The Polymer Industry

DO YOU HAVE ANY IDEA WHAT

BRAND IS THIS?
Industrial Use of Polymers
• Charles Goodyear,1839 -discovery of vulcanization in
rubber.
• After 1930: nylon, polyethylene and polyvinyl
chloride
 POLYMER

GREEK WORD
“poly” means many
“meros” means units.

• Polymers are substances that are made from the many repeating structural units
called monomers.
• Monomers may be of the same type or may be of different types.
• The formation of polymers from monomer units is called polymerization
• Made up of hundreds or Thousands of many identical Small Units (Monomers) of
CARBON, HYDROGEN, OXYGEN or SILICON atoms.
POLYMERIZATIO
N
• The process by which the monomer molecule
are linked to form a big polymer molecule
called 'polymerization'
• a process of bonding monomer, or
“single”together through a variety of reaction
mechanisms to form longer chains named
polymer
• in par with polymer, they exist with
monomers, which are small, single molecules
such as hydrocarbon and amino accid
CLASSIFICATION OF POLYMER
1. By Origin
2. By Monomer
3. By Thermal Response
4. By Mode of Formation
5. By Structure
6. By Application & Properties
7. By Tacticity
Natural Polymers

Bio Polymers
Origin of Polymers

Synthesic
Polymers
NATURAL POLYMERIC
MATERIAL
 occur in nature and can be
extracted.
 They are often water-based.

Example:
- Silk, wool, Starch, and natural
rubber
Cellulose - main constituent of
wood and paper.
Hevea Rubber
Tree
SYNTHETIC POLYMERS derived from
petroleum oil made by scientists and engneers.
BIOPOLYMERS
are polymers produced from
natural sources either chemically
synthesized from a biological
material or entirely biosynthesized
by living organisms.
I. NUCLEIC ACID POLYMERS
DNA & RNA - Carry
genetic information of the cell
 • Cr
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• Br s-
• Li lin
an
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ch
Based on Structure

ar d
ed
Po ch
Po
ly ai
ly
m n
m
ers Po
ers
ly
m
ers
1 2 3
LINEAR
POLYMERS
• Consist of a ng string of carbon-
carbon bonds
• These types of polymerss are often
quite flexible
• Van der Waal's forces and H-
bonding are the two main types of
interaction between the
• EX: Polyethylene, teflon, PVC,
Polypropylene
BRANCHED POLYMER
• Polymers with branches irregular intervals
along the polymer chain
• Leading to difficulty/ inability of chains to
pack very closely together
• Less crystalline and less dense
• Amount and type of branching also affects
physical properties such as viscosity and
elasticity.
• Branches often prevent chains from getting
close enough together for intermolecular
forces to work effectively.
CROSS-LINKED POLYMER
• Formed from bi-functional and tri-
functional monomers and contain strong
covalent bonds
• contain short side chains(crosslinks)
• Connect different polymer chains into a
“network”
• Adding cross-links between polymer chains
makes the polymer more elastic (they can
stretch and return to their original form
Homopolymers
• Homopolymer is a polymer
that is made up of only one
type of monomer unit.
• For example, polythene
(monomer unit is ethylene),
PVC ( monomer unit is vinyl
chloride), etc.
Copolymers
• A copolymer is a polymer that is
made up of two or more
monomer species. .
• The process in which a
copolymer is formed from
multiple species of monomers is
known as copolymerization.
• It is often used to improve or
modify certain properties of
plastics.
• Many commercially important
polymers are copolymers
Examples include polyethylene-vinyl acetate (PEVA), nitrile
rubber, and acrylonitrile butadiene styrene (ABS).
Classification of Copolymers
• Block Copolymers- When more than
one homopolymer units are linked
together via covalent bonds,
• Statistical Copolymers-polymers in
which two or more monomers are
arranged in a sequence that follows
some statistical rule.
• Alternating Copolymers- Alternating
copolymers contain a single main chain
with alternating monomers.
• Periodic Copolymers- feature a
repeating sequence in which the
monomers are arranged in a single
chain.
 • AD
1.

ON
TI
DI
BASED ON
POLYMERIZATION

• CO
2. ON
TI
SA
EN
ND
ADDITION POLYMERIZATION
• Formed by the repeated addition ofolefinic monomer without
elimination of any simple molecules.
CONDENSATION
POLYMERIZATION
• It is a form of a step-growth polymerization where
smaller molecules or monomers react with each other to
form larger structural units (usually polymers) while
releasing by-products such as water or methanol
molecule.
• The by-products are normally referred to as condensate.
CHARACTERISTIC OF CONDENSATION
POLYMERIZATION
• The molecules should have one or two functional groups (like alcohol, amine, or carboxylic acid
groups).
• The reaction occurs between two similar or different functional groups or monomers. It can
take place between a dimer and oligomer, one monomer and one dimer or between a chain
and another chain of polymers.
• Smaller molecules usually combine to form larger molecules.
• Mixed properties of both the molecules or functional groups are taken into consideration.
• A linear polymer is obtained as the condensation product when both functional groups are
difunctional.
• When one of the functional groups is tri- or tetra-functional, the polymer formed will be a
cross-linked polymer having a three-dimensional network.
• The average molecular weight decreases when monomers are added with one reactive group.
Therefore, the functionality of each monomer determines the average molecular weight and
cross-link density.
ELASTOMERS

BASED ON MOLECULAR FORCES

FIBERS

THERMOPLASTICS

THERMOSETTING
ELASTOMERS
• polymeric materials with irregular structure and weak intermolecular
attractive forces.
• Elastomers are capable of high extension (up to 1000%) under
ambient conditions.
• they have the particular kind of elasticity characteristic of rubber.
• elasticity is attributed to the presence of chemical and/or physical
crosslinks in these materials.
• normal state, elastomers are amorphous, and as the material is
stretched, the random chains are forced to occupy more ordered
positions
ELASTOMERS
• Releasing the applied force allows the elongated chains to return
to a more random state. Thus, the restoring force after elongation is
largely because of entropy.
• Elastomers can also be made from block copolymers containing
hard or rigid segments of polyurethane and soft or flexible
segments derived from the polyester or polyether diols with
degrees of polymerization generally above 15.
• Polyurethane elastomeric materials:
• exhibit good abrasion resistance,chemical resistance, and good tear strength
with a wide variation of flex_x0002_ibility available.
• also used in fabrics and sport_x0002_ing goods.
FIBERS
• An object with a length-to-diameter ratio of at least 100
• Fibers (synthetic or natural) are polymers with high molecular symmetry and
strong cohesive energies between chains; presence of polar groups.
• Fibers possess a high degree of crystallinity; presence of stiffening groups in
the polymer backbone, and of intermolecular hydrogen bonds
• Fibers are normally linear; long, thin, and threadlike, with great strength along
the fiber. These characteristics permit formation of this type of polymer into long
fibers suitable for textile applications.
• Typical examples of fibers include poly_x0002_esters, nylons, and acrylic
polymers such as polyacrylonitrile, and naturally occurring polymers such as
cotton, wool, and silk.
NYLON
• Nylon is used as general name
for all synthetic fibers forming
polyamides, i.e., having protein
like structure
• These are the condensation
polymers of diamines and
dibasic acids
• A number is usually suffixed
with the Nylon which reffers to
the number of carbon atoms
present in the diamine and the
dibasic acids respectively.
THERMOPLASTIC Polymers
• Are linear/slightly branched • Examples of commercial
long chain polymers, which can thermoplastics are:
be soften on heating & • polystyrene, polyolefins (e.g.,
reversibly hardened on cooling polyethylene and polypropylene),
repeatedly. nylon, poly(vinyl chloride), and
• Their hardness is a temporary poly(ethylene terephthalate)
property & varies with • Advantageously, waste
temperature and pressure. thermoplastics can be recovered
and refabricated by
application of heat and
pressure.
THERMOSETTING POLYMER
• are polymers whose individual chains have
been chemically linked by covalent bonds
during polymerization or by subsequent
chemical or thermal treatment during
fabrication.
• usually exist initially as liquids called
prepolymers; they can be shaped into desired
forms by the application of heat and
pressure.
• Once formed, these cross-linked networks
resist heat softening, creep and solvent
attack, and cannot be thermally processed or
recycled.
• Principal examples of thermosets: epoxies,
phenol-formaldehyde resins, and unsaturated
polyesters.
 POLYMER INDUSTRY
Polymers are used in shelter, clothing, health, food,
transportation, and almost every facet of our lives. In fact, it is
hard to imagine what the world would be like without
synthetic polymers. Production and fabrication of polymers
are major worldwide industries.
POLYMER STRUCTURE PROPERTY
THERMAL PROPERTIES
Polymers exhibit some interesting thermal properties that depend on
their structure and crystallinity.
Crystallinity: This refers to how organized the polymer chains are
within the material. Polymers can be:
• Amorphous: Chains are randomly arranged, with no ordered structure.
These exhibit a glass transition temperature (Tg).
• Semi-crystalline: Chains have both ordered crystalline regions and
disordered amorphous regions. They exhibit both Tg and a melting point
(Tm).
• Crystalline: Chains are highly organized in a crystal lattice structure. They
only exhibit a melting point (Tm)
Thermal stability.
• to be considered thermally stable or heat resistant, it
should not decompose <4000C; should retain its
useful properties at temperatures near the
decomposition temperatures.
• Aromatic polymers are used and applied in aerospace
industries (as fabrics for astronauts' clothing for
example) because of being resistant to high
temperatures.
Glass transition temperature Tg.
• Tg: The temperature at which an amorphous polymer changes from a hard and brittle state
(glassy) to a rubbery or flexible state. This happens because the polymer chains start to move more
freely (segmental motion). Below Tg, the polymer is stiff due to limited chain movement.
• Tm (melting point) : The temperature range where the entire polymer chain becomes mobile and
the polymer melts, transitioning into a liquid state.
• Relationship: Tg is typically one-half to two-thirds of Tm (in Kelvin) for many polymers.
• Tg depends on structure: The chemical structure of the polymer chain heavily influences its Tg.
Factors like backbone flexibility, side groups, and their arrangement all play a role.
• Polymers with flexible backbones and small side groups tend to have lower Tg (more flexible at
lower temperatures).
• Polymers with rigid backbones, especially those containing aromatic groups in the main chain,
have higher Tg (stay stiff at lower temperatures).
MECHANICAL PROPERTIES
• depend on many variables—molecular weight,
molecular weight distribution, morphology,
additives, temperature, time, and so on.
• much more dependent on molecular weight over a
very broad range, yet they too level off
(POLYAMIDES: 20,000-50,000) at high molecular
weight.
• Mechanical properties of a polymer are mainly determined by how much
stress a sample will withstand before the sample fails. At low strain (i.e.,
<1 percent), the deformation of most polymers is elastic where the
deformation is homogeneous and full recovery can occur over a finite
time.
• Among the mechanical properties that are of fundamen_x0002_tal interests
in commercial polymers are:
1. Tensile strength: It is a measure of resistance to stretching. Anything that
contributes to chain stiffening such as the presence of bulky side groups, cyclic
units, cross-linking, and crystallinity, will increase the tensile strength, but decrease
the tensile elongation.
2. Compressive strength: It is the extent to which a sample can be
com_x0002_pressed before it fails.
3. Flexural strength: It is a measure of resistance to breaking, or snap_x0002_ping,
when a sample is bent (flexed).
4. Impact strength: It is a measure of toughness, that is, how well a sample will
withstand the sudden onset of stress, like a hammer blow. Usually, chain stiffening
lowers the impact strength and increases embrittlement.
5. Fatigue: It is a measure of how well a sample will withstand repeated application of
tensile, flexural, or compressive stress.
6. Creep: It is the cold flow of a polymer. It is a measure of the change in strain when a
polymer sample is subjected to a constant stress (such as gravity).
7. Stress relaxation: It refers to the decrease in stress when a sample is elongated
rapidly to a constant strain.
TENSILE
STRENGTH
(ASTM D638)
Tensile strength
(measured using ASTM
D638) is a crucial test for
determining the maximum
stress a polymer can
withstand before it breaks
(yields or fractures) when
pulled apart
COMPRESSIVE
STRENGTH (ASTM
D695)
Ultimate compressive strength (the
maximum stress to rupture a test
sample)
Compressive strength at a specific
deformation (i.e. 0.1%, 1%,10% –
typically used for materials like
plastics that may not rupture)
Compressive yield strength (the stress
in psi as measured at the point of
permanent yield, zero slope, and on
stress-strain curve)
FLEXURAL
STRENGTH (ASTM
D790)
Flexural properties measure a
material’s resistance to bending
under load. The load at yield is
the flexural strength of the
material and is typically
expressed in psi. For plastics, the
data is usually calculated at 5%
deformation/strain (the loading
necessary to stretch the outer
surface 5%).
 Rockwell (ASTM D 785) or Indentation Hardness /
Durometer (ASTM D 2240)
The Rockwell test is typically chosen for
hard materials such as acetal, nylon, and
PEEK where creep is less of a factor in the
test results
The Durometer is reported for softer
materials such as urethane. The two scales
do not correlate and cannot be compared.
Data from a single scale is best used to
compare hardness for one material versus
another. Hardness data is best used to
compare materials. By itself the test is not
an indication of strength, wear performance
or abrasion resistance.
Izod Impact (ASTM D 256)
a pendulum arm swings to impact a
notched, cantilevered beam as shown below.
After fracturing the test specimen, the
pendulum continues to travel in the same
direction, but with less energy. This loss of
energy, measured in foot-pounds per inch
(ft-lb/in., or J/m) of beam thickness, is
known as the Izod impact strength. This test
can also be done with either an unnotched
specimen or with the notch reversed, in which
case it is reported as “unnotched” or
“reversed notch Izod” impact strength,
respectively.
SOLUBILITY
• Solvents are frequently used during the polymerization processes, during
fabrication (i.e., film casting, fiber formation, and coatings), and for the
determination of molecular weight and molecular weight distribution.
• Dissolution of a polymer sample in a solvent occurs in two stages.
• The first stage is a solvation process in which the solvent molecules diffuse slowly through
the polymer matrix to form a swollen, solvated mass called a gel.
• The second stage of dissolution consists of a breakdown of the swollen gel to give an
actual solution of polymer molecules in the given solvent.
• general, linear and branched polymers dissolve in the second stage, whereas
cross-linked polymers remain in a swollen condition. However,lack of solubility
does not necessarily mean that the polymer is of the network type; some linear
polymers defy all attempts to dissolve them.
GENERAL RULES FOR POLYMER
SOLUBILITY
1. Chemical structure: Polar polymers tend to dissolve in polar sol_x0002_vents,
and nonpolar polymers tend to dissolve in nonpolar solvents (like dissolves like).
Therefore, chemical similarity of a polymer and solvent is a fair indication of
solubility.
For example, ethanol can dissolve poly(vinyl alcohol) but not polystyrene, whereas
toluene can dissolve polystyrene but not poly (vinyl alcohol).
2. Molecular weight: In a given solvent at a particular temperature, the solubility of
a polymer decreases as its molecular weight increases.
3. Cross-linking: If a polymer is cross-linked to a significant degree, it
will only swell as a result of taking liquid into the network, but com_x0002_plete
dissolution does not occur.
4. Crystallinity: In general, solubility of a polymer decreases with an
increase in the degree of crystallinity, but it is possible to find solvents capable of
overcoming the crystalline bonding forces and hence dis_x0002_solving the
polymer. Also, solubility is enhanced by heating the poly_x0002_mer to a
temperature close to its crystalline melting point.
5. Branching: In general, solubility increases with increasing polymer
branching.
VISCOCITY of POLYMERS
• a measure of its resistance to flow. “As a material's
resistance to flow increases, its viscosity increases.”
• usually reported in:
• a unit called poise, which is dyne seconds per square centimeter (1
poise = 1O-1 Nsm-2).
• Pascal, which is Newton seconds per square centimeter (1 Pas =
10 poise).
POLYMERIZATION TECHNIQUE
Polymerization techniques: Polymerization reactions are exothermic
and the main concern during polymerization is to effectively dissipate
the heat from the reaction mixture to avoid explosion and also for
running heat sensitive polymer products. The main polymer processes
are
POLYMERIZATION TECHNIQUE
Homogenous polymerization process: In this process, the
polymerization occurs in one phase, may be in a solvents or in a
reaction vessel containing only monomer. So there two main methods,
solution and bulk polymerization respectively.
BULK POLYMERIZATION
• In mass polymerization, the whole system remains in a homogenous
phase, because the monomer is taken in the liquid state, the
initiator is dissolved in the monomer and the chain transfer agent
(if used to control the molecular weight) is also dissolved in the
monomer.
• The reaction mixture is heated or expose a UV light radiation
source for initiating the polymerization and is kept on a rotary
shaker for proper mixing the mass and uniform heat transfer.
• Only the initiator and the chan transfer agent is used therefore, the
product formed has a high degree of purity, i.e., without any
contamination of reactants and components.
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.
ADVANTAGES
• The system is simple and
requires a thermal insulation.
• the polymer is obtained pure
• minimun chances of
contaminaton
• Molecular weight distribution
with the use of a transfer agent.
DISADVANTAGES
• Heat trasnfer and mixing becomes
difficult as the viscosity of
reaction mass increases.
• The polymerization is obtained
with a broad molecular wwight
distribution due to the high
viscosity and lack of good heat
transfer.
• excessive heat due to exothermic
reaction may lead to explosion.
• Very low molecular weight are
obtained.
APPLICATION
• The method is used for the polymerization of liquid state monomers.
• Low molecular weight polymers obtained by this method, are used as
adhesive, plasticizers and lubricants
• Used in casting formulations
• Production of methyl methacrylate (MMA)(suspension also),
Polyamides, polycarbonates, polyethylene (low density),
terephthalate, polycaprolactam (nylon-6)
SOLUTION POLYMERIZATION
• The whole system is in a homogenous phase, because the monomer,
chain transfer agent (is used) and the initiator are dissolved in an inert
suitable solvent, while the ionic or coordination catalyst can either
be dissolved or suspended in the solvent medium.
• The temperature is easily controlled because the fact that the
monomer are dissolved in solvent and the upper limit of the whole
system depend upon the boiling point of the solvent.
• After the reaction is over the polymer is used as such in the form of
polymer solution or isolated by evaporating the solvent.
ADVANTAGES
• Heat removal is accomplished via
solvlux
• Inert solvent medium helps to
control viscosity and promote a
uniform heat transfer
• Solvent reduces viscosity, making
processing easier.
• Heating and stirring are much
easier than the bulk polymerization
• Conversion of monomers to
polymer is high and typically 80%-
90%.
DISADVANTAGES
• costly;use of costly solvents
• Polymer produced is low average
molecular weight (solvent act as chain
terminators) and is always
contaminated with traces of the solvent
• Polymer will also have to be isolated
from the solution either by
precipitation/ evaporation of the
solvent
• Environmental pollution due to solvent
release.
• Purity of product is also not as high as
that of bulk polymerization.
APPLICATION
• Production of polyacrylonitrile by free radicl polymerization and also
polyisobutylene by cationic polymerization.
• EXclusively used in the production of block co-polymers
• In the solution form, it can be directly used as adhesives and coatings.
• Polyethylene (high density), polybutadiene, polypropylene, butyl
rubber, polystyrene, polyisoprene and polyformaldehyde are produced
this way.
EMULSION POLYMERIZATION
• The technique is used for the production of large number of
commercial plastics & elastomers.
• The system consists of water insoluble monomer, dispersion medium
& emulsifying agents Or surfactants (soaps and detergents) and a
water soluble initiator (potassium persulphate / H,O,, etc).
• The monomer is dispersed in the aqueous phase, not as a discrete
droplets, but as a uniform emulsion.
• The size of monomer droplet is around 0.5 to 10 um in diameter
depending upon the polymerization temperature & rate of agitation.
EMULSION POLYMERIZATION
• The emulsion of monomer in water is stabilized by a surfactant.
• A surfactant has a hydrophilic and hydrophobic end in its structure.
• When it is put into a water, the surfactant molecules gather together
into aggregates called micelles.
• The hydrocarbon tails (hydfophobic) orient inwards & heads
(hydrophilic) orient outwards into water.
• The monomer molecules diffuse from monomer droplets to water &
from water to the hydrocarbon centre of micelles.
EMULSION POLYMERIZATION
EMULSION POLYMERIZATION
EMULSION POLYMERIZATION
Water
Monomer
Surfactant
Examples:
Synthetic rubber-styrene-butadiene (SBR), Polybutadiene,
Polychloroprene.
Plastics-PVC, polystyrene, Acrylonitrile-butadiene-styrene terpolymer
(ABS).
Dispersions-polyvinyl acetate, polyvinyl acetate copolymers,
latexacrylic paint, Styrene-butadiene, VAE
ADVANTAGES
• High molecular weight polymers
• fast polymerization rates.
• allows removal of heat from the
system.
• viscosity remains close to that of
water and is not dependent on
molecular weight.
• The final product can be used as
such .does not need to be altered
or processed
DISADVANTAGES
• Surfactants and polymerization
adjuvants -difficult to remove
• For dry (isolated) polymers, water
removal is an energy-intensive
process
• Designed to operate at high
conversion of monomer to Is
polymer. This can result in
significant chain transfer to polymer.
• Can not be used for condensation,
ionic or Ziegler-Natta
polymerization.
SUSPENSION POLYMERIZATION
• Liquid or dissolved monomer suspended in liquid phase like water
• Initiator used are monomer soluble e.g. dibenzoyl peroxide
• Thus, polymer is produced in heterogenous medium
• The size of monomer droplets is 50-200 μm in diameter.
• The Dispersion is maintained by continuous agitation and the droplets
are prevented to coalesce ( unite or merge) by adding small quantity
of stabilizers.
SUSPENSION POLYMERIZATION
• The stabilizers used are PVA, gelatin, cellulose are used along with
inorganic stabilizers such as kaolin, magnesium silicate, aluminum
hydroxide, calcium/magnesium phosphate, etc if necessary.
• As it concerns with droplets, each droplet is tiny bulk reactor. The
polymerization takes place inside the droplet & product formed being
insoluble in water.
• The product separated out in the form of spherical pearls or beads of
polymer.
• Hence the technique is also known as Pearl polymerization /
Granular polymerization / Bead polymerization.
SUSPENSION POLYMERIZATION
• The products are small uniform spheres. They can be used
directly for some applications as precursors of ion exchange
resins otherwise they can be extruded & chopped to form
larger, easily moulded pallets.
• They can be dissolved in a suitable medium for use as
adhesives & coatings.
• This technique is used to form PVC, Polyvinyl acetate,
Polystyrene, Styrene-divinyl benzene copolymer beads (used
for ion exchange) etc.
SUSPENSION POLYMERIZATION
ADVANTAGES
• The process is comparatively
cheap as it involves only water
instead of solvents.
• Viscosity increase is negligible.
• Agitation & temperature control
is easy.
• Product isolation is easy since
the product is insoluble in water.
DISADVANTAGES
• The method can be adopted only for water
insoluble monomers.
• It is difficult to control polymer size.
• Polymer purity is low due to the presence of
suspending & stabilizing additives that are
difficult to remove completely.
• Suspension polymerization reaction is highly
agitation sensitive.
• Larger volume of reactor is taken up by water.
• The method cannot be used for tacky
polymers such as elastomers because of the
tendency for agglomeration of polymer
particles.
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