Polymerization Techniques

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Polymerization reaction may take place in
any of the three states of matter-solid, liquid,
gas.
• The solid state reactions are usually slow,
they are not considered practical for this
reason.
• The gas-phase reactions do take place
but normally they require maintenance of
high temperatures, a condition in which
almost all high molecular weight polymers
become unstable.
• Hence almost all commercial process of
polymerization are liquid phase reactions3
LIQUID-PHASE REACTIONS:

Homogenous type

• Bulk Polymerization/Mass Polymerization

• Solution Polymerization

Heterogeneous type

• Emulsion Polymerization
• Suspension Polymerization/Pearl/Bead Polymerization

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The homogenous or heterogeneous terms refers
only to initial conditions of the system and are not to
the subsequent conditions.

For example, Polymerization of vinyl chloride by

mass polymerization method is considered a
homogenous type of reaction, because initially the
system is homogenous. But the polymer being
incompatible to the monomer phase, the system
subsequently becomes heterogeneous. Hence the
concept of homogeneity or heterogeneity is based
on only the initial conditions of the system
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 1. Bulk Polymerization :
In the reactor:-
- Liquid monomer
- Initiator
- Inhibitors
- Chain transfer agents

Homogeneous : polymer remains dissolved in monomers.

Ex. PMMA
Heterogeneous : aka. Precipitation polymerization
polymer is insoluble in its monomers.
Ex. Polyacrylonitrile, PVC

Problem : heat transfer not good

Make objects with a desirable shape by polymerization

6 in a mold.
 In this type of polymerization the
monomer is taken in liquid form.
 The initiators, chain transfer agent- used
to control the molecular weight are
dissolved in monomer.
 Now the system becomes homogenous.
The reaction mass is heated or exposed
to a radiation source for the purpose of
initiating the polymerization
 Reaction and is kept under agitation
for proper heat and mass transfer.

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 As the polymerization proceeds the viscosity
of the medium increases and mixing
becomes difficult leading to products with
very broad molecular weight distribution.
 The reaction is purely exothermic.
 The phenomenon in which the molecular
weight of a substance increase tremendously
is known as “Autoaccleration”
 Batch reactors are used for polymerization

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Model of Batch Polymerization

Monomer

I
I

I
I
Initiator

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 Pros & Cons of Bulk Polymerization
Advantage
• Obtain purest possible polymer
• Conveniently cast to shape
• Obtain highest polymer yield per
reactor volume
• High molecular weight and
molecular weight distribution.
• No solvent contamination
• Good flow characteristics
• Longest polymerization times
• Product can be used directly ,
no isolation is required due to its
resistance towards solvents
Disadvantage
• Difficult to control, high
viscosity
• Reaction has to be run slowly
• Cannot get high rate and high
MW at the same time
• Difficult to remove last traces
of unreacted monomer
• Heat removal is difficult
• Due to the formation of hot
spot explosion may possible
• Stirring become
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difficult after
30-40% conversion
Applications

• Casting PMMA sheets.

• Used in free radical polymerization of MMA or

styrene to get moulding powders.

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 2. Solution Polymerization
Solution Polymerization : Monomer dissolved into inert-
solvent / inhibitor
- Monomer
- Initiator
- CTA
- Inert solvent
Solvent helps controlling heat transfer from reaction.

Use for :
- Thermosetting condensation polymer (stop before gel point)

- Ionic polymerization
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- Ziegler-Natta solution process
• Monomer is dissolved in suitable solvent along
with chain transfer agents and initiators (free
radical initiator).
• Catalyst may be ionic or co-ordination catalyst
which can either dissolved or suspended.
• The presence of inert solvents medium helps to
control viscosity, increase and promote proper
heat transfer.
• Process maybe continuous/batch wise operation.
The product obtained is in liquid phase.
• Fore most cases water is taken as solvent
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Model of Solution Polymerization

Monomer
I

I
I Initiator
I

I
Solvent

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 Pros & Cons of Solution Polymerization
Advantage
• Reduces the tendency toward
autoacceleration
• Increases heat capacity/heat-
transfer
• Reduces viscosity
• Minimize runaway reaction
• Stirring is easy due to low
viscosity
• The product in liquid for can
be used directly as adhesive
• Mass transfer is easy
Disadvantage
• Solvent waste
• Need solvent separation &
recovery
• Have traces of solvent, monomer
• Lower yield
• Solvent may not be really inert
• (May interfere w/ rxn.-act as CTA
• High mol.wt polymers cannot be
manufactured by this process
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Applications

• Widely used for coating and adhesives.

• Industrial production of PAN by free radical
polymerization.
• Polyisobutylene by cationic polymerization use this
technique.
• Widely used for coating and adhesives.
• Industrial production of PAN by free
radical polymerization.
• Polyisobutylene by cationic polymerization use this
technique. 18
 3. Emulsion Polymerization
Emulsion Polymerization : Use emulsifier / soap

Initiator Water
Soap monomer (Hydrophilic)

-Reaction occurs in water phase until polymer gets very

hydrophobic and then dissolve back in the monomer region.

Ex. Latex - very very small particle stable in solution

- particle size << 1 m 19

- can generate very high MW. polymer

 This technique suits well for addition
polymerization.
 In this type apart from dispersed particles and
dispersion media several other components are
added.
 Usually the dispersion media is water.
 The monomer is dispersed in water in the form
of small droplets of diameter 1µm.
 These droplets have the natural tendency to
coalesce and gradually become larger and
forms immiscible layer.
 In order to discourage this tendency
emulsifying agents such as soap like materials
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are added.
 Apart from that surface tension regulators,
buffers, protective colloids are added.

 To prevent pre-mature coalescence and

precipitation of droplets of monomer

 As well as those of partially polymerized

polymer by preventing adhesion of sticky
drops
Mechanism involved in Emulsion Polymerization
Emulsifyingagent →Sodium or potassium
salts of organic fatty acids (soap)and
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sulphates
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 Emulsifying agent have inorganic head
(hydrophilic in nature) and organic
tail (hydrophobic in nature).
 These emulsifying agents are substances
with very low solubility in medium and
therefore as its concentration is increased,
the molecularly dispersed substances begins
to form molecular aggregates known as
micelles which exists either in spherical form
or thin layer.
 In micelles because of their hydrophilic
and hydrophobic ccharacteristics, the
molecules orient themselves so as to have
the tails towards centre and head towards
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water phase.
 When monomer is added which is organic in
nature prefers the interior of the micelle
because of organic environment.
 Micelle has the tendency to contract
because of surface tension.
 Hence the migration of monomer from
monomerdroplets to the interiors of micelle
continues till equilibrium is reached
betweenswelling and contracting tendencies
 When initiators are decomposed in
water phase it bounces around the solution
to create radicals.
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 At this point the surface area presented by
monomer-swollen micelle is much greater
than monomer droplets so the probability
for radicals to enter the monomer-swollen
micelle is very high.
 When the radicals enter the micelle it
initiates the reaction.
 When polymerization takes place within
micelle it lowers the concentration of
monomer so that a gradient is established
between monomer which in uninitiated
andinitiated one. Both diffuse.

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 Thus the uninitiated monomer swollen
micelles gradually disappear losing their
monomer content.
 When a second radical find its way into the
micelle, for the conditions prevailing within the
micelle the rate of termination is much greater
than the rate of propagation.
 Hence chain terminates eventually and
remains until a third radical enters, initiating
the growth of second chain and so on
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Emulsion Polymerization (cont.):

Typical ingredient

100 part (by wt.) monomer (water insoluble)

180 part water
2-5 parts acid soap
0.1-0.5 part water-soluble initiator
0-1 part CTA (monomer soluble)

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 Steps in Emulsion Polymeriztion

Water-soluble initiator Monomer swollen micelle

Polymer born in water Polymer moves to micelle

-growing polymer particle

-Monomers inside the micelle decrease

Unreacted monomers in other

micelles and in droplets diffuse
through water to the growing particles

Reaction terminates when 2nd radical gets in 28

reaction starts again for the 2nd chain when 3rd particle gets in.
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 Pros & Cons of Emulsion Polymerization

Advantage Disadvantage

• No chain transfer problem and • Because of several additives

heat transfer problem. The added to the system the product
products obtained in the form obtained in less pure when
of latex are directly usable compared
• Very high mol.wt can be to bulk polymerization.
obtained in very less time • To recover the polymer in the
nearly 1-2 hours, high average solid form considerable
chain lengths are achievable technology is needed.
• Suitable for ionic/radical • Use of very large quantities of
condensation water lowers the yield per
reactor volume
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 APPLICATIONS

 Most widely used industrial technique and

monomers such as vinyl chloride,
butadiene, chloroprene, vinyl acetate,
acrylates are polymerized by this
technique.
 Suitable for producing very high
mol.wt products

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 4. Suspension Polymerization :
Model of suspension polymerization

Suspending agent

(Hydrophobic)
(Hydrophilic)
monomer
+ Water
Initiator

Monomer into water,

suspending agents (Ex.Ionic detergent, barium sulfate)
- Ex. Polyvinyl alcohol
- Beads of polymer ( 10-1000 m) 32
 This method is employed to overcome some
of the disadvantages of emulsion
polymerization,
 for Example the tendency of small polymer
particles to adsorb impurities.
 The size of monomer dispersed is greater
compared to emulsion polymerization.
 Here the monomer is insoluble in dispersion
medium
 Initiator, suspension stabilizer are dispersed
in water or inert organic liquids provided the
monomer and polymer is insoluble in it.
 The mechanism is similar to mass and 33

solution polymerization.
 Unlike in emulsion polymerization where
close, intimate contact between the two
phases is established by emulsifying agent.
 each bead or pearl of the monomer in
suspension polymerization acts as minute,
discrete mass polymerization system.
 A protective colloid which is inert with
respect to the polymerization reaction and
which increase the viscosity of the
continuous phase is added so that it would
hydro-dynamically hinder the coalescence
of monomer droplets. 34
 A protective colloid such as Magnesium
carbonate is insoluble is the solution and
collects at the droplet-water interface by
surface tension and prevents the
coalescence of drops upon collision

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 Particle size is affect by the following four factors:

1. Stirring rate
2. Ratio of reactants
3. Suspension agent
4. Temperature

 The plant operator must control temperature, and the particle size (of the
growing polymer mass in the bubble.) If the particle size gets to large, the
particle will absorb too much heat. Particle size may be 0.01 to 0.5 cm, or as
low as 1 micron.
 A suspension agent is a material that gives a surface activation that keeps
droplets from become larger.

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Pros & Cons of Suspension Polymerization

Advantage Disadvantage
1. Easy heat removal 1. Low yield / reactor volume
and control 2. Traces of suspending agent on
2. Obtain polymer in a particle surfaces
directly useful from 3. Cannot run continuously
3. Theproduct obtained is
in granular form 4. Cannot be used for
which is convenient -condensation polymers
to handle, isolation
is eas -ionic or Ziegler-Natta
polymerization

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 Pros & Cons of some polymerization techniques
Pros Cons
Bulk - easy - Difficult to control temp. and heat transfer
- No contamination - High viscosity
Solution -good heat transfer - Need to use solvent –adding cost
-easy to control reaction temp. -Difficult to eliminate solvent entirely
-low viscosity -Solvents sometimes act as chain transfer agent 
-polymer produced may be used directly leading to lower MW polymer
in the solution form

Suspension - Good heat transfer
- easy to control reaction temp.
- low viscosity
- polymer produced may be used directly
as polymeric suspension
Emulsion -- Good heat transfer
- easy to control reaction temp.
- low viscosity
- polymer produced may be used directly
as polymer latex
Interfacial -Reaction is fast at room temp. and
pressure.  No need for high temp. like
in normal polycondensation.
-Can produce polymer in fiber form
- Good heat transfer
- low viscosity
-Need extra process in washing out suspending
agent/contaminants and drying the polymer beads
-Polymer beads may stick together and maybe
contaminated with suspending agent
-Good only for addition polymerization using
hydrophobic free radical initiator.
-Need extra process in washing out emulsifier/
contaminants and drying
-Good only for addition polymerization using
hydrophilic initiator.
-Limited to polycondensation where the two reactants
are insoluble in each other ex. Acid chloride (quite
expensive)
- Need extra process in recovering solvent and excess
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reactants