Polymerization reaction exotherm

Poly (methyl methacrylate) for molding or extrusion is produced commercially by fiee-radical-initiated suspension or bulk polymerization of methyl methacrylate. To minimize polymerization reaction exotherm and shrinkage, bulk polymerization, which is used in the production of sheets, rods and tubes, is carried out with a reactive syrup of partially polymerized methyl methacrylate, which has a viscosity... 

This is an exothermic, reversible, homogeneous reaction taking place in a single liquid phase. The liquid butadiene feed contains 0.5 percent normal butane as an impurity. The sulfur dioxide is essentially pure. The mole ratio of sulfur dioxide to butadiene must be kept above 1 to prevent unwanted polymerization reactions. A value of 1.2 is assumed. The temperature in the process must be kept above 65°C to prevent crystallization of the butadiene sulfone but below lOO C to prevent its decomposition. The product must contain less than 0.5 wt% butadiene and less thM 0.3 wt% sulfur dioxide. 

Properties. Tetrafluoroethylene (mol wt 100.02) is a colorless, tasteless, odorless, nontoxic gas (Table 1). It is stored as a Hquid vapor pressure at —20° C = 1 MPa (9.9 atm). It is usually polymerized above its critical temperature and below its critical pressure. The polymerization reaction is highly exothermic. 

Properties. VinyHdene fluoride is a colorless, flammable, and nearly odorless gas that boils at —82°C. Physical properties of VDF are shown in Table 1. It is usually polymerized above its critical temperature of 30.1°C and at pressures above 3 MPa (30 atm) the polymerization reaction is highly exothermic. 

In order to faciUtate heat transfer of the exothermic polymerization reaction, and to control polymerizate viscosity, percent reactives are adjusted through the use of inert aromatic or aUphatic diluents, such as toluene or heptane, or higher boiling mixed aromatic or mixed aUphatic diluents. Process feed streams are typically adjusted to 30—50% polymerizable monomers. 

Chemical Reactivity - Reactivity with Water No reaction unless in the presence of acids and caustics Reactivity with Common Materials Slow decomposition occurs, but generally the reactions are not hazardous Stability During Transport Stable if cool Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Violent, exothermic polymerization occurs at about 225 of. Acid fumes will also cause polymerization at ordinary temperatures Inhibitor of Polymerization None reported. 

Exotherm heat It is heat given off during a polymerization reaction by the chemical ingredients as they react and the plastic cures. 

This monomer is ethylene when R is hydrogen, propylene when R is a methyl group, styrene when R is a benzene ring, and vinyl chloride when R is chlorine. The polymers formed from these four monomers account for the majority of all commercial plastics. The polymers come in great variety and are made by many different processes. All of the polymerizations share a characteristic that is extremely important from the viewpoint of reactor design. They are so energetic that control of the reaction exotherm is a key factor in all designs. 

The other entries in Table 13.2 show that heat removal is not a problem for most ring-opening and condensation polymerizations. Polycaprolactam (also called Nylon 6) is an addition polymer, but with rather similar bond energies for the monomer and the polymer. The reaction exotherm is small enough that large parts are made by essentially adiabatic reaction in a mold. An equilibrium between monomer and polymer does exist for polycaprolactam, but it occurs at commercially acceptable molecular weights. 

While subtle differences between gels synthesized with different initiators may exist, they are not easy to anticipate. The most important concern is usually the polymerization rate induced by a given initiator concentration [7], Polymerization reactions are highly exothermic, so a fast initiation rate can lead to a rapid temperature increase since the initiation and polymerization rate both increase rapidly with temperature, this process becomes autocatalytic. Poor quality, irre-producible gels result on a production scale such a runaway reaction could be-... 

In the second dual photo/thermal initiation strategy, the approach described above is augmented by the inclusion of a thermal initiator. Upon illumination, active centers produced by fragmentation of the photoinitiator start the polymerization reaction. The heat evolved from the exothermic photopolymerization elevates the temperature of the system and results in the production of additional active sites by the thermal initiator. This dual initiating strategy provides both the cure on demand (temporal control) afforded by photopolymerization, and the completeness of cure provided by the thermal initiator. 

Water offers a number of important properties as a solvent for polymerization reactions. As well as its high polarity, which gives a markedly different miscibility with many monomers and polymers compared to organic solvents, it is nonflammable, nontoxic and cheap. Water also has a very high heat capacity that sustains heat exchanges in a number of very exothermic polymerizations. Largely because of these factors, polymerizations are now widely carried out in aqueous media, and, for example, more than 50% of industrial radical polymerizations are carried out in water [19]. 

The heat of reaction for vinyl polymers affects the thermal stability of the polymer during extrusion, and the thermal stability is related to the ceiling temperature. The ceiling temperature is the temperature where the polymerization reaction equilibrium is shifted so that the monomer will not polymerize, or if kept at this temperature all the polymer will be converted back to monomer. From thermodynamics the equilibrium constant for any reaction is a function of the heat of reaction and the entropy of the reaction. For PS resin, the exothermic heat of reaction for polymerization is 70 kj/gmol, and the ceiling temperature is 310 °C. Ceiling temperatures for select polymers are shown in Table 2.5. 

Exothermic Reaction A reaction which evolves heat. Refining processes such as alkylation, hydrogenation, and polymerization are exothermic. 

In the use of polystyrene, the polymerization reaction is exothermic to the extent of 17 Kcal/mol or 200 BTU/lb (heat of polymerization). The polystyrene produced has a broad molecular weight distribution and poor mechanical properties. The residual monomer in the ground polymers can be removed using efficient devolatilization equipment. Several reviews are worthwhile consulting [42-44],... 

In general, polymerization reactions have to be to performed with care. Based on the fact that Taiwan has the largest ABS copolymer production in the world, a group originating from there has presented a study on possible hazards that might arise in the course of the polymerization process (112,113). The prevention of unexpected exothermic reactions and related emergency relief hazard is essential in the safety control of ABS emulsion polymerization. Various scenarios were verified from abnormal conditions, including (113) ... 

The facts that the LCST of PNIPAAm is only 32 °C and the polymerization reaction is highly exothermic can also lead to problems with reproducibility of the gel synthesis. If the solution is deliberately warmed above the LCST during polymerization, an opaque gel with a permanently phase separated microstructure is formed [65]. Depending upon the initial solution temperature, initiator concentration and type, and heat transfer characteristics of the gel mold, the solution temperature can rise substantially during polymerization and alter the gel s properties. 

Foamed-in-place polyurethane is prepared by allowing a polyol [po y(ethy ene glycol), polyester alcohols, etc.] to react with a diisocyanate in the presence of an amine catalyst. The gas which creates the foam may be a dissolved material, such as a Freon, which volatilizes during the exothermic polymerization reaction.7 A second method involves the use of water in the reaction mixture this hydrolyzes part of the isocyanate to produce an amine and C02 gas. The Freon-formed material is preferred for the insulation of low-temperature apparatus because the thermal conductivity of the foam is greatly reduced at low temperatures by the condensation of the Freon in the cells. It is probable that the longterm effectiveness of this phenomenon must be maintained by surrounding the foamed plastic with an airtight enclosure which will prevent diffusion of air into and Freon out of the cells. 

---