Polymer Science and Fundamental.

Introduction To Plastics Materials
CORPORATE TRAINING AND PLANNING

Classification of Polymers

POLYMER
“The polymer (poly- many; mer-unit or parts) is a high

molecular weight compound, formed by the combination of
small molecules of low molecular weight”.
OR
“Polymers having long chain macromolecules, which are built

up by the linking together of a large number of small
molecules, called monomer”.

Basic Terms of Polymers
•Polymerization: “The process by which, monomer combine to

form polymers is known as polymerization”.
Degree of Polymerization (DP): “The numbers of repeating unit

present in it call degree of polymerization (DP)”.
Addition Polymerization: : ‘When molecules just add on to form

the polymer, the process is called ‘addition polymerization’
In ‘addition polymerisation’ the molecular weight of the polymer
is roughly equal, to that of all the molecules, which combine to
form the polymer.
Ex; Polyethylene, polypropylene
Condensation Polymerization: When, however, molecules do
not just add on but also undergo some reaction in forming
the polymer, the process is called ‘condensation
polymerisation’
• The molecular weight of polymer is lesser by the weight of
simple molecules eliminated during the condensation
process
• The condensation takes place between the two reactive
functional groups, like the carbonyl group (of an acid) and
hydroxyl group (of an alcohol) to form polyesters.
Ex. Nylon, PET

Polymer Material Properties Depends on
1. Degree of Polymerization
2. Molecular Weight of the Polymer
3. Molecular Weight Distribution
4. Glass Transition Temperature
5. Percentage of Crystallinity
6. Structure and Distribution of Chain Branching

Types of Polymers
A polymer consist of identical monomers or monomers of
different chemical structure and accordingly they are called
homopolymer and copolymers respectively. If the main chain
is made up of same species of atoms, the polymer is called
‘homochain polymer’ Graft copolymer are branched
structures in which the monomer segments on the branches
and backbone differ

The monomeric unit in a polymer may be present in a linear,
branched or cross-linked (three dimensional) structure

Tacticity
1. The head to tail configuration in which the functional
groups are all on the same side of the chain, is called
‘isotactic polymers’.
2. If the arrangements of functional groups are at random
around the main, it is called ‘atactic polymers’ e.g.
polypropylene.
3. If the arrangements of side groups is in alternating
fashion, it is called ‘synditactic polymers’
Where R = Alkyl Group

Functionality

Thermoplastics Polymers
Thermoplastics are resins that repeatedly soften when
heated and harden when cooled
Thermosetting Polymers
Thermosets are resins that undergo reaction during
processing to become permanently insoluble and infusible
due to they formed three-dimensional cross linked network
structure when heat is applied.
Characteristics of thermosetting resins:

1. During the hardening the cross-links are formed between
adjacent molecules, resulting in a complex, interconnected
network that can be related to its viscosity and performance
2. These cross-links prevent slippage of individual chains, thus
preventing plastic flow under addition of heat
3. If excessive heat is added after cross links, degradation
rather than melting will occur.
Ex: Phenolic Resin, Epoxy Resin, Polyester resin
Thermoplastics and Thermosetting Polymers
Structure of Thermoplastics and Thermosetting Polymers

Difference Between Thermoplastics and Thermosetting Polymers

Molecular weight of Polymers
“Molecular weight of a polymer is defined as sum of the

atomic weight of each of the atoms in the molecules, which is
present in the polymer”.
This distribution of molecular weights is caused by the

statistical nature of the polymerization process e.g. methane
(CH4) molecules have the same molecular weight (16), but all
polyethylene do not have the same molecular weight because

the statistical distribution of molecular weight may be
different for the different grade of the polyethylene and the
degree of polymerization may also be different.

Generalization of Concept

Number-average molecular weight
Mn=
 niMi =  wi
 ni  wi/Mi
Weight-average molecular weight
Mw=
 niMi 2
=
 wiMi
 niMi  wi
z-Average molecular weight
Mz=
 niMi  wiMi
=
3 2
 niMi  wiMi
2
Where,
n= Moles of molecules (n1 + n2 + n3 + ----------ni) i.e. weight
(w)/molecular weight (M)
w= Weight of individual molecules (w1 + w2 + w3 + ---------wi)
M= Molecular weight of each molecules

Number Average Weight (Mn)
The number average molecular weight is not too difficult to
understand. It is just the total weight of all the polymer
molecules in a sample, divided by the total number of polymer
molecules in a sample.
Consider a polymer, which contains four molecular weight
polymers in different numbers and weight and these

Total number of polymer in containing each entity of poly-1,
poly-2, poly-3 and poly-4 is = 15
Number of Poly-1 present in the polymer = 2
Number of fraction of poly-1 = 2/15
Similarly, Number of fraction of poly-2 = 4/15, Number of
fraction of poly-3 = 6/15, Number of fraction of poly-4 = 3/15
Contribution made by poly-1 towards the average weight of
polymer = number of fraction of each polymer x weight of each
poly entity
Therefore, each poly contribution is
(2/25) x 10 =1.33g, (4/15) x 20 = 5.33g, (6/25) x 100 =40g, (3/15) x
250 = 50g
Summing up the contribution to get Number Average Molecular
Weight=
1.33 + 5.33 + 40 + 50 = 96.66g
Total number of molecules (n) id given by
n  n1  n2  n3  n4  ...........   ni
ni
Number fraction of each molecule is =
 ni ni M i
Number average weight contribution of each entity is =
Number average weight molecular weight is
 ni
n1M 2 n2 M 2 n3 M 3 n4 M 4
   ...... 
n M i i
 Mn
 ni  ni  ni  ni n i

Weight Average Molecular Weight (Mw )
Total weight of each poly present in the polymer =1450g
Weight of poly-1 present in polymer = 20g
Weight fraction of poly-1 = 20/1450, Weight fraction of poly-2
= 80/1450, Weight fraction of poly-3 = 600/1450, Weight
fraction of poly-4 = 750/1450
Contribution made by each poly towards average weight of
polymer = weight fraction of poly-1x weight of each unit
For poly-1 (20/1450) x 10 = 0.14g
For poly-2 (80/1450) x 20 = 1.10g
For poly-3 (600/1450) x 100 = 41.38g
For poly-4 (750/1450) x 250 = 129.31g
Summing up the contribution made by each poly to get
weight average molecular weight is
0.14 + 1.10 + 41.38 + 129.31 = 171.93g
Total number of molecules (n) id given by

n  n1  n2  n3  n4  ...........   ni
Total weight of the polymer is = N M i i W
n1M 1 nM
Weight fraction of each molecule is =  1 1
W  n1M1
2
n1M 1M 1 ni M i
Weight average weight contribution of each entity is = n M
 i i  ni M i
Number average weight molecular weight is
 ni M i
2 2 2 2 2
n1M nM nM nM
1
 2 2  3 3  4 4 ......   Mw
 ni M i  ni M i  ni M i  ni M i n Mi i
For synthetic polymers Mw is greater than the Mn. If they are

equal than they will consider as perfectly homogeneous. (Each
molecule has same molecular weight).

Molecular weight and degree of polymerisation
Number of repeating unit in a polymer called as degree of

polymerisation (DP). DP provides the indirect method of
expressing the molecular weight and the relation is as
follows;
M = DP x m
Where, M is the molecular weight of polymer, DP is the
degree of polymerisation and m is the molecular weight of
the monomer
 n i (DP)i  n i (DP)i
2
(DP) n = and( DP ) w =
n i  n (DP)
i i
Each of these averages can be related to the corresponding

molecular weight average by the following two equations;
Mn = (DP)n.m
Mw = (DP)w.m
Influence of Molecular weight of Polymers
The influence of molecular weight on the bulk properties of
polyolefin's, an increase in the molecular weight leads to
Increase in:
• Melt viscosity
• Impact strength
Lowers in:
• Hardness
• Stiffness
• Softening point
• Brittle point
High molecular weight polymer does not crystallize so
easily as lower molecular weight material crystallizes due to
chain entanglement and that reflect in bulk properties of the
high molecular weight polymer.
• A high molecular weight polymer increases the mechanical
properties. Higher molecular weight implies longer polymer
chains and a longer polymer chain implies more
entanglement thereby they resist sliding over each other.
• Increasing the molecular weight and the chain length of the
polymer increases impact strength.
• Thermal properties can also improved by increasing the
molecular weight.

Polydispersity Index for Molecular weight of Polymers
Polydispersity is a very important parameter and it gives an

idea of lowest and the highest molecular weight species as
well as the distribution pattern of the intermediate molecular
weight species. Plastics processing are affected by the
molecular weight distribution.

Polydispersity Index for Molecular weight of Polymers

To bring into sharper focus the effect of molecular weight on
physical properties, a more generalized form of
representation is given in figure, mechanical strength is
plotted against 'DP .
The useful range of DP is from 200 to 2000, which
corresponds to its molecular weight 20000 to 200000

Determination of Molecular Weight

Determination of Molecular Weight
1.Number-average Molecular Weight
a) End-group Analysis:
If functional groups present in a given weight of the

sample and this is expressed as a functional group
equivalent/100 g. From knowledge of the functional group
equivalent and the functionality, The molecular weight is
calculated using the equation:
Functionality
Mn 
Functionalgroupequivalent
Then the functionality of the polymer sample can be given

by the equation
Functionality = molecular weight X functional equivalent

b) Measurement of Colligative Properties
1. Depression in freezing point (cryoscopy) and elevation in

boiling point (ebulliometry). As these two properties are
Colligative (i.e. depend only on the number of moles of a
solute present in a liquid and not on their nature).
2. Colligative properties are those that depend on the number
of species present rather than on their kind. From
thermodynamic arguments it may be shown that for very
dilute ideal solutions
ln 1   X 2
Where, 1 is the activity of the solvent in a dilute ideal
solution and X2 is the mole fraction of solute. From this
relationship the solute molecular weight may be calculated
if the weight fraction W2 is known.
n2 w2 M 1
X2  
n1 M 2 w1
The suitability of methods based on Colligative properties Vs Molecular Weight
Lowering of Vapour Pressure

The partial vapor pressure PI of solvent 1 over a solution is
lower than the vapor pressure over the pure solvent p 10.
This is expressed by Raoult's law:
0
p1  X 1 p1
Where X1 is the mole fraction of the solvent.
For a binary solution containing a mole fraction X 2 of solute

then,

0
p  p p
X 2  1 0 1  01
p1 p1
For a dilute solution,
n2 w2 M 1
X2  
n1 M 2 w1
Combining above two equation,
0
M p
M 2  w2 1 1
w1 p1
Assuming ideal solution behavior, the unknown molecular
weight is calculated from
w2 M sVs
Mn 
V2 wn

i) Ebulliometry
Ebulliometry is another technique for determining the

depression of the solvent activity by the solute. In this case
the elevation of the boiling point is determined. The boiling-
point elevation Tb is measured with sensitive thermocouples
or matched thermostats in a Wheatstone bridge. The
molecular weight M" is calculated from
Kbc
Mn 
Tb
Where c is the concentration of solute in g/1000g of solvent
and 2
RTb M
Kb 
1000H v
is the molal ebullioscopic constant. M is the molecular

weight of the solvent and Tb its boiling point; Hv is the molar
latent heat of vaporization of the solvent.
ii) Cryoscopy
The freezing point of a solution is depressed below that of the
pure solvent by an amount proportional to the mole fraction of
solute. The value for Mn is obtained from
Kfc
Mn 
T
Where c is the concentration of solute in g/1000 g of solvent
and
2
RTm M
Kf 
1000H fus
is the molal cryoscopy .constant; M is the molecular weight

of the solvent and Tm its melting point; Hfus is the molar
latent heat of fusion of the solvent.

c) Osmometry
I) Vapor-pressure Osmometry
The number-average molecular weight of the unknown

sample may then be calculated from this equation,
R    bm
bc
Mn 
R  
Where c is the concentration of solute in g/1000 g of solvent is

the straight line equation and the plot intercept of which would
provide Mn.

ii) Membrane Osmometry
The membrane osmometer apparatus basically measures
osmotic pressure of polymer solutions of known
concentration, say 1 g dl-1
As already mentioned the van't Hoff law forms the basis for
the determination of number average molecular weight, Mn
Following equation gives the relation ship between osmotic
pressure,  of polymer solution to Mn of the polymer
 / C  RT  A1  A2C  A3C 2  A4C 3  ......

Where, A1, A2 and A3 are the first, second and third virial
coefficients, C2 is the concentration of polymer solution and R
and T are the gas constant and temperature respectively. For
very dilute solutions (typically less than 1 g dl- I), the
concentration terms containing higher order powers can be
neglected and hence it can be written that
 / C  RT 1/ Mn  A2C 
Working Principle

2. Viscosity-Average Molecular Weight
The molecular weight is related to the intrinsic viscosity by

the Mark-Houwink relationship.
    M 
Where k and  are empirical constants and are

characteristic for a polymer solvent pair at a given
temperature.

sp / C      '   C
2
Huggins Equation
(ln rel ) / C     "  C

2
Kraemer Equation

Weight-average Molecular Weight
Light Scattering
When a beam of light is passed through a colloidal solution,
it is scattered. This is well-known Tyndall effect, which
results from the scattering of a part of the beam of light by
the colloidal particles in all directions. Since polymer
solutions can be considered as colloidal (lyophilic)
solutions and as the intensity of light scattered depends on
the size of colloidal particles (or polymer molecules)

KC / R90  HC /   1/ M w  2 BC
 KC  1
    2 BC
 R  0 Mw
 KC  1
  
 R  0 Mw
Where B is the second virial coefficient, C is the

concentration of the solution, and R90 is the Rayleigh ratio
at 90° observation angle. This ratio in a generalized case is

represented as R i.e. the Rayleigh ratio is determined at
an observation angle of 90°, R = R90'

Ultracentrifuge
Polymer solutions are lyophilic colloids arid these can be

made to settle down on the application of centrifugal force. The
ultracentrifuge is used to determine molecular weights. The
rate of the settling (sedimentation rate) of polymer molecules
depends on the size of the molecules:
SRT
MolecularWeight
D(1  dVsp )
Where Rand T are the gas constant and temperature in Kelvin

scale. The above equation is known as Svedberg equation.
For a polydisperse solute the correct averages for Sand D are
combined in the Svedberg equation

Gel Permeation Chromatography (GPC)
•The basic principle underlying the separation of different'

fractions of a polydispersed sample is based on the size of
individual polymer molecules that explore the pore system
of the column material.
•Large molecules are excluded from small pores and can

only diffuse into a restricted part of the pore system within
the beads while smaller ones would enter into the pores of
the bead.
•Thus large molecules would have less residence time and

would emerge first.

Working Principle of GPC

GPC Curve for standard polystyrene sample showing
elution volumes corresponding to different molecular
weight

*Relative methods and need calibration from standard polymers samples
**Indirect method and needs values of k and a for particular polymer -
solvent system

Glass Transition Temperature (Tg)
The temperature below, which a polymer is hard and above
which it is soft, is called the glass transition temperature (Tg).
Or
The molecular mobility is just starts above that temperature
or below which mobility arrested called Tg

Tg is unique to amorphous thermoplastics. It occurs at a
specific temperature that depends on pressure and specific
volume and is lower than melting point.

Tg
• The glass transition temperature is a measure of evaluating

the flexibility of polymer molecules and the type of response
the polymeric material would exhibit to mechanical stress.
• The glass transition temperature depends on the structure

and polarity of a polymer, which affects both chain flexibility
and intermolecular interaction.
• Since non-polar polymers have lower potential energy

barrier for rotation, their chain remains flexible and they have
low Tg. Chains based on aliphatic C-C bond and C-O bond are
quite flexible, on the other hand introduction of ring structure
into main chain has a marked stiffening effect which results
in higher Tg of such polymer.

• Rotation about a single C-C bond is also impended by the

substitutions of attached hydrogen atoms by methyl or other
attached hydrogen atoms by methyl or other attached to the
main chain carbon atom can influence the Tg.
•Inclusion of double bonds will stiffen the chain at the point of

inclusion but at the same time decrease the flexibility of
adjacent bond. The net effect may therefore be to reduce the
glass transition temperature.
• The presence of polar groups or atoms will result in high

glass transition temperature. Hydrogen bonding has a similar
effect to that of a polar group.

Glass Transition Temperature and Molecular Weight
K
Tg  Tg 
Mn
Where, Tg is the glass transition temperature at
infinite molecular weight and K and A are arbitrary constants.
1 1 A
 
Tg Tg Mn
For a given weight of the polymer, a low molecular weight

sample will have more chain end segments than a high
molecular weight sample.

Glass Transition Temperature and Plasticizer
1. The plasticizer substantially reduces the brittleness of

many amorphous polymers because its addition even in
small quantities markedly reduces the Tg of the polymer.
2. The effectiveness of plasticizer in lowering the Tg of a
polymeric composition is directly proportional to its Tg
and volume fraction of plasticizer
Tg  V1Tg1  V2Tg 2
1 w w
 1  2
Tg Tg1 Tg 2
The extent of reduction in the glass transition values is

called as’plasticizer efficiency'. The extent of reduction is
depends on factors such as solubility parameter, polarity
and density

Effect of Co-polymerization on Glass Transition Temperature
1 wA wB
 
Tg ( AB ) Tg ( A) Tg ( B )
Where Tg(A), Tg(B) and Tg(AB) are the glass transition
temperature of homo polymers A and B and the copolymer

AB respectively. that the glass transition temperature of a
copolymer will be in between those· of the. respective homo
polymers

Glass Transition Temperature and Melting Point
1
Tg  Tm For symmetrical polymers
2
2
Tg  Tm For unsymmetrical polymers
3
A combined version of these two equations, in which the

effect of molecular symmetry is not taken into account, is
also in vogue, as now shown:
1 Tg 2
 
2 Tm 3
Since this relation gives a range for Tg/Tm (rather than a

sharp value), it may more realistically reflect the thermal
behavior of polymers.

Crystallinity in Polymers
A small region of a macromolecules materials in which
portions of large molecules are arranged in regular way, is
called crystalline.
1. Crystallization imparts a denser packing of molecules,
thereby increasing the intermolecular forces of attraction.
2. This accounts for a higher and sharper softening point,

greater rigidity and strength and greater density. A
completely crystalline polymer tends to acquire
brittleness.
Amorphous Polymers
An ‘amorphous polymers’ is characterized by completely

random arrangement of molecules of polymer chain.
While a crystalline region (called crystallites)
embedded in amorphous random matrix. e.g. Polystyrene,
polyvinyl acetate and polymethyl methacrylate (all are having
bulky side groups attached at random to the main carbon
chain) are typically amorphous.
Crystalline and Amorphous Polymers
• Relatively short chains organize themselves into crystalline

structures more readily than longer molecules. Therefore, the
degree of polymerization (DP) is an important factor in
determining the crystallinity of a polymer.
• Polymers with a high DP have difficulty organizing into

layers because they tend to become tangled.
• As symmetrical molecules approaches within a critical

distance, crystal begins to form in the areas where they are
most densely packed.
• A crystallized area is stiffer and stronger. A non-crystalline

(amorphous) are more flexible.

Crystalline and Amorphous Polymers
• An increasing crystalline in polypropylene increased in
creep, heat and stress cracking as well as increased in mould
shrinkage.
•Crystallization tendency decreases by co-polymerization,

because it lowers the structural symmetry, so by controlling
the extent of co-polymerization, the relative extent of
crystallize.
• The amorphous region can be adjusted to get required

hardens, rigidity, heat resistance and flexibility.
• A crystallize or any amorphous polymer can also be made

flexible and plastics by adding plasticizer.
• The plasticizer neutralization of intermolecular forces of

attraction between macromolecules.

Performance of Crystalline and Amorphous Polymers
• Crystalline types of plastics are more difficult to process;

requiring more precise control during fabrication, have higher
melting temperature and melt viscosities, and tends to shrink
and warp more than amorphous types.
• They have a relatively sharp melting point.
• That is they do not soften gradually with increasing

temperature but remain hard until a given quantity of heat has
been absorbed.
• Heating and sudden quenching of crystalline materials will

lead to produce amorphous material. Its properties can be
significantly different than if it is cooled properly (slowly) and
allowed to re-crystallize.

Effect of Crystallization on the properties of polymers
The properties of polymer such as density, modulus,

hardness, permeability and heat capacity will be largely
affected by its crystallinity. Semi crystalline polymer, its
crystalline and amorphous region exhibit different
properties even than both the region are chemically same.
E.g. density of crystalline region will be higher than the
density of amorphous region. Most of the properties are
dependent on the percentage of the crystalline region
present in the polymer.

Effect of Crystallization on Processability
• strong crystalline forces may make the melting

temperature of crystalline polymer higher than
its thermal decomposition temperature, and thus
prevent thermal decomposition temperature.
• Fast and complete crystallization must be

occurring in the mold so that the molded piece can
be ejected rapidly without later distortion and
shrinkage

Effect of Crystallization on Mechanical Properties
• Packing of polymer molecules into crystalline lattice
generally restricts their mobility and stiffness their reversible
mechanical properties.
• Elongation in polymer that is near or above the glass

transition temperature generally decreases as crystallinity
increases.
• Creep and compliance creep of polymer, above the glass

transition temperature, are greatly reduced by crystallinity.
• Crystallinity often decreases impact strength and large

crystallites particularly produce brittleness as explained
below

Effect of Crystallization on Mechanical Properties

Effect of Crystallization on Thermal Properties

Effect of Crystallization on Electrical Properties
• Crystallinity restricts the mobility of polar groups in the

polymer molecules and thus affects dielectric properties of
the polymer.
• In the molten state thermal randomization of polar groups is

greater than orienting effects of an electric field and
dielectric constant rather low.
• With decreasing the temperature thermal randomization

decreases, the orienting and polarization effects of the
electric field remains and thus dielectric constant increases.

Effect of Crystallization on Electrical Properties

Effect of Crystallization on Optical Properties
• Crystallinity increases the density of the polymer, which

decreases the speed of light passing through it and thus
increases the refractive index
• When crystals are larger than the wavelength of visible light

about 400-700mµ lights passes through many successive
crystalline and amorphous area is scattered and clarity of the
polymer decreased.
• Large single crystal scatters light at wide angels and thus

causes haze.

Effect of Crystallization on Chemical Properties
• The tigtly packed regular structure of crystalline polymers is

so stable that it is impossible to break the lattice using
chemicals
• Liner amorphous polymers dissolve easily in a range of

organic solvents
• Crystalline polymers are usually insoluble and can be

dissolved only under limited condition in few specific solvents
• Crystalline polymers can be dissolve above their melting

point where sufficient thermal energy has already been
supplied to separate the polymer molecules from the tight
crystalline structure.
Effect of Molecular Weight on Crystallinity

Chemistry of Polymerisations

Functionality

Chain Growth Polymerisation
1. The monomers contain at least a double bond that
participates in the polymerisation reaction.
2. The initiators for chain polymerisation may be different
depending upon the nature of initiation i.e. free radical,
cation and anion.
3. The carbon-carbon double bond in vinyl monomers and
the carbon-oxygen double bond in aldehydes and
ketones are the two main types of linkages that undergo
chain polymerisation.
4. Important characteristics of chain polymerisation
5. Once the initiation occurs, the polymer chains form very
quickly i.e. in the time scale of 10-1 to 10-6 s,
6. The catalyst concentration needed is very low and that
means during the course of polymerisation only
monomers and polymer are present,
7. The process is exothermic
8. High polymers with molecular weights of 10,000 to 10
million can be obtained,)
Free radical polymerisation
1. The decomposition of peroxide type initiators in aqueous
systems is generally accelerated in the presence of a
reducing agent.
Initiation:
Proportion:
Termination:
Or Disproportion

Radical Molecule Reaction (Chain Transfer)
Although the three steps of initiation, propagation, and
termination are both necessary and sufficient for chain
polymerisation, other steps 'also takes places during the
polymerisation. As these often involve the reaction between
a radical and a molecule, they are conveniently so classified
Chain Transfer .
The reaction involves the transfer of an atom between the
radical and the molecule. If the molecule is saturated, like a
solvent or other additive, the atom must be transferred to
the radical.

The major effect of chain transfer to a saturated small
molecule (solvent, initiator, or deliberately added chain-
transfer agent) is the formation of additional polymer
molecules for each radical chain initiated.
Transfer to polymer and transfer to monomer with
subsequent polymerization of the double bond lead to the
formation of branched molecules.
The latter reaction has a pronounced effect on molecular
weight distribution and is important in the production of graft
copolymers.
The efficiency of compounds as chain transfer agents varies
widely with molecular structure. Aromatic hydrocarbons are
rather unreactive unless they have benzylic hydrogens.
Aliphatic hydrocarbons become more reactive when
substituted with halogens.
Carbon tetrachloride and carbon tetrabromide are quite
reactive. The reactivity of various polymer radicals to
transfer varies widely.
Inhibition and Retardation
A retarder is defined as a substance that can react with a
radical to form products incapable of adding monomer.
It both reduces the concentration of radicals and shortens
their average lifetime and thus the length the polymer chain.
In the simplest case, the retarder may be a free radical, such
as triphenylmethyl or diphenylpicrylhydrazyl, which is too
unreactive to initiate a polymer chain.
The mechanism of retardation is simply the combination or
disproportionation of radicals.
Inhibitors are useful in determining initiation rates; since their
reaction with radicals is so rapid that the decomposition of
inhibitor is independent of its concentration but gives directly
the rate of generation of radicals.
As a result, the length of the induction period before
polymerization starts is directly proportional to the number of
inhibitor molecules initially present. to one radical.
Cationic Polymerisation
The ionic mechanism of chain polymerisation also involves an
attack on the  electron pair of the monomer.
chain reaction initiated and propagated. Strong Lewis

acids such as -BF3 (generally called the 'catalysts' in
ionic polymerisation), in the presence of small amounts
of water or methanol (known as the 'co-catalysts'), form
hydrates, which exist as ion pairs:

The initiators used for this purpose, in addition to BF 3, AlCl3,
SnCI4 and TiCI4. Examples of monomers that can undergo
cationic polymerisation are isobutylene, styrene, methyl
styrene and many vinyl ethers.

It involves further two steps:
(i) Donation of a proton to the counter-ion (which is,
in fact, the reversal of the initiation step), resulting in the
formation of a double bond at the end of the growing polymer
molecule and the resultant arrest of the chain growth:
This process of donation of a proton and the re-formation of

the BF3 hydrate is called 'ion-pair precipitation'.
Formation of a covalent bond between the carbonium ion

and the counter-ion when the termination occurs by simple
‘coupling’

Anionic Polymerisation
The attack on the  electron pair of the monomer is done by a
negatively charged ion (an anion). Such a system has extra
electrons and the resultant negative charge attacks the 
electron pair away from end of the molecule.

Co-ordination Polymerisation
Polymerisation reactions, especially of olefins and Dienes,
catalysed by Organo-metallic compounds, fall under the
category of coordination polymerisation.
Where Mt represents transition metals such as Ti, Mo, Cr, V, Ni or Rh.
The coordinated metal-carbon bond formed in the

monomer catalyst complex acts as the active center from
where propagation starts.

coordination polymerisation is also known as insertion
polymerisation. The well-known Ziegler Natta Catalyst
belongs to this category for the polymerisation.

Ziegler-Natta Catalysts
The catalyst component consists of halides of IV-VIII group
elements having transition valence and the co-catalysts are
organo-metallic compounds such as alkyls, aryls and
hydrides of group I-IV metals.
Natta Monometallic Mechanism:

Cossee Mechanism

Step Polymerization
•The polymer build-up proceeds through a reaction

between functional groups of the monomers.
•The reaction takes place in a step-wise manner (i.e., one
after another), and the polymer build-up is, therefore, slow
(unlike in chain polymerisation where the chain growth is
very rapid).
•Although many known reactions with organic functional
groups can be made use of in step polymerisation,
condensation, addition, ring opening, amidation and ester-
interchange reactions are the most commonly used ones.
In step polymerisation reactions are accompanied by the
elimination of small molecules.

Polycondensation
Polycondensation is brought about by monomers containing
two or more reactive functional groups (such as hydroxyl,
carboxyl and amino) condensing with each other

For polycondensation the monomer should have:
•1. Those monomers should have two reactive
functional groups for polymerisation to proceed.
•2. That polymerisation proceeds by stop-wise reaction
between reactive functional groups.
•3. That only one type of reaction (i.e., condensation
reaction, in this case) between two functional
groups is involved in polymer formation.
•4. That the polymer formed still contains both the
reactive functional groups at its chain ends (as end
group) and, hence, is 'active' and not 'dead', as in
chain polymerization.

Polyaddition Polymerisation

Ring-opening Polymerisation

Miscellaneous Polymerization Reactions
Electrochemical Polymerisation
Once the initiating species is formed at the electrode, the

initiation and propagation are similar to those taking place
under the free radical, anionic or cationic polymerisation.

Metathetical Polymerisation
Olefine metathesis is basically an exchange reaction wherein

the alkyIidene moieties of the reactant molecules are
redistributed through the cleavage and re-forming of olefinic
double bonds, to form new product molecule

Group Transfer Polymerisation
This process used for an organo-silicon initiator and a bi

fluoride catalyst, ,  unsaturated esters, ketones, nitrile and
carboxamides can be polymerized to provide excellent yields of
polymers of narrow molecular weight distribution.

Polymerisation Techniques
Bulk Polymerisation
a. The monomer is taken in the liquid state and the
initiator is dissolved in the monomer. The chain transfer
agent, whenever used to control the molecular weight, is also
dissolved in the monomer itself.
b. The whole system is, therefore, in a homogeneous
phase. The reaction mass is heated or exposed to a radiation
source for initiating the polymerisation and is kept under
agitation for proper mass and heat transfers.
c. As the polymerisation proceeds, the viscosity of the
medium increases and mixing becomes progressively
difficult, leading to products with very broad molecular
weight distribution.

The major Disadvantages are:
1. The medium gets viscous, the diffusibility of the growing
polymer chains becomes restricted, the probability of chain
collision becomes less, termination becomes difficult, active
radical sites accumulate and the rate of polymerisation
increases enormously.
2. This whole phenomenon is called 'auto acceleration' and,
sometimes, the uncontrolled exothermic reaction can lead to
an explosion.
Some advantages:
3. Bulk polymerisation, however, is quite simple and the
product obtained has a high purity since, except the initiator
and the chain transfer agent, no other additive that could
contaminate the product is used. The polymer obtained can
also be used as such since no isolation from other
components is involved.
4. Ex: vinyl chloride to get PVC resin
Solution Polymerisation
a. In solution polymerisation, the monomer is dissolved in a
suitable inert solvent along with the chain transfer agent.
b. The free-radical initiator is also dissolved in the solvent
medium, while the ionic and coordination catalysts, can either
be dissolved or suspended.
c. The presence of the inert solvent medium helps to control
viscosity increase and promote a proper heat transfer.
The major disadvantage of the solution polymerisation
technique is:
1. The selected solvent cannot be completely ruled out and
hence, it is difficult to get very high molecular weight products.

2. The polymer formed will also have to be isolated from
the solution either by evaporation of the solvent or by
precipitation in a non-solvent, and removal of their final
traces is always extremely difficult.
3. Solution polymerisation techniques, nevertheless, can
advantageously be used where the polymer is used in its
solution form, as in the case of certain adhesives and coating
compositions, or in systems where the polymer formed is
insoluble in its monomer or solvent and precipitates out as a
slurry and is amenable for easy isolation.
4. Polyacrylonitrile by free-radical polymerisation and that
of polyisobutylene by cationic polymerisation, use the
solution technique. Block co-polymers are also made
exclusively by this technique

Suspension Polymerisation
 Only water-insoluble monomers can be polymerised
by this technique. The initiators are monomer soluble.
 The monomer is suspended in water, in the form of
fine droplets, which are stabilized and prevented from
coalescing by using suitable water-soluble protective
colloids, surface active agents and by stirring.
 The size of the monomer droplets formed depends on
the monomer-to-water ratio, the type and concentration of
the stabilizing agents and also on the type and speed of
agitation employed.
 Since each monomer droplet is isolated and
independent of the other droplets, it can be visualized to act
as an independent bulk polymerisation nucleus.
 The continuous aqueous phase separating the
monomer droplets acts as an efficient heat transfer medium
and, hence, the exothermic is well controlled.
Advantages
1. Since water is used as the heat transfer medium, the
process is also economical as compared to solution
polymerisation.
2. As the entire bulk of the monomer is divided into
innumerable any droplets control on the kinetic chain length of
the polymer formed is also quite 'good, resulting in a fairly
narrow 'molecular weight distribution of the product.
3. Polymerisation proceeds to 100% conversion and the
product is obtained as spherical beads or pearls. (For this
reason, this technique is also known as bead or pearl
polymerisation).
4. Isolation of the product becomes easy as this involves
only filtration of the beads and removal of the surface-active
agents and protective colloids by water washing.
5. The water washed and dried product can be used as
such for moulding purposes or can be dissolved in a suitable
medium for use asCORPORATE
adhesives and coatings.
TRAINING AND PLANNING
Emulsion Polymerisation
1. As in the case of suspension polymerisation, in
emulsion polymerisation too, the monomer is dispersed in
the aqueous phase not as discrete droplets, but as a
uniform emulsion.
2. The emulsion is stabilized by surface-active agents
(surfactants), protective colloids and also by certain
buffers. The surfactants can be anionic (alkali salts of fatty
acids and of aryl and alkyl sulfonic acids), cationic (alkyl
amine hydrochlorides and alkyl ammonium halides) or non-
ionic (alkyl glycosides and saccharose esters of fatty
acids).
3. Surfactants serve the purpose of lowering the surface
tension at the monomer water interface and facilitate
emulsification of the monomer in water.

1. Owing to their low solubility, surfactants get fully
dissolved or molecularly dispersed only at low
concentrations. Beyond a particular concentration, the
excess quantity does not get molecularly dispersed, out
forms molecular aggregates known as 'micelles', and an
equilibrium is set up between the dissolved surfactant
molecules and the aggregated ones.
• 2. The highest concentration, wherein all the molecules are in
a dispersed state, or the concentration beyond which only
micelle formation is possible, is known as the 'critical micelle
concentration' (CMC).
• 3. Emulsifier molecules are made of two parts: a long non-
polar hydrocarbon' chain to which is attached a polar group
such as -COONa, -S03Na, -NH2HCl or -NBr.
• 4. In micelle formation, the emulsifier molecules aggregate in
such a way that the polar end of the molecules align
themselves outward and. the hydrocarbon ends come close
to each other at the interior.
5. Due to the close proximity of the hydrocarbon ends of all
emulsifier molecules, the interior of the micelle acts as a
hydrocarbon phase where the monomer can be soIubilize.
When the monomer is added and agitated, emulsification
takes place.
• 6. The resultant emulsion is a complex system a molecular
solution of the emulsifier in water is the continuous phase
wherein the monomer droplets and micelles (having the
soIubilize monomer at their interior) are uniformly dispersed.
• 7. If the monomer is slightly soluble in water, then the
aqueous emulsifier solution phase will also dissolved in it.

Melt Polycondensation
1. This technique is used for the polymerisation of
monomers, which have at least one solid component, and do
not decompose around their melting points.
2. The temperatures involved in melt polycondensation are
rather high and, hence, the reaction has to be carried out in an
inert atmosphere of N2 or CO2 to avoid such side reactions as
can lead to oxidation, decarboxylation, degradation etc.
3. The reaction is carried out under reduced pressure to
facilitate removal of the byproduct, which becomes essential if
a high molecular weight product is aimed at.
4. Removal of the byproduct becomes extremely difficult at
later stages of the reaction, as there is considerable increase in
the viscosity of the medium, like in bulk polymerisation.
5. Ex: polyethylene terephthalate, nylon 6, 6

Solution Polycondensation
1. The reactants are taken as a solution in a suitable inert
solvent. The reaction can be carried out at comparatively lower
temperatures during which heat and mass transfer processes
are easier than in the melt technique.
2. The solvent can also serve as an entrapping agent for the
byproduct formed and hence, the removal of the byproduct
becomes easy. Owing to the presence of the solvent phase,
however, the kinetic probability of chain growth is low and this
leads to a reduced rate and a low degree of polymerisation.
Many of the liquid polyester resins based on glycols and unsa
turated dicarboxylic acid are prepared by this technique using
high boiling aromatic hydrocarbons as solvent with which the
water (byproduct) forms an azeotrope and, hence, can be
removed easily.

Interfacial Condensation
1. Polymerisation is allowed to proceed at the interface
between an aqueous and an organic medium. Reactants
having highly reactive functional groups, which can readily
react at ambient temperatures to form condensation products,
are suited to this technique.
2. The polymer formation at the interface is a diffusion
controlled process, very high molecular weight products can
be achieved by this technique.
3. The two solutions are very thoroughly agitated so as to
form an emulsion wherein the interface surface/volume ratio is
increased tremendously and, hence, both the rate and degree
of polymerisation become very high
4. Preparation of fully aromatic polyarnides from tereph
tholoyl chloride and paraphenylene diamine is a typical
example:

1. The diamine is dissolved in water and the acid chloride
in chloroform or carbon tetrachloride. When the two solutions
are brought in contact with each other, at the interface, the
diamine molecules diffuse into the organic phase and react
with the acid chloride, resulting in the formation of a polymer,
which precipitates out immediately.
2. The byproduct formed (HCI) diffuses back into the
aqueous phase and gets dissolved. The precipitate is formed
at the interface in the form of a thin film and, when removed
from the system, exposes a fresh surface of the acid chloride
to the organic phase resulting in the formation of the fresh
quantity of the polymer.
3. As the polymer is formed, it precipitates out and, under
the influence of high-speed agitation, forms slurry. The
polymer is isolated from the slurry and washed free of
adherent reactants.

Solid and Gas Phase Polymerisation
Solid phase polymerisation is mostly restricted to chain·
polymerisation. Also, since such polymerisation is
restricted to low temperatures, thermal activation of the
reaction is quite difficult and, hence, the photo or radiation-
activation technique is resorted to.

Gas phase polymerisation is known in the case of very few
olefinic monomers. The disadvantage of the system is that it
has a very poor heat transfer. The two methods used in the
gas phase polymerisation are: (i) spraying the catalyst
(usually Zeigler-Natta type) into the gaseous monomer and
(ii) feeding the gaseous monomer into a fluidised bed made
up of the catalyst particles. In both the cases, the polymer is
obtained as a free-flowing powder. Polymerisation of
ethylene and p-xylene can be cited as examples for gas
phase polymerisation.

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Introduction To Plastics Materials

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

“The polymer (poly- many; mer-unit or parts) is a high

“Polymers having long chain macromolecules, which are built

CORPORATE TRAINING AND PLANNING

•Polymerization: “The process by which, monomer combine to

Degree of Polymerization (DP): “The numbers of repeating unit

Addition Polymerization: : ‘When molecules just add on to form

CORPORATE TRAINING AND PLANNING

2. Molecular Weight of the Polymer

3. Molecular Weight Distribution

4. Glass Transition Temperature

6. Structure and Distribution of Chain Branching

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

branched or cross-linked (three dimensional) structure

CORPORATE TRAINING AND PLANNING

Where R = Alkyl Group

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

Characteristics of thermosetting resins:

Structure of Thermoplastics and Thermosetting Polymers

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

“Molecular weight of a polymer is defined as sum of the

This distribution of molecular weights is caused by the

polyethylene do not have the same molecular weight because

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

M= Molecular weight of each molecules

CORPORATE TRAINING AND PLANNING

Total number of molecules (n) id given by

CORPORATE TRAINING AND PLANNING

Total number of molecules (n) id given by

For synthetic polymers Mw is greater than the Mn. If they are

CORPORATE TRAINING AND PLANNING

Number of repeating unit in a polymer called as degree of

Each of these averages can be related to the corresponding

CORPORATE TRAINING AND PLANNING

Polydispersity is a very important parameter and it gives an

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

If functional groups present in a given weight of the

Then the functionality of the polymer sample can be given

CORPORATE TRAINING AND PLANNING

1. Depression in freezing point (cryoscopy) and elevation in

Lowering of Vapour Pressure

For a binary solution containing a mole fraction X 2 of solute

CORPORATE TRAINING AND PLANNING

CORPORATE TRAINING AND PLANNING

Ebulliometry is another technique for determining the

is the molal ebullioscopic constant. M is the molecular

is the molal cryoscopy .constant; M is the molecular weight

CORPORATE TRAINING AND PLANNING

The number-average molecular weight of the unknown