Module-2

Polymer Chemistry
A PowerPoint Presentation on Water
Prepared by Dr. Dibakar Deb
 SYLLABUS

Polymer Chemistry
 Plastics pollution

The favorite properties of plastics are that they are inert and won't react
with what is stored in them. They also are durable and won't easily
decay, dissolve, or break apart. These are great qualities for things you
keep, but when you throw them away, they won't decompose.
 WHAT IS A POLYMER

 A word polymer is a combination of two Greek words,

“Poly” means “many” and “Meros” meaning “parts or
units”.
 A polymer is a large molecule of which is formed by
repeated linking of the small molecules called
“monomers”.

n(CH2=CH2) (-CH2-CH2-)n
ethylene polyethylene
 DEGREE OF POLYMERIZATION

• Degree of polymerisation (DP): The no. of repeating

unit(n)Degree of polymerisation=Molecular wt of the
polymeric network/molecular wt of the repeating unit The
number of repeating units in the chains of which a polymer
is made up is called degree of a polymerization (n).

• Polymers with high degree of polymerization are

called the “High Polymer”.

• High polymers have very high molecular mass

(10000 to 1000000 u) and are called macromolecules.
 Degree of Polymerization
Degree of Polymerization (P) = M/m;
Where, M= Mass of Polymer; m = mass of monomeric unit

3 Polymerisation
CH2 CH2 CH2 CH2
3

Ethylene
polyethylene

Degree of polymerisation (P) = 3

7
 NOMENCLATURE OF MACROMOLECULES

• A macromolecule may consist of monomer of

identical or different chemical structure and
accordingly they are called Homopolymers or
copolymers (or Heteropolymers).

A A A A … Homopolymers

A A B A … Copolymers
 LINKING OF POLYMERS

• Polymers can be linear, branched or cross-linked. The

monomer may be arranged in the chain at random or
regularly.

(LINEAR POLYMER)
A A A A … … B B B

A A A A A A

A A A

(BRANCHED POLYMER)
 CROSS-LINKED POLYMER

A A

A A A

A A A A A A

A A A

A A A A A A

(CROSS-LINKED POLYMER)
 Functionality
The number of reactive sites present in a monomer is called functionality
1.

O
Linear chain polymer is formed if the functionality of the
HO C CH2 NH2
monomer is only two (Bifunctional)

2. Ex. Glycine

O
O
HO C CH2 NH2
OH CH2 CH C OH
NH2

Ex. Serine
O
Cross linked chain polymer is formed if
OH CH2 CH C OH the functionality of the monomer is more
than two (multifunctional)
NH2
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 Classification based on Structure
1. Linear polymers
consist of long and straight chains. E.g., Polyvinyl chloride

2. Branched chain polymers

contain linear chains having some branches, e.g., low density polymer.

3. Cross-linked or Network polymers

formed from bi-functional and tri-functional monomers and contain
strong covalent bonds e.g. bakelite, melamine,
 Classification based on Source

• 1. Natural
E.g., Proteins, Cellulose, Starch, Rubber
Classification of Polymers
2. Semi-synthetic polymers
E.g., Cellulose derivatives - Cellulose acetate
(Rayon)

3. Synthetic polymers
E.g., Buna-S, Buna-R, Nylon, Polythene, Polyester.
 Classification based on Molecular Forces

1. Elastomers
eg. Buna-S, Buna-N, neoprene
2. Fibers
eg. Polyesters, Polyamides.
3. Thermoplastic polymers
eg. Polythene, Polystyrene, PVC.
4. Thermosetting polymers
eg. Bakelite, urea-formaldelyde resins
Order of strength :-
Thermosetting > Fibres > Thermoplastics > Elastomers
 Mechanism of Addition polymerization
Addition polymerization proceeds by the initial formation
of some reactive species such as free radicals or ions and by
the addition of the reactive species to the other molecule,
with the regeneration of the reactive feature.
Classification based on mode of Polymerization

• 1. Addition polymers
formed by the repeated addition of monomer molecules
possessing double or triple bonds
n(CH2=CH2) -(CH2 -CH2 )-
Ethylene polyethylene

2. Condensation polymers
formed by repeated condensation reaction between two different
bi-functional or tri-functional monomeric units.
eg. terylene (dacron), nylon 6, 6, nylon 6.

n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH)

[-NH(CH2)6NHCO(CH2)4CO-]n + nH2O
(Nylon 6:6)
 Addition or chain polymerization

1. Free radical mechanism:- Alkenes or dienes and their derivatives are

polymerized in the presence of a free radical generating initiator (catalyst)
like benzoyl peroxide, acetyl peroxide, t-bu peroxide, etc.

This process involves in 3 steps –

a) Chain initiation step - addition of phenyl free radical formed by the peroxide to the
ethene double bond ,thereby forming a larger radical.

b) Chain propagation step - repetition of this sequence with new and bigger radicals.

c) Chain terminating step - the product radical thus formed reacts

with another radical to form the polymerized product.

Some of polymers formed by this process are-

Polytetrafluroethene (Teflon), Polyacrylonitrile, Polyethylene, etc.
 CHAIN INITIATION STEP S

In chain initiation step, a free radical is first generated as a

result of physical or chemical effect, which is responsible for
the further continuation of the chain polymerization
i) Initiation: When the initiators are heated or exposed to sunlight, they
undergo hemolytic decomposition forming highly reactive species known as
free radicals. The free radical attacks the double bond of the monomer and
initiates the chain reaction. Example: when dibenzoyl peroxide initiators are
heated or exposed to sunlight.
 CHAIN TERMINATION STEP

ii) Propagation: The reactive monomer again reacts with another unsaturated
monomer and converts it into reactive monomer and growth of the polymer chain
continues.
CHAIN TERMINATION STEP
CHAIN TERMINATION STEP
 CONDENSATION POLYMERIZATION

In condensation polymerization, the chain growth is

accompanied by the elimination of small molecules. The
molecules are in the form of the water molecule H2O,
CH3OH, etc.
 Step Growth polymerization
It involves a repetitive condensation reaction between two
bi-functional monomers.
Eg. Formation of Nylon 6,6

nH2N(CH2)6 NH2 + nHOOC(CH2)4COOH 553K

High pressure

[-HN-(CH2) 6-NH-CO-(CH2)4-CO-]n +H2O

HH9

Nylon6,6
 Copolymerization
Copolymerisation is a polymerization reaction in which a mixture
of more than one monomeric species is allowed to polymerize and form
a copolymer. For example, a mixture of 1, 3 – butadiene and styrene can
form a copolymer.
Examples of Daily Use Polymers
 Polyethylene(PE)/Polythene

There are mainly two types of polythene:

Low density polythene(density range of
0.910–0.940 g/cm3):It is obtained by the
polymerisation of ethene under high pressure
of 1000-2000 atm at a temperature of 350-
570 K in the presence of traces of oxygen or a
peroxide initiator.
It is created by free radical polymerization.
 Properties:
1. High degree of short and long chain
branching.
2. intermolecular forces is less.
3. Tough but highly flexible & ductile.
4. Chemically inert.

Uses: Insulation of electricity carrying wires

and manufacture of squeeze bottles, toys and
flexible pipes.
  High density polythene(density >= 0.941 g/cm3):
formed when addition polymerisation of ethene
takes place in a hydrocarbon solvent in the
presence of a catalyst such as triethylaluminium
and titanium tetrachloride (Ziegler-Natta catalyst)
at a temperature of 333-343 K and under a
pressure of 6-7 atm.
 Properties:
1. low degree of branching(lack of branching is
ensured by an appropriate choice of catalyst &
reaction conditions).
2. stronger intermolecular forces and tensile
strength,
3. Chemically inert.
 Uses:for manufacturing buckets, dustbins, bottles,
water pipes etc.

 Environmental issue
Although polyethylene can be recycled, most of the
commercial polyethylene ends up in landfills, and in
the oceans such as the Great Pacific Garbage Patch.
Polyethylene is not considered biodegradable, except
when it is exposed to UV from sunlight. Under UV
lights tertiary carbon bonds in the chain structures are
the centres of attack. The UV rays activate such bonds
to form free radicals, which then react further with
oxygen in the atmosphere, producing carbonyl groups
in the main chain.
 Polystyrene
• Polystyrene is actually an aromatic polymer that is
made from the monomer styrene. It is a long
hydrocarbon chain that has a phenyl group attached
to every carbon atom. Styrene is an aromatic
monomer, commercially manufactured from
petroleum. Polystyrene is a vinyl polymer,
manufactured from the styrene monomer by free
radical vinyl polymerization.
 Properties

• Polystyrene is generally flexible and can come

in the form of moldable solids or viscous
liquids.
• The force of attraction in polystyrene is mainly
due to short range van der Waals attractions
between chains.
 Uses

• The outside housing of computer, housings of

most kitchen appliances, model cars and
airoplanes, toys, molded parts in car are all made of
polystyrene.
• It is also made in the form of foam that is used
for packaging and insulating.
• Polystyrene is generally flexible and can come in the
form of moldable solids or viscous liquids.
 Polyvinyl chloride

• It is a vinyl polymer constructed of repeating

vinyl groups (ethenyls) having one of their
hydrogens replaced with a chloride group.

• Obtained by heating a water emulsion of

vinyl chloride in presence of benzyl peroxide/
hydrogen peroxide in an autoclave under high
pressure.
 Properties

1. Colorless & odorless

2. Non-inflammable & chemically inert
3. Resistant to light,O2, inorganic acid & alkalis.
4. Greater stiffness & rigidity than polyethylene
but brittle.
 PVC

Most widely produced plastic

 Unplasticized PVC: Highly rigid but brittle, for making sheets,
tank lining, helmets ,mudguards etc.
 Plasticized PVC(by adding plasticizers e.g. phthalates):
Making continuous sheets of varying thickness, hoses, pipes,
construction, table covers, conveyor belts etc.
 Polytetrafluoroethylene (TEFLON)

• It is obtained by polymerization of water-emulsion of

tetrafluoro ethylene, under pressure and in the
presence of benzoyl peroxide as a catalyst.
 Properties

• Due to presence of high electronegative

fluorine in structure of TEFLON, strong
interchain forces are present which make it
extremely tough.
• High softening point (350°c).
• It has high chemical resistance.
• It has good mechanical and electrical
properties(high-performance substitute for
polyethylene)
 Uses

 It is used in insulating motor, transformers.

 It is used in making wires.
 Non-stick cookware coatings are made
from TEFLON for eg. In frying pan.
 Also used for making gaskets, tank linings, pipes and tubes for
chemical industries.
 Used for making non lubricating bearings.
 one of the lowest coefficients of friction against any solid.
 Poly(methyl methacrylate)

• Is a transparent thermoplastic, often used as a

light or shatter-resistant alternative to glass.
Synthetic polymer of methyl methacrylate.
Can be made by all types of moulding
processes.
 Properties

1. Strong & light weight

2. Good impact strength ,higher than both glass
& polystyrene.
3. Transmits up to 92% of light & filters UV
lights.
4. coefficient of thermal expansion is relatively
high.
5. Its properties can be modified to suit
requirements.
• Uses: Making aquarium glasses; automobile
headlights; spectator protection(e.g.- in ice
hockey rinks); Aircraft windows; Helmet
visors; making acrylic paints; bone cement,
contact lenses etc.
 AcrylonitrileButadieneStyrene

•Monomers:-Acrylonitrile , Butadieene, Styrene

•Formula :-(C8H8·C4H6·C3H3N)n

•Production :-Copolymer made by polymerizing styrene and acrylonitrile in the

presence of polybutadiene. The proportions can vary from 15 to 35% acrylonitrile, 5 to
30% butadiene and 40 to 60% styrene.

•Properties :-The styrene gives the plastic a shiny, impervious surface. The butadiene,
a rubbery substance, provides resilience even at low temperatures.Mechanical
properties vary with temperature.

•Application :-
1. Used to make light, rigid, molded products such as piping .
2. Musical Instruments such as plastic clarinet.
3. Golf club heads :- Used due to its good shock absorbance
4. Used as a colorant in tattoo inks.
Bakelite, a phenol-formaldehyde polymer, was the first
completely synthetic plastic, first made by Leo
Baekeland in 1907. Baekeland and an assistant started
their research in 1904 looking for a synthetic substitute
for shellac.
Bakelite was commercially introduced in 1909. Bakelite
was first used to make billiard balls, but, later, was used
to make molded insulation, valve parts, knobs, buttons,
knife handles, many types of molded plastic containers
for radios and electronic instruments, and more.
Phenolic reins set to rigid, hard, scratch resistant, infusible, water resistant, insoluble
solids, which are resistant to non-oxidizing acids, salts and many organic solvents,
but are attacked by alkalis, because of the presence of free hydroxyl group in their
structures, They posses excellent electrical insulating character.

Phenol - formaldehyde polymers are the oldest synthetic polymers. These are
obtained by the condensation reaction of phenol with formaldehyde in the
presence of either an acid or a base catalyst. The reaction starts with the initial
formation of o-and/or
p-hydroxymethylphenol derivatives, which further react with phenol to form
compounds having rings joined to each other through –CH2 groups. The initial
product could be a linear product – Novolac used in paints.
Novolac on heating with formaldehyde undergoes cross linking to form an infusible
solid mass called bakelite.
1.Plastic items like telephone parts,cabinets,heater handles.
2.Phonograph records
3.Electrical switches and berings used in propeller shafts in paper industry.
4.Soft bakelite used as binding glue for
laminated,wooden plants and in varnishes
5.Sulphonated bakelite are used as ion exchange resins.
6.For impregating fabrics,wood and paper.

valve parts, knobs, buttons, Phonograph records

Melamine resin or melamine formaldehyde (also shortened to melamine) is a
hard, thermosetting plastic material made from melamine and
formaldehyde by polymerization at 80°C.

Melamine formaldehyde resin gives water white products,have good tensile strength,
good electrical insulation, good chemical resistance, great hardness and good
abrasion resistance.
The resin is formed by condensation co-polymerisation of melamine and formaldehyde.
It is a quite hard polymer and is used widely for making plastic crockery
under the name Melamine. The articles made from melamine polymer do
not break even dropped from considerable height. They are also used as
laminates and for making decorative items. In paper industry to improve
wet strength of paper. In fabric treatment as finishing agent.
 Polyurethanes are made from a dialcohol and diisocyanate monomers. The isocyanate
compounds contain the functional group (O=C=N-). A rearrangement reaction leads to
the formation of the urethane linkage. Technically polyurethane is not a condensation
polymer since no molecules are lost, but the functional group does rearrange.
For example, Perlon-U (a crystalline polymer) is obtained by the reaction of 1,4-
butane diol with 1,6-hexane diisocynate
1.Polyurethanes are less stable than polyamides(nylons) at elevated temperature.
2.They are characterized by excellent resistance to abrasion and solvents.

Polyuraethenes are used as coatings, films, foams,adhesives and elastomers.

Resilient polyurethene fibres (spandex) are used for foundation garments and swim
suits.They also find use as a leather substutute(corfoam). They are used to cast to
produce gaskets, and seals.
Silicone polymers do not have carbon as part of the backbone structure. The although
silicon is in the same group as carbon in the periodic table, it has quite different
chemistry.
Many silanes are known which are analogous to the hydrocarbons with Si-Si bonds.
These compounds are not very stable and hence not very useful.
Silicones on the other hand have an alternating -Si-O- type structure. This basic
structural unit is found in many rocks and minerals in nature including common sand.
Various organic groups such as methyl or the benzene ring may be bonded to the silicon
as shown in the graphic on the bottom.
Silicones are water repellent, heat stable, and very resistant to chemical
attack. They find many uses in oils, greases, and rubberlike materials.
Silicone oils are very desirable since they do not decompose at high
temperature and do not become viscous. Other silicones are used in
hydraulic fluids, electrical insulators and moisture proofing agent in fabrics.
Silicones have a number of medical applications because they are chemically
inert. A good deal of controversy has involved the the use of silicone in
polyurethane bags as breast implants. Again they were used because they
were thought to be very inert and resistant to dissolving or other reactions.
Reports have cited increased cancer risk and severe immune responses from
possible leakage of the silicone from the implants.
EPOXY RESIN
 THE ORIGIN OF EPOXY RESINS
The first commercial attempts to prepare resins
from epichlorohydrin were made in 1927 in the
United States. Credit for the first synthesis of
bisphenol-A-based epoxy resins is shared by Dr.
Pierre Castan of Switzerland and Dr. S.O.
Greenlee of the United States in 1936. Dr.
Castan's work was licensed by Ciba, Ltd. of
Switzerland, which went on to become one of the
three major epoxy resin producers worldwide.
Ciba's epoxy business was spun off and later sold
in the late 1990s and is now the advanced
materials business unit of Huntsman Corporation
of the United States. Dr. Greenlee's work was for
the firm of Devoe-Reynolds of the United States.
Devoe-Reynolds, which was active in the early
days of the epoxy resin industry, was sold to Shell
Chemical (now Hexion, formerly Resolution
Polymers and others).
A new method of synthesis of high molecular weight epoxy resins is presented.
All reactions were performed in a multi-mode microwave reactor
“Plazmatronika” (microwave frequency - 2,45GHz, maximum of microwave
power - 300W). Shortening of the reaction time for all processes performed in
the microwave reactor, in comparison to conventional heating, was observed.

Synthesis of high molecular weight epoxy resins under microwave

irradiation
 PROPERTIES
Epoxy is a copolymer; that is, it is formed from two different
chemicals. These are referred to as the "resin" and the "hardener".
The resin consists of monomers or short chain polymers with an
epoxide group at either end. Most common epoxy resins are produced
from a reaction between epichlorohydrin and bisphenol-A, though the
latter may be replaced by similar chemicals. The hardener consists of
polyamine monomers, for example Triethylenetetramine (TETA). When
these compounds are mixed together, the amine groups react with
the epoxide groups to form a covalent bond. Each NH group can react
with an epoxide group, so that the resulting polymer is heavily
crosslinked, and is thus rigid and strong.
The process of polymerization is called "curing", and can be controlled
through temperature and choice of resin and hardener compounds;
the process can take minutes to hours. Some formulations benefit
from heating during the cure period, whereas others simply require
time, and ambient temperatures.
 APPLICATION
The applications for epoxy-based materials are extensive and include
coatings, adhesives and composite materials such as those using
carbon fiber and fiberglass reinforcements (although polyester, vinyl
ester, and other thermosetting resins are also used for glass-
reinforced plastic). The chemistry of epoxies and the range of
commercially available variations allows cure polymers to be
produced with a very broad range of properties. In general, epoxies
are known for their excellent adhesion, chemical and heat resistance,
good-to-excellent mechanical properties and very good electrical
insulating properties. Many properties of epoxies can be modified (for
example silver-filled epoxies with good electrical conductivity are
available, although epoxies are typically electrically insulating).
Variations offering high thermal insulation, or thermal conductivity
combined with high electrical resistance for electronics applications,
Wind Energy applications
Epoxy resin is used in manufacturing the rotor blades of wind turbines. The resin is
infused in the core materials (balsa wood, foam) and the reinforcing media (glass,
fabric). The process is called VARTM, i.e. Vacuum Assisted Resin Transfer Moulding.
Due to excellent properties and good finish, epoxy is the most favoured resin for
composites.

Aerospace applications

Electrical systems and electronics

Paints and coatings
Adhesives

Industrial tooling and composites

Consumer and marine applications

Nylon is used as general name for all synthetic fiber forming polyamides,
i.e., having a protein like structure. These are the condensation polymers of
diamines and dibasic acids A number is usually suffixed with the
Nylon which refers to the number of carbon atoms present in the diamine
and the dibasic acids respectively.

Nylon-6,6 is obtained by the polymerisation of adipic acid with hexamethylene

diamine.
It is produced by the self condensation of caprolactum.

Beckmann Rearrangement
1.They are translucent,whitish,horny,high melting polymers .
2.They posses high temperature stability and high abrasion resistance.
3.They are insoluble in common organic solvents(like methylated spirit,benzene
and Acetone), and soluble in phenol and formic acid.
4.Their mouldings and extrusions have good physical strengths(especially high
impact strength) and self lubricating properties.

1.They are light, horny, and high melting.

2.They are insoluble in common solvents.
3.They have good strength.
4.They absorb little moisture ; and are thus ’drip-dry’ in nature.
5.They are very flexible and retain original shape after use.
6.They are resistant to abrasion.
7.On blending with wool, the strength and abrasion resistance of the latter increases.
1.Nylon-6,6 is primarily used for fibres, which find use in making socks, ladies hoses,
dresses, carpets,etc.
2.Nylon-6 is mainly used for moulding purposes for gears, bearings, electrical
mountings, etc. These bearings and gears work quietly without any lubrication.
3.They are also used for making filaments for ropes, bristles for tooth brushes and
films, tyre cords,etc.
 POLYCARBONATES

Repeating chemical structure unit of

Polycarbonate made from bisphenol A
 SYNTHESIS
•The main polycarbonate material is producted by the reaction of
bisphenol A and phosgene (COCl2). The first step involves treatment
of bisphenol A with sodium hydroxide, which deprotonates the
hydroxyl groups of the bisphenol A.

(HOC6H4)2CMe2 + 2 NaOH → (NaOC6H4)2CMe2 + 2 H2O

•The diphenoxide ((NaOC6H4)2CMe2) reacts with phosgene to give a

chloroformate, which subsequently is attacked by another phenoxide.
The net reaction from the diphenoxide is:

(NaOC6H4)2CMe2 + COCl2 → 1/n [OC(OC6H4)2CMe2]n + 2 NaCl

 In this way, approximately one billion kilograms of

polycarbonate is produced annually
 Uses of polycarbonates
1) Domestic wares
2) Electrical insulator in electronic industries
3)Other uses for polycarbonate
include greenhouse enclosures, automobile
headlights, outdoor fixtures, and medical industry
applications, though the list is virtually endless.
POLYMERIZATION TECHNIQUES

POLYMERIZATION TECHNIQUES
1. Bulk polymerization
2. Solution polymerization
3. Suspension polymerization
4. Emulsion polymerization
 BULK POLYMERIZATION
• Mass or block polymerization: Polymerization of the undiluted monomer.
carried out by adding a soluble initiator to pure monomer (in liquid state).
• The mixture is constantly agitated & heated to polymerization temperature.
• Once the reaction starts, heating is stopped as the reaction is exothermic.
• The heat generated is dissipated by circulating water jacket.
• Viscosity increases dramatically during conversion.
• The method is used for the polymerization of liquid state monomers.
• It is usually adopted to produce polystyrene, polyvinyl chloride, polymethyl
methacrylate and low density polyethylene.
 ADVANTAGES OF
BULK POLYMERIZATION

• The system is simple and requires thermal insulation.

• The polymer obtained is pure.
• Large castings may be prepared directly.
• Molecular weight distribution can be easily changed with the use of a chain
transfer agent.
• The product obtained has high optical clarity
• High rates of polymerization
• High degree of polymerization
• High purity of product
• High molar mass polymer are produce
 DISADVANTAGES OF
BULK POLYMERIZATION

Disadvantages
• Heat transfer and mixing become difficult as the viscosity of reaction mass
increases.
• The problem of heat transfer is compounded by the highly exothermic nature of
free radical addition
polymerization.
• The polymerization is obtained with a broad molecular weight distribution due
to the high viscosity and lack of good heat transfer.
• Very low molecular weights are obtained.
• Increase in the reaction viscosity with conversion.
• *difficulty in removing heat.
• *auto-acceleration
• *if the polymer formed is insoluble in the monomer (such as acrylonitrile, vinyl
chloride) ==> precipitating of the polymer and we can not apply the kinetics.
 SOLUTION POLYMERIZATION

• Solution polymerization is a method of industrial polymerization. In this procedure,

a monomer is dissolved in a non-reactive solvent that contains a catalyst.
• The reaction results in a polymer which is also soluble in the chosen solvent. Heat
released by the reaction is absorbed by the solvent, and so the reaction rate is
reduced. Moreover the viscosity of the reaction mixture is reduced, not allowing
auto-acceleration at high monomer concentrations. Once the maximum or desired
conversion is reached, excess solvent has to be removed in order to obtain the pure
polymer.
SOLUTION POLYMERIZATION
SOLUTION POLYMERIZATION
 SOLUTION POLYMERIZATION

Advantage
• Hence, solution polymerization is mainly used for applications where the
presence of a solvent is desired anyway, as is the case for varnish and adhesives.
It is not useful for the production of dry polymers because of the difficulty of
complete solvent removal.
• This process is one of two used in the production of sodium polyacrylate, a
superabsorbent polymer used in disposable diapers.
• Notable polymers produced using this method are polyacrylonitrile (PAN) and
polyacrylic acid (PAA).
• This method is used to solve the problems associated with the bulk
polymerization because the solvent is employed to lower the viscosity of the
reaction, thus help in the heat transfer and reduce auto-acceleration.

Disadvantage
• Reduce monomer concentration which results in decreasing the rate of the
reaction and the degree of polymerization.
• Solvent may cause chain transfer.
• Clean up the product with a non solvent or evaporation of solvent.
 SUSPENSION POLYMERIZATION

• This method is used also to solve the problem of heat transfer. It is similar to bulk
polymerization where the reaction mixture is suspended as droplets in an inert
medium. Monomer, initiator and polymer must be insoluble in the suspension media
such as water.

• Suspension polymerization is a heterogeneous radical polymerization process that

uses mechanical agitation to mix a monomer or mixture of monomers in a liquid
phase, such as water, while the monomers polymerize, forming spheres of polymer.

• This process is used in the production of many commercial resins, including polyvinyl
chloride (PVC), a widely used plastic, styrene resins including polystyrene, expanded
polystyrene, and high-impact polystyrene, as well as poly(styrene-acrylonitrile) and
poly(methyl methacrylate).
 SUSPENSION POLYMERIZATION

• This is one of procedure used to induce radical polymerization with a vinyl group
monomer. A polymerization process in which an insoluble monomer is dispersed
and suspended by continuous strong agitation in a liquid phase, usually water, and
it became monomer droplet with the size of 0.01~1mm. In addition, the
polymerization in which soluble initiator (for example: benzoyl peroxide or
azobisisobutyronitrile) is added in the monomer. Poly-addition reaction such as
polyurethane may also performed in a suspended form.

• Suspension polymerization most commonly used as industrial manufacturing

method in order to get polymer for forming material such as polystyrene,
polymethylmethacrylate, polyvinyl acetate, polyvinyl chloride, because a polymer
with a high degree polymerization is obtained with the polymerization and
generated polymer isolation is easy.
SUSPENSION POLYMERIZATION
 EMULSION POLYMERIZATION

• This is similar to suspension polymerization except that the initiation is soluble in

suspension media and insoluble in the monomer.
• The reaction product is colloidally stable dispersion known as latex.
• The polymer particles have diameter in the range of (0.05 - 1 μm) smaller than
suspension.
• Emulsion polymerization is a type of radical polymerization that usually starts with an
emulsion incorporating water, monomer, and surfactant. The most common type of
emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the
oil) are emulsified (with surfactants) in a continuous phase of water. Water-soluble
polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used
to act as emulsifiers/stabilizers.
 EMULSION POLYMERIZATION

• The name "emulsion polymerization" is a misnomer that arises from a

historical misconception. Rather than occurring in emulsion droplets,
polymerization takes place in the latex particles that form spontaneously in
the first few minutes of the process. These latex particles are typically 100 nm
in size, and are made of many individual polymer chains. The particles are
stopped from coagulating with each other because each particle is surrounded
by the surfactant ('soap'); the charge on the surfactant repels other particles
electrostatically. When water-soluble polymers are used as stabilizers instead
of soap, the repulsion between particles arises because these water-soluble
polymers form a 'hairy layer' around a particle that repels other particles,
because pushing particles together would involve compressing these chains.
 EMULSION POLYMERIZATION

Emulsion polymerization is used to manufacture several commercially important

polymers. Many
of these polymers are used as solid materials and must be isolated from the aqueous
dispersion
after polymerization. In other cases the dispersion itself is the end product. A
dispersion resulting
from emulsion polymerization is often called a latex (especially if derived from a
synthetic rubber)
or an emulsion (even though "emulsion" strictly speaking refers to a dispersion of an
immiscible
liquid in water). These emulsions find applications in adhesives, paints, paper coating
and textile
coatings. They are often preferred over solvent-based products in these applications
due to the
absence of VOCs (Volatile Organic Compounds) in them.
EMULSION POLYMERIZATION
Advantages
High molecular weight polymers can be
made at fast polymerization rates. By contrast,
in bulk
and solution free radical polymerization, there
is a tradeoff between molecular weight and
polymerization rate.
The continuous water phase is an excellent
conductor of heat, enabling fast
polymerization rates
without loss of temperature control.
Since polymer molecules are contained
within the particles, the viscosity of the
reaction medium
remains close to that of water and is not
dependent on molecular weight.
The final product can be used as is and does
not generally need to be altered or processed.
Disadvantages
Surfactants and other polymerization
adjuvants remain in the polymer or are difficult
to remove
For dry (isolated) polymers, water removal is
an energy-intensive process
Emulsion polymerizations are usually
designed to operate at high conversion of
monomer to
polymer. This can result in significant chain
transfer to polymer.
Cannot be used for condensation, ionic or
Ziegler-Natta polymerization, although some
Cannot be used for condensation, ionic or
Ziegler-Natta polymerization, although some
exceptions are known.
 Plastics
• Plastics are high molecular weight organic materials
which can be moulded into any desired shape by the
application of heat and pressure in the presence of
catalyst.

Constituents of plastics:
1. Resins
2. Plasticizers
3. Fillers or Extenders
4. Lubricants
5. Stabilizers
6. Pigments
7. Anti-oxidants
8. Catalysts or Accelerators
 Plastics
Resins:
• They are basic binding materials and hold the constituents together.
• They are generally linear polymers with low molecular weight to
enhance fusibility and mouldability.
• It is then converted into crosslinked form during moulding in the
presence of a catalyst.
• E.g. Thermoplastic resins and thermosetting resins.

Plasticizers:
• They improve flow for processing by reducing the intermolecular
force of attraction
• E.g. Dioctylphthalate, oleate and organic phosphates

Fillers:
• They increase the tensile and compressive strength of plastics.
• They also reduce the shrinkage during setting of the plastics.
• E.g. Mica, quartz, limestone, acrylics
 Plastics
Lubricants:
• They makes the moulding process easier and also provide glossy finish to
the final product.
• E.g. Waxes, oils and soaps

Stabilizers:
• They increase the thermal stability during processing.
• E.g. Stearates of lead, barium and cadmium.

Pigments:
• They provide colours to the plastics
• TiO2, ZnO – White; Cr2O3 – Green, Carbon black – black, Red lead - Red
• Anti-oxidants: They protect against oxidative degradation
• E.g. Phenyl p-napthyl amine, diphenyl p-phenylene diamine

Catalysts:
• They are added to accelerate the polymerization of fusible resin into cross-
linked infusible form especially for thermosetting plastics.
• E.g. H2O2, benzoyl peroxide
Thermoplastic Polymers
 Definition

• These are linear or slightly branched long

chain polymers, which can be softened on
heating & reversibly hardened on cooling
repeatedly.
• Their hardness is a temporary property &
varies with temperature.
It can be reprocessed, so sometimes also
referred as green plastics.
 Structure

Thermoplastics possess weak intermolecular

forces(e.g. Van der Waal) & don’t have
crosslinks.
 Examples

 Cellulose derivatives
- 1) Cellulose acetate
- Cellulose nitrate
 Polyethenic/vinyl resins
- 2) Polyethylene
- 3) Polypropylene
- 4) Polyvinyl acetate
- 5) Polyvinyl chloride
- 6) Polystyrene
- 7) Teflon
- 8) Acrylic
- 9) Polysulfone
- 10) Polyester
 Structure
Polycarbonates received their name because they are
polymers containing carbonate groups (-O-(C=O)-O-). Most
polycarbonates of commercial interest are derived from rigid
monomers. A balance of useful features including temperature
resistance, impact resistance and optical properties position
polycarbonates between commodity plastics and engineering
plastics
 (1)The number-average molecular weight for a
discrete distribution of molecular weights is given
as

where N is the total number of molecular-weight

species in the distribution.
(2) The weight-average molecular weight is given as
A measure of the molecular-weight distribution is given by the ratios of molecular
-weight averages.
For this purpose, the most commonly used ratio is Mw/Mn, which is called the
polydispersity index or PDI.

PDI= Mw/Mn

Mw/Mn = 1 monodisperse
Polymer sample consisting of molecules all of which have the same
chain length

Mw/ Mn > 1 polydisperse

Polymer consisting of molecules with the variety of chain length
 Processing (or) moulding (or) compounding of plastics
Compounding or moulding is a process by which the polymer resins are mixed with
some additives like fillers, plasticizers, stabilizers etc to impart some special
properties to the moulded final product.

Ingredients of a plastic

Additives Examples Function/Importance

1. Resins Thermoplastic and Basic binding materials and holds

thermosetting resins the constituents together. Major part
of the plastics. Thermosetting resins
transferred in to crosslinked plastics
during moulding in presence of a
catalyst
2. Plasticizers Dioctylphthalate (DOP) To improve the elasticity and to
Adipate, Oleate, reduce the brittleness of the plastics.
Organic Phosphate Also improves the flow of polymer
during the process

12/8/2019 98
Additives Examples Function/Importance

3. Fillers (or) Mica, quartz, Limestone, Increases the tensile and compressive
Extenders Nylon strength of plastics. They reduce the
shrinkage during the process of setting

4. Lubricants Waxes, Oils, soaps To make the moulding process smooth and
give the glossy finish to the final product

5. Stabilizers Stearates of Pb, Ba and Cd To increase the thermal stability of a

polymer

6. Pigments TiO2, ZnO (white), chromium

oxide (green), carbon black, To provide colours to the moilded articles
Read Lead

Phenyl, n-napthyal amine, Protection against oxidation

7. Anti-Oxidants
Diphenyl-p-
phenylenedimaine

8. Catalyst H2O2 and Benzoyl peroxide Added only in the case of thermosetting
resins to increase the rate of polymerisation

99
 Different types of Moulding technique

The moulding is different for various polymer depends on their thermal behaviour and
nature of the resins.

1. Compression moulding Used for moulding the

2. Transfer moulding thermosetting polymers

3. Injection moulding Used for moulding the thermo

polymers
4. Extension moulding and

5. Blow moulding Used for moulding the bottle

type articles which has narrow
neck

100
 1. Compression Moulding of plastics

Pressure • The process of molding a material in a confined shape by

Pressure = 70 kg/cm2 applying pressure and usually heat.
• Almost exclusively for thermoset materials
• Used to produce mainly electrical products

Top moulding part of the die

(plunger)
•A force of 2900psi is usually required
for moldings up to 1inch (25 mm) thick.
•An added 725psi should be provided
Guide pins for each 1inch (25 mm) increase.

Molten polymer with ingredients in

the cavity at 200oC

Bottom moulding part of the die with cavity (the

shape of the cavity decides the shape of the final
product)

Extraction pin
Pressed plastic
material
12/8/2019 101
 2. Transfer Moulding of plastics
This is exclusively used for thermosetting plastics. The resin ingredients mixture is preheated in a preheating chamber.
When the moulding mixture becomes plastic then it is forced through a orifice into the hot mould by using the plunger.
After setting time it is taken out. Complicated shapes can be made.

Heaters
Plunger (top molding
part)

Charger (plastic ingredients)

Sprue

Molding Cavity

Bottom molding part

Ejector pin

A process of forming articles by fusing a plastic material in a chamber

then forcing the whole mass into a hot mold to solidify.
Used to make products such as electrical wall receptacles and circuit
breakers
Molded
plastic

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 3. Injection Moulding of plastics
Clamping Molding part Injection part

*
Cavity
Hopper Hydraulic
screw drive
Barrel

Heater bands

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 Pressing of molten polymer using die and plunger in Injection Molding

The feeding or injection of hot

plastic

This method is generally used for

thermoplastics.

Die The moulding composition is heated in a

suitable chamber connected by a duct
leading to the mould.
The hot softened plastic is then forced under
high pressure into the relatively cool mould
The cavity in which the molten plastic will
cavity where it is set by cooling and the
Plunger be fed and pressed
moulded object is then ejected.
The temperature range used is 90 to 260oC.

12/8/2019
* Source: http://www.idsa-mp.org/proc/plastic/injection/injection_process.htm 104
 4. Extrusion Moulding of plastics
It is a process in which the molten plastic material is forced through a die which produces
a continuous extrudate (product) in the form of final product. This process is used mainly
for the production of films tubes, rods, hoses.
It also used for the coating cables with PVC and other plastics.

Raw materials
Molten
polymer Die

Extruded pipe

Screw Heater
conveyer Cooling of final
product

105
Thank you