METHODS OF POLYMERIZATION Polymerization reaction may take place in any of the three states of mattersolid, 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 reactions. LIQUID-PHASE REACTIONS: Homogenous type Bulk Polymerization/Mass Polymerization Solution Polymerization Heterogeneous type Emulsion Polymerization Suspension Polymerization/Pearl/Bead Polymerization 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. MASS POLYMERIZATION 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. 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. Batch reactors are used for polymerization. The

phenomenon in which the molecular weight of a substance increase tremendously is known as Autoaccleration Advantages High purity. High molecular weight and molecular weight distribution. Disadvantages High viscosity. Stirring becomes difficult after 30-40% conversion. As said above the mol.wt increases enormously which leads to autoaccleration. Due to gel effect/transdorff effect Rp is very high. Heat removal is difficult. Hot spots may form and explosion may possible. Removal of last traces of unreacted monomer is difficult.

No solvent contamination. Good flow characteristics. Longer polymerization time for high molecular weight polymers (nearly 1016 hrs.) Product can be used directly and no isolation is required due to its resistance towards solvents. Applications

Casting PMMA sheets. Used in free radical polymerization of MMA or styrene to get moulding powders. SOLUTION POLYMERIZATION 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 may be continuous/batch wise operation. The product obtained is in liquid phase. For most cases water is taken as solvent.

Advantages Heat transfer easy due to presence of solvent

Stirring is easy because the solution is low viscous Mass transfer is easy The product obtained is in liquid form and can be directly used for applications such as adhesives

Disadvantages High mol.wt polymers cannot be manufactured by this process because addition of solvent lowers monomer concentration which lowers rate of polymerization Complete removal of solvent is more difficult Polymer obtained is Impure Requires drying to be used as solid