Polymerization process

Process conditions:
Homogeneous polymerization:
a)
Bulk
b)
Solution
2. Heterogeneous polymerization
a)
Suspension
b)
Emulsion
1.

Concerning:
Molecular Weight
Rate (kinetics)
Heat effects (thermodynamics)

Bulk polymerization

The bulk addition polymerization is the

simplest of all polymerization processes
Bulk polymerization is the conversion of
monomer into a polymer without the aid of a
solvent
A bulk addition polymerization is a
homogeneous system with an organic initiator.

For bulk polymerization, there are two

possibilities:
a) polymer soluble in monomer
(example: polystyrene)
Polystyrene is soluble in styrene to infinite
molecular weight.
Therefore, some physical changes occur with
increasing molecular weight (e.g., viscosity,
etc.)

b) polymer insoluble in monomer

(example: vinylidine chloride)

The above probably implies that polyvinylidine chloride precipitates

out of the solution of vinylidine chloride monomer when it reaches a
certain molecular weight.

If the polymer is insoluble in the monomer, the rate of initiation is

proportional to the monomer concentration, the initiator
concentration, and the inverse square of K over t

The higher the temperature, the lower the molecular weight of the
polymer produced. ( at higher temperatures, the initiator
decomposes to form radicals at a faster rate, then for a given
amount of monomer with more radicals present more polymer
chains will be started
(initiated), and the resulting polymers
will have a lower molecular weight.

ADVANTAGES:
There is no problem with getting solvent
out of the finished product (since no
solvent is used.)
2. High rates of polymerization
3. High degrees of polymerization
4. High purity
1.

Disadvantages:
1.

Rapid increase of viscosity leads to inefficient stirring

2.

Difficult to remove heat evolved upon polymerization.

The thermal conductivity of monomers and polymers is
low, and as the viscosity builds up, the ability for heat
transfer via convection is substantially diminished. If
the heat energy cannot be dissipated, temperature
rises, and at higher temperatures the reaction is going
to go faster, so this is a positive feedback loop with
disastrous consequences.

3.

For bulk polymerization, removal of unreacted

monomer can be a problem. This is a large concern if
your safe polymer was prepared from monomers
which are toxic.

Solution Polymerization

The main advantage of a diluent (either water or

an organic solvent) is to take up the heat of
polymerization.
For solution polymerizations, there are two
possibilities:
a) monomer is soluble and the polymer is
soluble in the diluent:
(example: polystyrene in toluene)
b) monomer is soluble and the polymer is
insoluble in the diluent:
(example: acrylonitrile in chloroform)

a) If both the monomer and the polymer system

are soluble in the solution

(i.e. no polymer precipitation), then as the

polymerization occurs:
a) The viscosity of the solution increases.
b) The rate of polymerization will decrease with
time.
The rate of polymerization is proportional to
monomer concentration, initiator
concentration, and the inverse square of (K
multiplied by t.)

b)
the polymer is insoluble in the solution
above a certain molecular weight

(i.e., the polymer precipitates out at that

molecule weight) then the viscosity is
more likely to remain fairly constant.
Dimerization termination is more likely,
and the rate of chain transfer is faster.
Heat effects are much better

Advantage of solution polymerization

Solvent acts as a diluents and aids in
removal of heat of polymerization.
2. Solvent reduces viscosity, making
processing easier.
3. Thermal control is easier than the bulk
1.

Disadvantage of solution
polymerization
1.
2.

3.

4.

Difficult to remove solvent from final form,

causing degradation of bulk properties.
Environmental pollution due to solvent release.
The removal of the diluents from the
polymer requires a distillation, and that
costs an appreciable amount of money.
Chain transfer to solvent occurs, leading to low
molecular weights.

Addition polymerizations are usually

carried out bulk and solution
polymerizations.
Condensation polymerizations are carried
out mostly without solvents (Bulk)

Suspension Polymerization
(Pearl Polymerization)

The reaction mixture (monomer, inorganic

stabilizer, oil-soluble initiator) is suspended as
droplets in water (where it is insoluble).
Therefore, there are two separate phases
throughout the whole process; water and
organic, and the starting point may be 10 parts
of the former, and 1 part of the latter.
The water phase becomes the heat transfer
medium. Since it is a continuous phase, viscosity
changes very little as the monomer converts to
polymer, so the heat transfer is very good.

 The

initiator used can be water

soluble or organic soluble
[benzoyl peroxide, AIBN, or
(NH4)2(SxO4)y.] Usually the
initiator is organic soluble.

Droplets

(Particle size ) may be 0.01

to 0.5 cm, or as low as 1 micron.

This process needs:

a)

Vigorous agitation : consistent, efficient, and controlled

throughout the reaction to keep the droplets apart. A
suspending agent can also be used.

suspension agent is a material that gives a surface

activation that keeps droplets from become larger
(droplets coming together to form larger droplets is
called coalescence.)
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. This probably relates to the
idea that as the volume of a sphere increase, the ratio
of surface area to volume decreases, and this ratio
relates to heat transfer.
A typical suspending agent : PVA dissolved in the
aqueous phase

Continue
b) Dispersion stabilizers dissolved in the
aqueous phase
c) In this system, the monomer must be either :
1) insoluble in water or
2) only slightly soluble in water, so that
when it polymerizes it becomes insoluble
in water.

 The

particle size is affect by the

following four factors:
stirring rate
ratio of reactants
suspension agent
temperature

Suspension polymerization is similar to bulk

polyerization, and it could be considered "bulk
polymerization within a droplet."
Therefore, in suspension polymerization,
initiation, propogation, and termination take
place inside the droplet.
The speed at which the reaction takes place for
a given temperature is the same, and just as for
bulk polymerization, the kinetics or rates are
proportional to monomer concentration.
The properties of the polymer are similar to
those of the same polymer made by a bulk
polymerization.

Suspension polymerization is used

only in free radical type processes. The
monomer is mechanically dispersed in a
media, usually water. There are cases
where an organic media is used in which
neither the polymer nor the monomer are
soluble in the organic media.
when using gases ; Example ; the
polymerization of vinyl chloride (a gas at
room temperature) pressure and
containment are concerns.

The advantages of Suspension

Polymerization
better heat control of the reaction
b) Low viscosity due to suspension
c) separation is much easier than in
solution polymerization. Can be isolated
by filtration or this stable latexes and
dispersions can be used directly in
coatings, paints and adhesives.
d) Polymer yields in the form of beads (0.12 mm)
a)

The disadvantage of Suspension

Polymerization
a)

b)
c)
d)

Cannot be used for whose Tg is less than the

polymerization temperature, or else aggregation will
occur.
Must separate and purify polymer, or accept
contaminate product.
It only applies to free radical process. Ionic catalysts
don't work because they compete with water
Agitation is critical because as the viscosity within
the bead rises, the reaction rate increases suddenly.
This leads to a surge in heat generation which does
not usually occur in solution or emulsion
polymerization

Emulsion polymerization

Emulsion:

A stable colloidal suspension as milk,

consisting of an immiscible liquid
dispersed and held in another liquid by a
substance called an emulsifier

Emulsifiers : Surfactants

Amphipathic (dual personalities)

At a certain concentration of surfactant in water,

surfactant congregate and form micelle above critical
micelle concentration (CMC)

Spherical with 20-100

Contain 50-150 molecule

The hydrocarbon (10-20 C) core provide sites for

polymerization.

Micelle became swollen by monomer molecules.

Micelles are in equilibrium with free surfactants

Emulsion polymerization :

Polymerization that takes place in a

emulsion typically incorporating water,
monomer and surfactant

Therefore from the definition:

Immiscible liquid : hydrophobic monomer
Mother liquor : water
Emulsifier : surfactant /soap

Surfactant (PVA, Hydroxyl ethyl cellulose)

+water
Dissolved until CMC is reached

Monomer
+
(MMA / styrene)

water soluble initiator

(peroxide / persulfates)

EP are performed via

Free radical
Product

Anionic / cationic
(rapid quenced by water)

Latex
(dispersion of particulate
polymer in water : 0.05-2m

Location of the monomer:

In a large monomer droplets (10,000 )
floating around in water. There are
about 1010-1011 monomers droplets/cm3
b) Some of the monomer may be dissolved
in water (unlikely)
c) Monomer may be found in micelles
(exactly what we want)
a)

EP Mechanism:
Can be carried out as:
Batch reaction
2. Starve fed reaction (most cases) to
insure good distribution of monomers
into the polymer backbone chain.
1.

Initiation:
Initiator migrates into micelle and react
with a monomer molecules.
(initiator attacks monomer in the micelle
that has a large surface area than the
larger monomer droplets)
Polymerization starts

Micelle is now referred as particle

Propagation

Monomer migrates from the large monomer

droplets to the micelle to sustain polymerization.
On average, there is one radical / micelle
All monomer is consumed in EP. Therefore latex
can be used without purification (important for
paints and coatings)
Each micelle can be considered as mini bulk
polymerization except no unreacted monomer
and no thermal hot-spots

Termination
Monomer in the micelle quickly
polymerized and the growing chain
terminates
More monomer from the droplets diffuses
to the growing particle where more
initiators will eventually react

Molecular weight??
Rate of polymerization = rate of
disappearance of monomer
Monomer disappear faster when there are
more particle. Therefore, in order to have
more particles, we must have more
micelle.
For that reason : [initiator]???

Polymers that are made

commercially via EP:
Polyvinyl acetate
Polychloroprene
PMMA
PVC
Polyacrylamide
Copolymers of PS,Polybutadiene and PAN

Advantages:
a)

b)
c)
d)

Continuous water phase is an excellent

conductor of heat and allow heat to be
removed from the system. Therefore, rate
increased.
Viscosity 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 / processed.
Able to control particle structure

Disadvantages
a)

Contamination by the surfactant. Cause

water sensitivity