers and coagulants
It needs further purification by other chemical techniques
GLASS TRANSITION TEMPERATURE (T
g
):
Amorphous polymers do not have sharp melting points
They possess softening point
At low temperature, polymers exist as glassy substances
Since the molecular chains can not move at all easily in
this state, the solid tends to shatter, if it is hit
If the solid polymer is heated, eventually it softens and
becomes flexible
This softness and flexibility is obtained at the
glass transition temperature
So the glass transition temperature can be defined as
the temperature below which an amorphous polymer is
brittle, hard and glassy and above the temperature
it becomes flexible, soft and rubbery
Glassy state rubber state
(Hard brittle plastic) (soft flexible)
In the glassy state of the polymer, there is
neither molecular motion nor segmental motion
When all chain motions are not possible, the rigid solid results
On heating beyond Tg segmental motion becomes possible
but molecular mobility is disallowed. Hence flexible
The glassy state and the glass transition
In general for ordinary compounds of low molar
mass:
crystalline solid
liquid
N
|
H
H
|
C
|
H
1
]
1
1
1
1
1
1
6
N
|
H
O
||
C
H
|
C
|
H
1
]
1
1
1
1
1
1
4
N
|
H
O
||
C
N
|
H
H
|
C
|
H
1
]
1
1
1
1
1
1
6
N
|
H
O
||
C
H
|
C
|
H
1
]
1
1
1
1
1
1
4
N
|
H
O
||
C
+
+
+
+
+
+
H
C
H
H
C
H
H
C
H
H
C
H
+
+
+
+
+
+
nylon 6,6
polyethylene
Hydrogen bonds
Van der Waals bonds
With H-bonds vs vdW bonds, nylon is expected to have (and does) higher Tg.
The presence of H-bonds between the polymer molecules
increases the Tg
The presence of a plasticizer reduces the Tg of a polymer
The plasticizers are usually dialkyl phthalate esters,
such as dibutyl phthalate, a high boiling liquid.
C
C
O
O
O
O
CH
2
CH
2
CH
2
CH
3
CH
2
CH
2
CH
2
CH
3
dibutyl phthalate
The plasticizer separates the individual polymer chains
from one another. It acts as a lubricant which reduces
the attractions between the polymer chains.
The Tg of a polymer is influenced by its molecular weight
However, it is not significantly affected if molecular weight is
around 20000
With increase in molecular mass, the Tg increases
PE (low Mw)
PE (high Mw)
-110
0
C
- 90
0
C
e.g.,
The glass transition temperature helps in choosing the right
processing temperature
It also gives the idea of
thermal expansion
heat capacity
electrical and mechanical properties
Callister,
Fig. 16.9
T
Molecular weight
T
g
T
m
mobile
liquid
viscous
liquid
rubber
tough
plastic
partially
crystalline
solid
crystalline
solid
T
m
: melting over wide range of T depends upon history of sample,
a consequence of lamellar structure
thicker the lamellae, higher the T
m
.
T
g
: from rubbery to rigid as T lowers
STRUCTURE PROPERTY RELATIONSHIP OF POLYMERS
Macromolecules show a wide range of properties which are
quite different from those of respective monomers
They may be
elastic or rigid
hard or soft
transparent or opaque
have strength of steel but can have very light weight
soften on heating or
can set to a hard mass on cooling the melt
These properties may vary from one type of polymer to
another and even among the same type
The fundamental parameters which influence the
structure-property relationship are
molecular mass
polarity
crystallinity
molecular cohesion
stereochemistry of the molecules
the nature of polymeric chains and
The properties like tensile strength, crystallinity,
elasticity, resistance to chemicals, wear and tear
depend mostly on the polymer structure
Tensile Strength
This can be discussed based on
the forces of attraction and
slipping power
Based on forces of attraction:
Strength of the polymer is mainly determined by
the magnitude and distribution of attraction forces
between the polymer chains
These attractive forces are of two different types
primary or covalent bond
secondary or intermolecular forces
In straight chain and branched chain polymers,
the individual chains are held together by
weak intermolecular force of attraction
strength increases with increase in chain length
(in turn increase in molecular weight)
as the longer chains are entangled (anchored) better
In cross-linked polymers, monomeric units are held together
only by means of covalent forces
Increase in Strength
Linear Polymers: Polyethylene, polyvinyl chloride (PVC),
polystyrene, polymethyl methacrylate (plexiglass), nylon,
fluorocarbons (teflon)
Branched Polymers: Many elastomers or polymeric rubbers
Cross-linked Polymers: Many elastomers or polymeric rubbers are
cross-linked (vulcanization process); most thermosetting polymers
Network Polymers: Epoxies, phenol-formaldehydes.
Examples:
Based on slipping power:
It is defined as the movement of molecules one over the other
It depends on the shape of the molecule
E.g., polyethylene molecule is simple and uniform
the movement of molecules one over other is easy
i.e., slipping power is high
Hence it has less strength.
in case of poly vinyl chloride (PVC), the bulky chlorine atoms are
present along the chain length hence movement is restricted
i.e., slipping power is less
Hence PVC has higher strength than PE
Cl
Cl Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl Cl
Cl
Plastic deformation
When a polymer is subjected to some stress in the form
of heat or pressure or both, permanent deformation in
shape takes place, which is known as plastic deformation
Slippage is more in case of linear molecules than branched
and cross-linked, because of the presence of only the weak
intermolecular forces
Hence linear molecules show greatest degree of
plastic deformation, under pressure
at high pressure and temperature, the weak
Vander waals forces between molecules become
more and more weak
Such type of materials are called thermoplastic materials
No slippage occurs in case of cross-linked molecules,
because of only primary covalent bonds are present
throughout the entire structure
i.e., plasticity does not increase with rise in temperature
or pressure or both
Such type of polymers are known as thermosetting polymers
However, when considerable external force
or temperature exceeding the stability of material is applied,
it will result in total destruction
Crystallinity
Polymers are part crystalline and part amorphous
An amorphous state is characterized by complete
random arrangement of molecules
crystalline form by regular arrangement of molecules
crystalline
region
amorphous
region
A linear polymer will have a high degree of crystallinity,
and be stronger, denser and more rigid.
The more lumpy and branched the polymer, the less dense
and less crystalline.
The more crosslinking the stiffer the polymer.
And, networked polymers are like heavily crosslinked ones.
Isotactic and syndiotactic polymers are stronger and
stiffer due to their regular packing arrangement.
Polymers with a long repeating unit or
with low degree of symmetry do not crystallize easily
Optical properties: crystalline -> scatter light (Bragg)
amorphous -> transparent.
Most covalent molecules absorb light outside visible spectrum, e.g.
PMMA (lucite) is a high clarity tranparent materials.
Which polymer more likely to crystallize? Can it be decided?
Linear and highly crosslink
cis-isoprene
Not possible to decide which might crystallize. Both not likely to do so.
Networked and highly crosslinked structures are near impossible to
reorient to favorable alignment.
H
+
+ H
2
0
Networked
Phenol-Formaldehyde
(Bakelite)
Polystyrene (PS) possess greater strength when compared to
PE and PVC because of the presence of bulky phenyl group.
R
Which polymer more likely to crystallize? Can it be decided?
alternating
Poly(styrene-Ethylene)
Copolymer
Alternating co-polymer more likely to crystallize than random ones, as they are
always more easily crystallized as the chains can align more easily.
random
poly(styrene - ethylene) copolymer
Which polymer more likely to crystallize? Can it be decided?
Linear syndiotactic polyvinyl chloride Linear isotactic polystyrene
Linear and syndiotactic polyvinyl chloride is more likely to crystallize.
The phenyl side-group for PS is bulkier than the Cl side-group for PVC.
Generally, syndiotactic and isotactic isomers are equally likely to crystallize.
For linear polymers, crystallization is more easily accomplished as chain
alignment is not prevented.
Crystallization is not favored for polymers that are composed of
chemically complex mer structures, e.g. polyisoprene.
Chemical Resistance
Chemical resistance of the polymer depends upon the
chemical nature of monomers and
their molecular arrangement
As a general rule of dissolution,
like materials attract and unlike materials repel
Thus a polymer is more soluble in structurally similar solvent
polymers containing polar groups like OH, - COOH etc.,
usually dissolve in polar solvents like water, ketone, alcohol etc.,
e.g.,
but these are chemically resistant to non-polar solvents
Similarly non-polar groups such as methyl, phenol dissolve
only in non-polar solvents like benzene, toluene, etc.,
polymers of more aliphatic character are more soluble in
aliphatic solvents, hence chemical resistance is less in
aliphatic solvents and more in aromatic solvents
polymers with more aromatic groups dissolve more in
aromatic solvents, hence chemical resistance is less in
aromatic solvents and more in aliphatic solvents
Polymers containing ester groups (e.g., polyesters) undergo
Hydrolysis with strong alkalis at high temperature
Implies less chemical resistance in alkalies
Polyamides like nylon containing NHCO group can undergo
easily the hydrolysis by strong acid or alkali
Polymers containing residual unsaturation e.g., rubbers
(natural and some synthetic) easily undergo degradative
oxidation in air in presence of light or ozone
Because of the dissolution of polymers in suitable solvents,
there occurs softening, swelling and loss of strength of
polymer material
The tendency of swelling and solubility of polymers
in a particular solvent decreases with increase in
molecular weight
Linear polymers have lower resistivity than branched chain
and cross linked polymers
Permeability of the solvents in the polymers also depends
on crystallinity
crystalline polymers exhibits higher chemical resistance than
less crystalline polymers because of denser packing
Elasticity
Elasticity of the polymer is mainly because of the uncoiling and
recoiling of the molecular chains on the application of force
a polymer to show elasticity the individual chains should not
break on prolonged stretching
Breaking takes place when the chains slip over the other
and get separated
So the factors which allows the slippage of the molecules
should be avoided to exhibit an elasticity
The slippage can be avoided by
introducing cross-linking at suitable molecular positions
introducing bulky side groups such as aromatic and
cyclic groups on repeating units
introducing non-polar groups on the chains
a polymer to show elasticity, the structure should be
amorphous
By introducing a plasticizer the elasticity of polymer
can enhance
to get an elastic property, any factor that introduces
crystallinity should be avoided
Molecular Weight of Polymers
A simple compound has a fixed molecular weight
e.g., acetone has mol. Wt. of 58 (regardless of how it is made)
in any given sample of acetone, each molecule
has the same molecular weight
This is true for all low molecular weight compounds
In contrast, a polymer comprises molecules of different
molecular weights
hence, its molecular weight is expressed in terms of an
average value
e.g., ethylene gas, which is a low mol. wt. compound
each of its molecules have the same chemical structure and
hence, a fixed molecular weight of 28
upon polymerization, it forms polyethylene and we encounter
an indefinite chemical structure of --(-CH
2
CH
2
-)
n
where n can change its value from one polyethylene
molecule to another present in the same polymer sample
When ethylene is polymerized to form polyethylene,
a number of polymer chains start growing at any instant,
but all of them do not get terminated after growing to the
same size
The chain termination is a random process
hence, each polymer molecule formed can have a
different number of monomer units and thus
different molecular weights
So, a sample polymer can be thought of as a mixture of
molecules of the same chemical type, but of different
molecular weights
In this situation, the molecular weight of the polymer can
only be viewed statistically and expressed as some average
of the Mol. Wt.s contributed by the individual molecules that
make the sample
the molecular weight of a polymer can be expressed by
two most and experimentally verifiable methods of averaging
(i) Number average
(ii) weight average
Number average molecular mass of a polymer can be defined
as the total mass of all the molecules in a polymer sample
divided by the total number of molecules present
The molecular mass of a polymer can use either
number fractions or the weight fractions of the
molecules present in the polymer
In computing the number average molecular mass of a
polymer, we consider the number fractions
Assume that there are n number of molecules in a
polymer sample
n
1
of them have M
1
molecular weight (each)
n
2
of them have M
2
molecular weight
n
i
of them have M
i
molecular weight
Total no. of molecules (n) is given by
n = n
1
+ n
2
+ n
3
+ n
4
+ n
5
+ n
6
+ + n
i
No. of molecules in fraction 1 = n
1
i
1
n
n
1 fraction of fraction Number
i
1 1
n
M n
1 fraction by on contributi weight Molecular
Similarly,
Molecular weight contribution by other fractions are
;
n
M n
;
n
M n
;
n
M n
i
3 3
i
2 2
i
1 1
i
i i
n
M n
Number average molecular mass of the whole polymer
is given by
+ + + + +
i
i i
i
4 4
i
3 3
i
2 2
i
1 1
n
n
M n
........ .......... ..........
n
M n
n
M n
n
M n
n
M n
M
i
i i
n
n
M n
M
In computing the weight average molecular mass
of a polymer, we consider the weight fractions
Total weight of the polymer (W) is given by
W = n
i
M
i
Weight of fraction 1 = W
1
= n
1
M
1
i i
1 1 1 1
M n
M n
W
M n
1 fraction of fraction weight
1
i i
1 1
M
M n
M n
1 fraction by on contributi weight Molecular
,
_
i i
2
1 1
M n
M n
Molecular weight contribution by other fractions are
;
M n
M n
;
M n
M n
;
M n
M n
i i
2
3 3
i i
2
2 2
i i
2
1 1
i i
2
i i
M n
M n
Weight average molecular mass of the whole polymer
is given by
+ + + + +
i i
2
i i
i i
2
4 4
i i
2
3 3
i i
2
2 2
i i
2
1 1
w
M n
M n
....... ..........
M n
M n
M n
M n
M n
M n
M n
M n
M
i i
2
i i
w
M n
M n
M
Polymers: Molecular Weight
number average, M
n
weight average, M
w
N
i
: no. of molecules with degree of polymerization of i
M
i
: molecular weight of i
Ratio of M
w
to M
n
is known as the polydispersity index (PI)
PI = 1 indicates M
w
= M
n
, i.e. all molecules have equal
length (monodisperse)