Heat of polymerization

Addition polymerization is an exothermic process, and the change in enthalpy is typically in the range 34 to 160 kJ molThe particnlar valnes differ for each monomer and are influenced by several factors, i.e., (1) the energy difference between monomer and polymer resulting from resonance stabilization of the double bond by the substituent or by conjugation, (2) steric strains in the polymer imposed on the new single bonds by substitnent interactions, and (3) polar or secondary bonding effects. 

The large heat of polymerization can have serious practical consequences, especially when polymerizations are rapid, and can even lead to thermal explosions. To avoid these defects, the rate of the process must be controlled or other practical expediencies adopted. Heat removal is particularly problematic in bulk polymerizations taken to high conversions as the reaction mixtures become very viscous, and efficient stirring becomes difficult. 

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Nxylylene system, substituents affect it only to a minor extent. AH parylenes are expected to have a similar molar enthalpy of polymerization. An experimental value for the heat of polymerization of Parylene C has appeared. Using the gas evolution from the Hquid nitrogen cold trap to measure thermal input from the polymer, and taking advantage of a peculiarity of Parylene C at — 196°C to polymerize abmptiy, perhaps owing to the arrival of a free radical, a = —152 8 kJ/mol (—36.4 2.0 kcal/mol) at — 196°C was reported (25). The correction from — 196°C to room temperature is... 

Several recent patents describe improvements in the basic belt process. In one case a higher soHds polymerization is achieved by cooling the starting monomer until some monomer crystallizes and then introducing the resulting monomer slurry onto the belt as above. The latent heat of fusion of the monomer crystals absorbs some of the heat of polymerization, which otherwise limits the soHds content of the polymerization (87). In another patent a concave belt is described which becomes flat near the end. This change leads to improved release of polymer (88). 

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical (72—74) and radiation-initiated (75) polymerizations are also well known. At a constant temperature, the initial rate of the bulk or solution radical polymerization of acrylic monomers is first order with respect to monomer concentration and one-half order with respect to the initiator concentration. Rate data for polymerization of several common acrylic monomers initiated with 2,2 -azobisisobutyronittile (AIBN) [78-67-1] have been determined and are shown in Table 6. The table also includes heats of polymerization and volume percent shrinkage data. 

A schematic of a continuous bulk SAN polymerization process is shown in Figure 4 (90). The monomers are continuously fed into a screw reactor where copolymerization is carried out at 150°C to 73% conversion in 55 min. Heat of polymerization is removed through cooling of both the screw and the barrel walls. The polymeric melt is removed and fed to the devolatilizer to remove unreacted monomers under reduced pressure (4 kPa or 30 mm Hg) and high temperature (220°C). The final product is claimed to contain less than 0.7% volatiles. Two devolatilizers in series are found to yield a better quaUty product as well as better operational control (91,92). 

Methacrylates Heat of vaporization, kJ/g" Heat capacity, J/(g-K) Heat of polymerization, kJ / mol ... 

In the recipes shown in Table 2, the amount of water can vary widely, depending on the available heat-transfer capacity of the reactor and the rate of polymerization. Each of the monomers has a heat of polymerization of about 75 kj/ mol (18 kcal/mol), so removing the heat of polymerization to control temperature is often the limiting factor on rate of polymerization. 

Commercial chloroprene polymerization is most often carried out in aqueous emulsion using an anionic soap system. This technique provides a relatively concentrated polymerization mass having low viscosity and good transfer of the heat of polymerization. A water-soluble redox catalyst is normally used to provide high reaction rate at relatively low polymerization temperatures. 

Polymerization in aqueous solution of acrylamide can also be fulfilled in thin layers (up to 20 mm) applied on a steel plate or a traveling steel band. Polymerization is initiated by persulfates, redox system, UV or y radiation. Polymerization proceeds in isothermal conditions as the heat of polymerization is dissipated in the environment and, additionally, absorbed by the steel carrier. Nonadhesion of the polymer to the carrier is ensured by the addition of glycerol to isopropyl alcohol or by precoating the steel band with a film based on fluor-containing polymers. This makes polymerization possible at a high concentration of the monomer (20-45%) and in a wider process temperature range. This film of polyacrylamide is removed from the band, crushed, dried, and packed. 

The polymerization in method [III] will probably be unsuitable for industrial production due to the heat of polymerization, but it can be used to produce a freeze-thaw stable adhesive with rapid drying and good adhesion to paper, which cannot be obtain by other polymerization methods. However, the water resistance of the latex film is not improved. 

This method was first applied by McCormick27 and by Bywater and Worsfold11 to the system a-methylstyrene/poly-a-methyl-styrene, and the free energy, entropy and heat of polymerization as well as the ceiling temperature were determined. Similar studies concerned with the system styrene/polystyrene are being carried out in our laboratories. 

Polymerization thermodynamics has been reviewed by Allen and Patrick,323 lvin,JM [vin and Busfield,325 Sawada326 and Busfield/27 In most radical polymerizations, the propagation steps are facile (kp typically > 102 M 1 s l -Section 4.5.2) and highly exothermic. Heats of polymerization (A//,) for addition polymerizations may be measured by analyzing the equilibrium between monomer and polymer or from calorimetric data using standard thermochemical techniques. Data for polymerization of some common monomers are collected in Table 4.10. Entropy of polymerization ( SP) data are more scarce. The scatter in experimental numbers for AHp obtained by different methods appears quite large and direct comparisons are often complicated by effects of the physical state of the monomei-and polymers (i.e whether for solid, liquid or solution, degree of crystallinity of the polymer). 

Monomer Formula Explosion Causing Environment Explosion Prevention Techniques Heat of Polymerization in kcal/mole Ignition Temp,°C Polymerization Techniques... 

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