Bulk Mass Polymerization

From the point of view of the polymerization process, bulk (mass) polymerization produces the purest PVC because only initiators and vinyl chloride are used in the process. Bulk polymerization is capable to yield 99.9% pure polymer. In suspension polymerization, a suspending agent is added in addition to initiator, which decreases the purity of suspension PVC to about 99.8%. Microsuspension polymer contains emulsifier and its piuity can be approximately 98.8%. Emulsion polymer may contain more emulsifier and initiator rests and its purity can be estimated as 98%. All these results are quite good for commercial product and PVC can be considered as a relatively pure polymer. More admixtures are usually introduced on the compounding stage from various contaminations and brought together with additives. 

Bulk (Mass) Polymerization 5 1.5 Processing of Polymers for Biomedical Devices 19... 

Free-radical polymerizations are highly exothermic. A typical adiabatic temperature rise for bulk (mass) polymerization of 200-500°C may not be uncommon. The overall activation energy for polymerization is in the order of 80 15 kj mol . The dramatic increase in the heat load during the gel-effect period can result in loss of temperature control, non-isothermal reactor operation and potential rimaways. Non-isothermal operation, aside from safety concerns, can also adversely affect product quality. 

Solution poly condensation polymerization is used when the temperatures needed to melt the monomer are too high or when bulk (mass) polymerization is too exothermic and hazardous. With solution polymerization, monomers and polymerization initiators are dissolved in a nonmonomeric liquid solvent at the start of polymerization. The solvent is usually a solvent for the polymer and copolymer product. 

Bulk (mass) polymerization is the polymerization of monomers to polymers without the presence of solvents or dispersants. Bulk polymerization is typically exothermic. Polymerization requires only monomer and a catalyst or accelerator. Bulk polymerization is used for many polycondensation polymerizations and chain-growth polymerizations. It is used with liquid monomers and also with gases and sohds. Heat stabilizers can be introduced during high-temperature polymerizations. 

In mass polymerization bulk monomer is converted to polymers. In solution polymerization the reaction is completed in the presence of a solvent. In suspension, dispersed mass, pearl or granular polymerization the monomer, containing dissolved initiator, is polymerized while dispersed in the form of fine droplets in a second non-reactive liquid (usually water). In emulsion polymerization an aqueous emulsion of the monomer in the presence of a water-soluble initiator Is converted to a polymer latex (colloidal dispersion of polymer in water). 

Because PS is brittle with little impact resistance under normal operating conditions, early work was done to impart impact resistance. The best known material from this work is called HIPS, which is produced by dispersing small particles of BR in with the styrene monomer. Bulk or mass polymerization of the styrene is begun producing what is referred to as... 

The bulk polymerization effects the special needs to remove the heat of reactions, and moreover, high conversions cannot be reached because the viscosity of the polymer increases drastically with conversion. In order to avoid a high viscosity of the end product before discharging, the mass polymerization is carried out in solution. Ethylbenzene is a common solvent. 

Commercial polystyrene manufacturing techniques are based either on a suspension process if the material is to be foamed or on a bulk polymerization process for GPPS and IPS. ABS-type polymers can also be produced via emulsion polymerization. Figure 2.5 shows the differences in emulsion and mass polymerization processes and the resulting morphology. Typically,... 

Polyfvinyl chloride) (PVC) is produced by mass, suspension, and emulsion processes. Mass polymerization is an exatiiple of a heterogeneous bulk system. PVC is virtually insoluble in vinyl chloride because the polymer is about 35% more dense than the monomer under normal polymerization conditions. Vinyl chloride, however, is quite soluble in polymer. The two phases in PVC polymerizations are pure monomer and monomer-swollen polymer. Polymerization proceeds in both phases, but it is very much faster in the polymer-rich phase because the mobility of macro radicals and mutual termination reactions are. severely restricted (cf. Section 6.13.2). 

Free radical polymerization of neat monomer in the absence of solvent and with only initiator present is called bulk or mass polymerization. Monomer in the liquid or vapor state is well mixed with initiator in a heated or cooled reactor as appropriate. The advantages of this method are that it is simple, and because of the few interacting components present, there is less possibility for contamination. However, vinyl-type polymerizations are highly exothermic so that control of the temperature of bulk polymerization may be difficult. Also, in the absence of a solvent viscosities may become very high toward the end of a polymerization, which could make stirring difficult, and add to the difficulty of heat removal from the system. The advantages of this system, however, are sufficiently attractive for this to be used commercially for the free radical polymerization of styrene, methyl methacrylate, vinyl chloride, and also for some of the polymerization processes of ethylene [7]. 

Free-radical polymerizations are carried out by a variety of processes that require different design considerations with respect to recipe of polymerization and physical conditions for the process and process equipment. Generally free-radical polymerizations are carried out by four different processes (a) bulk or mass polymerization, (b) solution polymerization, (c) suspension polymerization, and (d) emulsion polymerization. 

Free-radical polymerizations are commonly carried out by four different processes (a) bulk or mass polymerization, (b) solution polymerization, (c)... 

---