Paper 2 sem 1

Dr. Bapu R. Thorat

Assit. Professor of Chemistry
Government College of Arts and Science, Aurangabad,
Maharashtra 400060
7/21/2023 1
Unit 1:
Molecular mass and size of polymers:
Degree of polymerization and molecular weight, Practical significance of molecular weight,
Average degree of polymerization, Threshold molecular weight, numerical problems.
Average Molecular Weight, Average molar mass – Number average, weight average, z-
average, Viscosity average molecular weight and molar mass, numerical problems, Molecular
mass distribution curve. Polydispersity and polydispersity index of polymers. Examples of
monodispersed and polydispersed polymers. Molecular mass & mechanical properties. Size of
polymer molecules.

Unit 2:
Determination of Molecular mass of Polymers:
Absolute and relative methods of molecular mass determination. Determination of No.
average molecular mass – End group analysis, Membrane Osmometry, Ebulliometry,
cryoscopy & Vapour pressure osmometry; Weight average molecular mass-
ultracentrifugation (principle only), Light scattering method (No experimental details
expected), viscosity average molecular mass, Gel permeation (Size-Exclusion)
chromatography.
Unit 3:
Polymer reactions:
Introduction, Addition - hydrogenation, hydrohalogenation;
Substitution (Electrophilic, Nucleophilic and free radical) - Halogenation,
Chlorosulphonation of polyethylene, alkylation of Poly(vinyl bromide),
SN reactions on PVC, Nitration, Sulphonation, Halogenation, chloromethylation of aromatic
ring, solvolysis, isomerization, Cyclization, epoxidation reaction, Vulcanization
Condensation reactions of specific groups hydroxyl- Acetylation and Xanthation of
cellulose

Unit 4:
Polymerization techniques:
Introduction, Homopolymerization and heteropolymerization, Bulk polymerization, Solution
polymerization, Suspension polymerization, Emulsion polymerization, Melt Polymerization,
Interfacial condensation polymerization and their Salient features and disadvantages.
 Polymers - What are they?
• Polymers are a special kind of macromolecule
• The word polymer comes from the Greek words “poly,” meaning “many”, and “meres,”
meaning “parts” or “repeating units” - Many repeating parts.
• A Polymer consists of a large chain of repeating molecules (monomers) that are
attached in an end to end fashion.
repeat repeat repeat
unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

• Polymer chains are HUGE!

• Polymers typically consist of between 20,000 and 40,000 individual monomers
• Polymer chains are flexible, and usually “clump” together into a smaller shape,
• This enables the individual chains to interact and become entangled,
• This helps to give a polymer its strength and flexibility.
 Polymers - What are they?
The functionality of a monomer is the number of sites it has for bonding to other
monomers under the given conditions of the polymerization reaction.
❖ Bifunctional monomer, i.e., monomer with functionality two, can link to two other
molecules under suitable conditions forming linear polymer;
❖ Polyfunctional monomer is one that can react with more than two molecules under
the conditions forming cross linked polymer.
Bifunctional Monomers

Trifunctional Monomers Mixture Monomers

 Polymers – types of polymers
According to the types of monomer, polymers are classified as – homopolymer and
copolymer.
➢ The addition polymers formed by the polymerization of a single monomeric species are
known as homopolymers,
➢ The polymers made by addition polymerization from two different monomers are
termed as copolymers.

copolymers homopolymers

➢ The number of repeating units; monomers (n or x) in the chain so formed is called the
‘degree of polymerization’ (DP = n).
➢ Polymers with a high degree of polymerization are called ‘high polymers’ and those with
low degree of polymerization are called oligopolymers (short chain polymers or
oligomers); but n > 30.
Polymerisation C C
n H2C CH2 H2 H2
n
Ethylene Polyethylene
 Polymers – types of polymers
Crystalline Semi - crystalline Amorphous or non-crystalline

Crystallinity

Isotactic (stereoregular) Linear

Syndiotactic (alternative) Tacticity Polymer Structure Branched

Atactic (stereo irregular)

Cross linked or network

Origin
Natural Semisynthetic Synthetic
rubber, silk, cellulose, proteins, starch synthetic rubber; cellulosics Polyethylene, polypropylene, poly-
styrene, polybutadiene,
Application and Physical properties

Rubbers Fibres Plastics

Natural rubber, polybutadiene, Cotton , natural silk, rayons, etc
SBR, nitrile rubber,
Thermoplastics Thermosetting
Step-growth or condensation Polyethylene, polypropylene, Phenolic resin, amino resins,
Polyesters and polyamides poly-styrene, nylon polyamides, etc epoxy resins, etc
Mode of formation Chain-growth or addition
Polyethylene and other polyolefins, Polystyrene
 Polymer reactions
A functional group present in macromolecules

Polymer reactions (Aliphatic/aromatic

and small molecules exhibit equal reactivity

backbone or side chain or terminal

Chemical reactions of polymer similar
to simple organic molecule

Solvolysis Addition (unsaturated Hydrogenation

group reactions)
bond)
Isomerization Hydrohalogenation

Cyclization Condensation (two Acetylation and

functional groups) Xanthation of cellulose
Epoxidation reaction
Substitution (replacement Halogenation
Vulcanization of one by other) Nitration
of rubber
Sulphonation
chloromethylation
SN reactions on PVC
alkylation of Poly(vinyl bromide)
Chlorosulphonation of polyethylene
 Polymer reactions
all reactants,
Reactions that take place in intermediates, and
homogeneous fluid media end products fully
soluble

Chemical reactions of All elementary steps involve The other reacting

macromolecules and small only individual functional species are small
molecules are same if groups and mobile

The steric factors in the low molecular weight compounds

selected for comparison must be similar to those of the
large molecules

Examples: The activation energy for the photochemical cis–trans isomerization of

azobenzene residues on the backbones of flexible polymeric chains and cis–trans
isomerization of azo-aromatic polymers is same; therefore rate of isomerization is also same.
 Polymer reactions
In some cases, unequal reactivity of macromolecules was observed:

1. In bimolecular reactions that are diffusion-controlled.

2. When neighboring group participations become significant.

3. When the properties of the polymers in solution are altered by gelation.

4. When the tacticities of the polymers affect neighboring group

interactions.
5. When heterogeneous conditions affect accessibility to
the reactive sites.

A functional groups present in the polymer molecules can may undergoes chemical
changes or reactions leads to the formation of modified or new polymeric structures
with entirely new properties and applications.
 side chain
having -SH
group
co-polymer of ethylene and
mercaptoamido ethylene mild oxidation (on
mere exposure in air)

break S-S- cross linking’s cross linked

disulfide and forming bridged

or cross linked polymer
Water insoluble
used for the hair setting
set to the required curl pattern
 Hydrogenation
A unsaturated group in the organic molecule can undergoes hydrogenation

Polymers or co-polymers with double bonds on the backbone can also be

hydrogenated. Polyisoprene can be hydrogenated to get a polymer resembling an
alternating copolymer of ethylene and propylene.

Polyisoprene copolymer of ethylene and propylene

Atactic 1,4-polybutadiene and syndiotactic-1,2-polybutadiene can be hydrogenated at
1000C and 50 bar pressure of hydrogen with a soluble catalyst {[(Ph)3-P]3RhCl}.
Butadiene acrylonitrile copolymers can also be hydrogenated quantitatively with this
rhodium catalyst under mild conditions.
 Hydrogenation
Hydrogenation of carbon-to-nitrogen double bonds in polymer backbones and in the pendant
groups can be carried out with lithium borohydride.

Styrene-butadiene rubber can be hydrogenated to a copolymer of styrene and ethylene.

Syndiotactic polystyrene can be hydrogenated over Ni/SiO2 and Pd/BaSO4 catalysts.

❑ Ni catalyst yields complete hydrogenenation when low molecular weight polymer.
❑ Hydrogenation of high molecular weight polystyrene, however, is incomplete.
❑ On the other hand, the Pd catalyst yields completely hydrogenating material.
 Halogenation

It was fairly complex, because several reactions occur simultaneously. These appear to be: (1)
additions to the double bond; (2) substitutions; (3) cyclizations; and (4) cross-linkings.

Halogenation reactions of unsaturated polymers follow two simultaneous paths, ionic and
free radical.
Ionic mechanisms give soluble products from chlorination reactions of polybutadiene.
The free-radical mechanisms, on the other hand, cause cross-linking, isomerization, and
addition products.
Substitution reactions take place in brominations with N-bromosuccinimide. Brominations of
polybutadienes with N-bromosuccinimide yield a-brominated polybutadienes.

By contrast, chlorination of polybutadiene in benzene is a straightforward addition reaction

of the halogens to the double bonds.

With saturated polymers such as polyethylene, chlorination can be carried out by a

substitution reaction through a radical chain process:

❑ polyethylene which is a tough thermoplastic

❑ 30% of chlorine, is a rubbery material
❑ beyond 50% become somewhat rigid
❑ 70% chlorination, polymer become
❑ quite brittle
 Hydrohalogenation
Hydrogen chloride can also adds across the double bond, as in the following reaction:

Hydro chlorination of natural rubber is often accompanied by cyclization. trans-1,4 and 1,2-
Polybutadiene can be hydro halogenated under mild conditions with gaseous HCl.
 Chlorosulfonation of polyethylene

Polyethylene can also be chlorosulfonated through a substitution process:

Chlorosulfonated polyethylene is known for its solvent, chemical and flame resistant
characteristics.
 Alkylation of Poly(vinyl bromide)

The alkylation of poly(vinyl bromide) was performed by using organolithium compounds

forming alkyl substituted product with the replacement of bromine.
 Nitration

Nitration of polystyrene was originally carried out by using nitrating mixture of nitric and
sulfuric acids mixture. Polymer dissolves in it and a nitro derivative forms at 500C within 3
hrs.

Here too, however, a loss in

molecular weight accompanies
the reaction.

Nitration of isotactic polystyrene yields a more crystalline

product (about 1.6 NO2/ring) than the parent compound.

Polystyrene can be nitrated under mild

conditions using acetyl nitrate.
The product contains approximately 0.6
nitro groups per each benzene ring.

The nitro groups of

polynitrostyrene are reduced by
phenyl hydrazine that acts as a
hydrogen donor further
diazotized to polymeric free-
radicals.
 Sulphonation Reactions of polymers
Sulfonation reactions of polystyrene and its copolymers with divinyl benzene are carried out
commercially to prepare ion exchange resins.

Partial sulfonations of polystyrenes

are achieved in the presence of ethers.

When more than 50% of the aromatic

rings are sulfonated, the polymers
become water-soluble
At lesser amounts of sulfonation, 25–50%, the polymers are solvent-soluble.

chlorinated hydrocarbons with

a complex of dioxane-SO3 Complexes of ketones with SO3

The ratio of sulfonation is more favorable for poly(vinyl toluene) than it is for polystyrene at
the same conditions.
 Chloromethylation of aromatic ring

Chlorodimethyl ether (a carcinogen) is a good solvent for these polymer reactions and
common reagent.

❑ Stannic chloride is a very effective catalyst for this Friedel-Craft reaction.

❑ Cross linking via chloromethyl group is side reaction leads to formation of rigid polymer.
 Chloromethylation of aromatic ring

Another technique of chloromethylating polystyrene is to react it with methylal and thionyl

chloride in the presence of zinc chloride.

Chloromethyl-substituted polystyrenes can also be prepared from poly(p-methyl

styrene)s by treating them with aqueous sodium hypochlorite in the presence of a phase
transfer catalysts, like benzyltriethylammonium chloride.
The conversions of methyl to chloromethyl groups can be as high as 20% without any
detectable morphological changes.
 Chloromethylation of aromatic ring

Chloromethylation of polyarylether sulfones, polyphenylene oxide, phenolic resins

carried by using chlorodimethyl ether and stannous chloride
 Isomerization Reactions

With gamma radiation

direct excitation of the p-electrons of the double bonds to antibonding orbitals
where free and geometric interconversions are possible.

1,4-polyisoprene
 Cyclization (rubber) reaction

❑ Cyclization as side reaction take places easier in isoprene rubber than in butadiene rubber

❑ Cyclization occurs under influence of heat, light, ultraviolet or nuclear radiation or

also in presence of cation-donor catalysts (mineral, organic, Lewis’s acids)

Mostly bi- or tri-cyclic structures

are created in later process stages

isolated cyclic structures

❑ Gradually their unsaturation and elasticity is reduced as result of successive

cyclization of isoprene and natural rubber, and their toughness is increasing.

❑ At high cyclization degree, these are changing onto thermoplastic powdery

products having excellent adhesive properties, mainly to metallic materials.

❑ The cyclization takes places either during its mixing with suitable initiator
on rollers or in mixers and also in latex
 Cyclization
reactions of
polyisoprene can be
catalyzed by TiCl4
and by sulfuric
acid

In a similar manner, polymers with pendant unsaturation undergo cyclization reactions in

benzene in the presence of BF3 or POCl3, yielding ladder structures.

TiCl4/
sulfuric acid carbon cations

Butadiene rubbers have lower tendency to

cyclization than polyisoprene rubbers
six-membered monocyclic
and fused polycyclic units
Polyacrylonitrile converts to a red solid when heated above 2000C.
Further heating of the red residue to about 3500C or higher converts it to a black brittle
material. This black material has a ladder structure:

The double bonds shift in natural rubber when it is heated to temperatures of 1500C or
above.

Many other polymeric structures can rearrange under proper conditions. For instance,
poly(4,4’-diphenylpropane isophthalate) rearranges upon irradiation with UV light to a
structure containing o-hydroxybenzophenones.
 Epoxidation
Liquid polybutadiene get epoxidized by using hydrogen peroxide in the presence of
organic acids or their heavy metal salts.
❑ Reaction conditions - molecular weights of the polymers is small, because it is easier
to handle lower viscosity solutions.
❑ Use peracetic acid in place of hydrogen peroxide.
❑ Most efficiently leads the formations of organic peracids in situ with cationic
exchange resins acting as catalysts.
❑ Polybutadienes that are high in 1,4-structures tend to epoxidize more readily and yield
less viscous products.
❑ The epoxidation reaction can also be carried out on poly(1,4-cyclopentadiene):

Perbenzoic acid is an effective reagent in chloroform and in methylene chloride

solutions at 0–200C. Monoperphthalic and p-nitroperbenzoic acids are also efficient
epoxidizing agents.
SN reactions on PVC
Solvolysis
 Mercerization

The chemical treatment of cotton known as mercerization.

swelling the cotton by concentrated alkali solution

Chemical treatment
of cotton known as washing out the alkali
mercerization
Formation of' alkali cellulose

it is somewhat more amorphous better dyeability

lower in density lower tensile strength

increased water absorption higher extensibility

 Regenerated Cellulose

Regenerated cellulose describes cellulose which has been dissolved by virtue of the
production of a soluble chemical derivative, cellulose xanthate, and subsequently
reprecipitated.

When prepared as a fiber, regenerated cellulose is known as viscose or (viscose) rayon.

Traditionally, both viscose and cellulose acetate have been known as rayons.

As a film, regenerated cellulose is known by the generic term cellophane.

 Manufacture (Cellulose modifications)

Purified cellulose usually obtained from wood pulp

Cellulose with aqueous NaOH at room temperature for 15 min to 2 hr

alkali or soda cellulose

Excess alkali is then pressed out

aged for several days at 25-30°C to promote oxidative degradation of the chains to the
desired degree of polymerization

25-30°C for 1-3 hr addition of carbon disulfide -10% CS2

evacuated to remove excess CS2
cellulose xanthate

Where, R is a cellulose residue

The average degree of xanthation is about one CS2 for every two cellulose residues.

Reaction takes place heterogeneously by the addition of liquid or gaseous CS2 to the alkali
cellulose crumbs, the xanthation in some regions may correspond to the dixanthate or higher.
 Cellulose xanthate

dissolved in dilute NaOH

completely soluble - solution is known as viscose

Cannot easily be coagulated and must be allowed to "ripen" for a few days

Cellulose xanthate is essentially unstable and decomposes gradually - hydrolysis and saponification

Cellulose residues have been regenerated

viscose is then spun into a bath containing sulfuric acid

Regeneration of the remaining cellulose residues and coagulate the polymer

Native cellulose → steeping/pressing → shredding → aging → xanthation → dissolving in

sodium hydroxide → filtration → ripening/deaeration → regeneration in acid bath →
stretching → cutting → finishing → drying.
 Viscous rayon

Normal Tenacity

Viscose rayon normally has a tenacity of 2-2.5 g/denier, somewhat lower than that of cotton
(3-5 g/denier).

Its wet tenacity is only about half the dry value but is still adequate for laundering

The moisture absorption of viscose is about twice that of cotton

The elasticity is not high (typically 15% elongation at break), and the fiber shows
considerable viscoelastic character

Viscose of normal tenacity is primarily an apparel fiber, but its popularity is declining

High Tenacity
A high-tenacity product (3-6 g/denier) is produced by stretching the fibers just short of their
breaking point in the spinning bath; considerable orientation is introduced.

High tenacity rayon has lower elongation and moisture absorption than the apparel material

This market has, however, virtually disappeared with the increased use of nylon, polyester,
and steel for that purpose
 Cellophane
the viscose solution - xanthate solution
extruded as film

immersed in a bath of ammonium and sodium sulfate and dilute sulfuric acid

precipitates the cellulose film/sheet

passed through various washing, bleaching, and desulfurizing baths

a bath of glycerol, glucose, or a polyhydric alcohol, which is imbibed & acts as a plasticizer

dried

coated with a mixture of' nitrocellulose and various plasticizers and waxes

thin (0.001-0.002 inches) film tensile strength is good

permeability of the uncoated film to water vapor and to water-soluble gases is extremely high
used as a wrapping and packaging material
its tear strength, impact strength, and resistance to flexing are poor
 Cellulose acetate
polyhydric alcohol - cellulose can undergo esterification reaction in presence mineral acid
part of the acid is replaced by an acid chloride or anhydride because with other organic acids, including
acetic acid, equilibrium is well to the left and ester formation does not take place.
Sulfuric acid is also utilized in the reaction mixture - as a catalyst & dehydrating agent

cotton linters or wood pulp form the raw material

acetylation – by acetyl chloride or acetic anhydride

acetylation - the triacetate derivative

Mixture is held at about 50°C until the desired chain degradation achieved - indicated by the
viscosity of the mixture.

added to a large amount of 25-35% acetic acid

acetone-soluble diacetate, or an acetyl content of about: 30%.

precipitates the polymers in finely divided form

polymer is washed and dried

dissolved in acetone for the spinning operation

 Cellulose acetate

Fiber Properties and Applications

❑ Traditional acetate fiber (diacetate) has a tenacity of 1.2-1.5 g/denier and about the same
moisture absorption as cotton.

❑ It tends to soil less and wash more easily than viscose.

❑ Cellulose acetate is thermoplastic, pleats and creases can be permanently set.

❑ It is less susceptible to creasing and wrinkling in use than viscose because its resilience is
greater.
❑ With the advent of spinning processes using methylene chloride, cellulose triacetate
became popular as an apparel fiber.
❑ Its properties are improved over those of the diacetate in moisture absorption, wrinkle
resistance and creep retention, dyeability, and speed of drying.
 Cellulose acetate
Plastics Properties and Uses
Cellulose acetate was introduced in sheet, rod, and tube form (as well as in lacquers and
dopes) around the time of World War I.
Different articles of it was made by popular injection-molding material containing nearly
50-55% acetyl content by weight which somewhere between the diacetate and the triacetate
in composition.
Higher acetyl content gives poorer flow but better moisture resistance; lower acetyl content
gives better impact strength.
Cellulose acetate molded and extruded articles are used where extreme moisture resistance
is not required.
Cellulose acetate is also utilized in sheet form but thin films are cast from solution onto
polished metal surfaces.
The films are used in photography, for wrapping, and for making small envelopes, bags,
and boxes for packaging.
 Vulcanization of rubber
❑ Natural rubber becomes soft at high temperature (>335 K) and brittle at low
temperatures (<283 K) and shows high water absorption capacity.

❑ Soluble in non-polar solvents and is non-resistant to attack by oxidizing agents

❑ In 1893, Charles Goodyears discovered that addition of sulphur to hot rubber cause
changes that improve its physical properties in a spectacular manner. This process is
called vulcanization.
Addappropriate additive (accelerator and
Heating a mixture of raw rubber with sulphur
or dipping it in a solution of S2Cl2 in CS2 + activator) at a temperature range between
373K to 415K

sulphur forms cross links at the reactive sites of

double bonds and thus the rubber gets stiffened

In the manufacture of tyre

rubber, 5% of sulphur is
used as a crosslinking agent

Larger amounts of sulfur giving -brittle,

but quite strong, ebonite as the amount of
S is increased to about 40%
 Vulcanization depends upon:
❑ The amount of sulphur used: by increasing the amount of sulphur, rubber can be hardened
❑ Temperature
❑ Duration of heating.

slight The tensile strength 10 times the

broader useful temperature range (-40 tackiness of vulcanized rubber tensile strength
to 1000C) compared to raw rubber’s is very good. of raw rubber
useful temperature range (10 – 600C)

low elasticity Excellent resilience i.e.,

articles made from it returns to
easy to manipulate the vulcanized the original shape when the
Advantages of
rubber to produce the desired deforming load is removed
vulcanization
shapes

resistant to i) Organic solvents like better resistance to moisture,

petrol, benzene, CCl4, ii) Fats and oxidation, abrasion
oils, but it swells in them

a better electrical higher resistance to wear and

insulator Ex: Ebonite tear compared to raw rubber
 Polymerization techniques

1. Addition polymerization
• Bulk polymerization
• Solution polymerization
• Suspension polymerization
• Emulsion polymerization
2. Condensation polymerization
• Melt polycondensation
• Solution polycondensation
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.
 Bulk polymerization
Advantages Disadvantages
• The system is simple and • Heat transfer and mixing
requires thermal insulation. become difficult as the
• The polymer is obtained pure. viscosity of reaction mass
• Large castings may be increases.
prepared directly. • Highly exothermic.
• Molecular weight • The polymerization is
distribution can be easily obtained with a
changed with the use of a
chain transfer agent. broad molecular weight
distribution due to the
high viscosity and lack of
good heat transfer.
• Very low molecular weights
are obtained.
 Solution polymerization
❑Some disadvantages of bulk polymerization
(heat transfer and high viscosity) are eliminated
in solution polymerization.
❑Monomer along with initiator dissolved in
solvent, formed polymer stays dissolved.
❑The mixture is kept at polymerizaion
temperature & constantly agitated.
❑Depending on concentration of monomer, the
viscosity of solution does not increase.

❑ After the reaction is over, the polymer is used as such in the form of polymer
solution or the polymer is isolated by evaporating the solvent.
❑ Polymer so formed can be used for surface coating.
❑ It is used for the production of Polyacrylonitrile, PVC, Polyacrylic acid,
Polyacrylamide, Polyvinyl alcohol, PMMA, Polybutadiene, etc.
• Advantages
• Solvent acts as a diluent & helps in facilitating
continuous transfer of heat of polymerization.
Therefore temperature control is easy.
• The solvent allows easy stirring as it decreases
the viscosity of reaction mixture.
• Solvent also facilitates the ease of removal of
polymer from the reactor.
• Viscosity build up is negligible.
• Disadvantages
• To get pure polymer, evaporation of solvent is required additional technology,
so it is essential to separate & recover the solvent.
• The method is costly since it uses costly solvents.
• Polymers of high molecular weight polymers cannot be formed as the solvent
molecules may act as chain terminators.
• The technique gives a smaller yield of polymer per reactor volume, as the
solvent waste the reactor space.
• The purity of product is also not as high as that of bulk polymerization.
Removal of last traces of solvent is difficult.
Suspension polymerization
• Liquid or dissolved monomer suspended in liquid phase like water.
• Initiators used are monomer soluble e.g. dibenzoyl peroxide.
• Thus, polymer is produced in heterogeneous 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
such as PVA, gelatin, cellulose along with inorganic stabilizers 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.
• The products can be used directly 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 Disadvantages
• The process is comparatively • The method can be adopted only for water
cheap as it involves only water insoluble monomers.
instead of solvents. • It is difficult to control polymer size.
• Viscosity increase is negligible.
• Polymer purity is low due to the presence of
• Agitation & temperature control suspending & stabilizing additives that are
is easy. difficult to remove completely.
• Product isolation is easy since the • Suspension polymerization reaction is
product is insoluble in water. 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.
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 / H2O2, 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 μm in diameter depending
upon the polymerization temperature & rate of agitation.
 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 (hydrophobic) 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

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
 Emulsion polymerization
Advantages Disadvantages
• High molecular weight polymers ❑ Surfactants and polymerization
• fast polymerization rates. adjuvants - difficult to remove

• 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
❑ For dry (isolated) polymers, water
removal is an energy-intensive
process
❑ Designed to operate at high
conversion of monomer to polymer.
This can result in significant chain
transfer to polymer.
❑ Can not be used for condensation,
ionic or Ziegler-Natta
polymerization.
 Type Advantages Disadvantages
Homogeneous
Bulk (batch type) Minimum contamination. Simple Strongly exothermic Broadened
equipment for making castings molecular-weight distribution at high
conversion. Complex if small particles
required
Bulk (continuous) Lower conversion per pass leads Requires agitation, material transfer,
to better heat control and separation, and recycling
narrower molecular weight
distribution
Solution Ready control of heat of Not useful for dry polymer because of
polymerization Solution may be difficulty of complete solvent removal
directly usable
Heterogeneous
Suspension Ready control of heat of Continuous agitation require
polymerization Suspension or Contamination by stabilizer possible
resulting granular polymer may Washing, drying, possibly compacting
be directly usable required
Emulsion Rapid polymerization to high Contamination with emulsifier, etc.,
molecular weight and narrow almost inevitable, leading to poor color
distribution, with ready heat and color stability Washing, drying, and
control Emulsion may be directly compacting may be required.
usable
 Melt Polymerization
❑ All reactants are mixed together, heat and reaction temperature is elevated above the melt
temperature of the resulting polymer.
❑ The production of polyethylene terephthalate from dimethyl terephthalate and ethylene
glycol, and nylon 66 are prepared by using melt polycondensation technique.
❑ In this method, one of the monomers used is solid, which cannot decompose around its
melting point.
❑ Polymerization can be carried out in an inert atmosphere of N2 or CO2 to avoid side
reactions such as oxidation, decarboxylation, etc.
❑ Sometimes, the reaction is carried out under reduced pressure to initiate the removal of
the byproduct.
Disadvantageous
❑ Removal of the byproduct becomes extremely difficult because there is much increase in
the viscosity of the medium.
❑ The polymer formed is in molten state at the reaction temperature and it is important to
isolate it from the reactor during hot condition, otherwise it will solidify inside the
reactor and removal becomes very hard.
❑ e.g. Polyester and polyamides fibers are formed from melt condensations.
 Interfacial condensation polymerization

❑ A variation in solution polymerization is

called as interfacial polymerization.
❑ In this method, one monomer of a
condensation pair is dissolved in one liquid,
and other member of the pair is another
liquid.
❑ The liquids are insoluble in one another.
❑ The polymers are not soluble in any forms at
the interface between them.
❑ Also, one of the phases generally also
contains an agent reacts with the molecule
of condensation to drive the reaction of
completion.
 Advantages:

❑ Reaction proceeds very rapidly at room temperature and atmospheric pressure.

❑ In contrast to the long time, at high temperature and pressure associated with
polycondensation reaction.
❑ Separation of polymers from the interface is easier even during reaction

Disadvantages:

❑ Separation of solvents and unreacted monomers may come too high.

Polymerization techniques used in the production of some commercial polymers

Polymer Polymerization technique

Polyamides
Polycarbonates
Bulk
Poly(ethylene terephthalate)s
Polycaproamide (nylon-6)
Polysulphide
Suspension
Poly(vinyl chloride)
Polyformaldehyde
Polyethylene (high density)
Polyisoprene Solution
Polypropylene
Polystyrene
Styrene-Butadiene copolymer
Emulsion
Poly(vinyl acetate)
Poly(methyl methacrylate) Bulk, suspension
Polyethylene (low density) Bulk, solution