Supercritical polymerization reactions

Runaway reaction or polymerization—e.g., vinyl chloride monomer (Kim-E and Reid, The Rapid Depressurization of Hot, High Pressure Liquids or Supercritic Fluids, chap. 3, in M. E. Paulaitis et al., eds.. Chemical engineering at Supercritical Fluid Conditions, Ann Arbor Science, 1983, pp. 81-100)... 

Supercritical fluids have also been used purely as the solvent for polymerization reactions. Supercritical fluids have many advantages over other solvents for both the synthesis and processing of materials (see Chapter 6), and there are a number of factors that make scCCH a desirable solvent for carrying out polymerization reactions. As well as being cheap, nontoxic and nonflammable, separation of the solvent from the product is achieved simply by depressurization. This eliminates the energy-intensive drying steps that are normally required after the reaction. Carbon dioxide is also chemically relatively inert and hence can be used for a wide variety of reactions. For example, CO2 is inert towards free radicals and this can be important in polymerization reactions since there is then no chain transfer to the solvent. This means that solvent incorporation into the polymer does not take place, giving a purer material. 

Radical polymerization can be carried out under homogenous as well as heterogenous conditions. This difference is classified based on whether the initial mixture and/or final product are homogenous or heterogenous. Some homogenous mixtures become heterogenous as polymerization proceeds as a result of insolubility of the resulting polymer in the reaction media. There are many other specialized processes that are used to synthesize materials via free-radical polymerization. These include interfacial polymerization, gas phase reactions ( popcorn polymerization ), as well as the use of specialized media like supercritical fluids. Current research efforts include the study of such... 

In a patent entitled Supercritical Polymerization of Olefins, Cottle (1966) describes a process for reacting and separating polymers made from olefins. In this case propylene is reacted to polypropylene in a process using a catalyst and operating at conditions above the critical temperature and pressure for propylene T. = 91.9°C, = 46.2 bar). At the end of the reaction the system... 

The low rates observed in supercritical CO2 are most likely due to the fact that CO2 is a much weaker solvent than dioxane. Despite the failure to observe enhanced reactivity in this system, the success of Noyori and coworkers suggests that investigation of other CO2 reactions, particularly polymerizations, (135,136) in supercritical CO2 is worthwhile. Many such reactions remain unexplored in supercritical CO2 including catalytic reactions between butadiene and CO2, (137) formation of isocyanates, (138,139) urethanes, (139-143) ureas, (144,145) and polyureas (146,147) from CO2 and amines, and production of cyclic carbonates from CO and epoxides. 

Because of its tunable density and low viscosity, synthetic organic chemists are beginning to utilize supercritical C02 as a medium for exploring reaction mechanisms and solvent cage effects [10,11]. Asymmetric catalysis represents an area in which supercritical C02 may be useful as a solvent [12]. For polymerization reactions, in particular, the solvency of C02 as a medium and the plasticization effects of C02 on the resulting polymeric products represent the properties of central importance. These significant properties of C02 are explored in detail below. When all of these factors are combined with the fact that C02 may obviate the use of much more expensive and hazardous solvents,... 

In 1994, we reported the dispersion polymerization of MM A in supercritical C02 [103]. This work represents the first successful dispersion polymerization of a lipophilic monomer in a supercritical fluid continuous phase. In these experiments, we took advantage of the amphiphilic nature of the homopolymer PFOA to effect the polymerization of MMA to high conversions (>90%) and high degrees of polymerization (> 3000) in supercritical C02. These polymerizations were conducted in C02 at 65 °C and 207 bar, and AIBN or a fluorinated derivative of AIBN were employed as the initiators. The results from the AIBN initiated polymerizations are shown in Table 3. The spherical polymer particles which resulted from these dispersion polymerizations were isolated by simply venting the C02 from the reaction mixture. Scanning electron microscopy showed that the product consisted of spheres in the pm size range with a narrow particle size distribution (see Fig. 7). In contrast, reactions which were performed in the absence of PFOA resulted in relatively low conversion and molar masses. Moreover, the polymer which resulted from these precipitation... 

The use of a copolymerizable macromonomer constitutes another approach to the dispersion polymerization of MMA. We have recently demonstrated the utility of this approach in C02 by employing a PDMS monomethacrylate as the stabilizer (see Fig. 8) [121], Although several groups have studied the behavior of polysiloxanes in C02 [54,55,57], this work represents the first successful use of PDMS based polymeric stabilizers in C02. The reactions were conducted in either liquid C02 at 30 °C and 75 bar or supercritical C02 at 65 °C and 340 bar. 

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