Heat Transfer in Industrial Polymerizations

Free radical polymerizations are highly exothermic reactions, with adiabatic temperature rises for bulk monomers typically ~ 200 300 C (adiabatic temperature rise is the temperature increase that would occur on complete polymerization if no heat were removed from the system). If there is a process disturbance leading to a thermal runaway condition, the heat generation rate can exceed the heat removal In industrial polymerizations, the cooling systems heat removal capacity often becomes a limiting factor. When a reaction is scaled up, the heat generation rate increases in direct proportion to the reaction volume, while the heat removal capacity increases in proportion to the surface area available for heat transfer. The ratio of surface area to reactor volume decreases as the reactor size increases, and therefore it can be expected that at some scale the cooling systems safe operating capacity will be exceeded by the heat generation rate from the desired polymerization reaction. The use of a nonreactive component such as the aqueous phase in suspension or emulsion polymerization, or a solvent in solution polymerization, provides aheat sink that absorbs some of the heat of reaction. This advantageous feature is offset by the reduction in reactor productivity caused by the relatively low overall monomer loading. Failure to adequately control temperature can have deleterious effects on the product quality and pose serious safety issues. As previously discussed, free-radical polymerizations are highly temperature-sensitive.

Mixing Effects in Polymerization Reactors

The importance of mixing, the contacting of fluid elements from different parts of the reaction vessel with each other, has been the subject of several studies. Mixing can directly affect the kinetics, molecular weight, and composition in radical polymerizations by homogenizing local concentration gradients, but can also indirectly play an important role through its role in reducing thermal gradients in a reactor. In a small laboratory reactor, good mixing is usually readily achieved and therefore the polymer properties and reaction rate are unlikely to be influenced by mixing effects. However, similar to thermal effects, mixing effects become more apparent as reactor size increases because effectively mixing the entire reaction mixture becomes more difficult. Within the chemical process industries, polymerization reactions offer a particularly challenging problem because of the large increase in viscosity accompanying the conversion from monomer ( ~1cP for liquids) to polymer (>105cP). Some processes are designed to not require mixing. For example, PMMA can be polymerizedin large sheets. By having large surface areas available for heat transfer, adequatetemperature control is achieved without the need to provide mixing during polymerization.

Heterogeneous polymerizations such as suspension and emulsion utilize an aqueous, low-viscosity continuous phase to ensure that good mixing can be maintained throughout polymerization, with the viscosity increase confined to the dispersed phase (particles). Solution polymerization provides low viscosity and can promote mixing, but requires the removal of solvent from the polymer that is typically energy-intensive and costly. Some monomers are polymerized in bulk (e.g., styrene). The processes will often employ more than one reactor in series, since different reactor configurations and agitators will be required as the viscosity increases. The polymerization of gaseous monomers in free-radical processes poses unique challenges. The highpressure process for polymerizing ethylene to make low-density polyethylene (LDPE) is an established technology and still widely practiced, despite the importance of ZieglerNatta and metallocene catalysts in producing high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE). LDPE is highly branched (with long- and short-chain branches) with a broad molecular weight distribution, and for some applications offers processing and property advantages over the HDPE and LLDPE resins, which have narrower molecular weight distributions and short-chain branches. LDPE is manufactured in high-pressure adiabatic autoclaves [<30,000 psi (lb/in.2)] or cooled tubular reactors (<40,000 psi). The temperature and pressure conditions are maintained to keep the polymer in solution within the reactor. Monomer conversion per pass is low (15- 30%), with the unreacted ethylene separated from the solid LDPE powder as it exits the reactor and then recycled back to the inlet. The polymerizations are extremely fast and exothermic, with the potential for explosion if the radical concentration inthe reactor becomes too high.