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Polymerization

techniques

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:
1.

2.
3.
4.

There is no problem with getting


solvent out of the finished product
(since no solvent is used.)
High rates of polymerization
High degrees of polymerization
High purity

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
Dispersion stabilizers dissolved in the
b)
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
a)
b)
c)

d)

better heat control of the reaction


Low viscosity due to suspension
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.
Polymer yields in the form of beads
(0.1-2 mm)

a)

b)
c)

d)

The disadvantage of
Suspension Polymerization

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 molec

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-

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

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