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 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.
2.
3.
Solution Polymerization
b)
the polymer is insoluble in the solution
above a certain molecular weight
Disadvantage of solution
polymerization
1.
2.
3.
4.
Suspension Polymerization
(Pearl Polymerization)
The
Droplets
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
b)
c)
d)
Emulsion polymerization
Emulsion:
Emulsifiers : Surfactants
Emulsion polymerization :
Monomer
+
(MMA / styrene)
Anionic / cationic
(rapid quenced by water)
Latex
(dispersion of particulate
polymer in water : 0.05-2m
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
Propagation
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]???
Advantages:
a)
b)
c)
d)
Disadvantages
a)