It was found that the copolymers of sodium acrylate (AA‐Na) with styrene (St) and of sodium methacrylate (MAA‐Na) with methyl methacrylate (MMA) could polymerize vinyl monomers in an aqueous phase without the usual initiator. Interestingly, there was a definite composition of the copolymer for the polymerization of a given monomer; for example, when poly(St‐co‐AA‐Na) was used, St, MMA, vinyl acetate, ethyl acrylate, methyl acrylate, and acrylonitrile were polymerized by the copolymer having mole ratios of AA‐Na:St of 0.61:0.29, 0.47:0.53, 0.38:0.62, 0.30:0.70, 0.24:0.76, and 1.00:0, respectively. The copolymers of various compositions can form hydrophobic areas (HAs) in the water phase. As has been repeatedly reported, the polymerization proceeds in the HAs, and the following new hypothesis was recently proposed that the hard (the less hydrophilic) HA prefers to incorporate the hard monomer and the soft (the less hydrophobic or the more hydrophilic) HA prefers to incorporate the soft monomer. The results mentioned above support this hypothesis.
We have proposed a concept of hard and soft hydrophobic areas (HA) and monomers. In order to verify such a concept, two series of experiments were carried out. Poly(styrene-alt-disodium maleate) (1) and poly(styrene-altsodium methyl maleate) (2) were used as initiating macromolecules for the copolymerizations of styrene/methyl methacrylate (MMA) and acrylonitrile/MMA. When 1 was used, MMA was more easily polymerized than styrene. Inversely, when 2 was used, styrene was more easily polymerized than MMA. Poly(styrene-co-sodium acrylate) (3) substances with various compositions were used as intiators for the copolymerizations. The produced copolymers of MMA and styrene were found to have a larger content of MMA as the mole ratio of acrylate in 3 became higher. Inversely, the produced copolymers of MMA and acrylonitrile had a larger content of acrylonitrile as the mole ratio of acrylate became higher. Those results could be reasonably explained by the concept of hard and soft hydrophobic areas and monomers.
SynopsisThe polymerization of vinyl monomer initiated by an aqueous solution of poly(vinylbenzy1trim-ethy1)ammonium chloride (Q-PVBACl) was carried out at 85OC. Styrene, p-chlorostyrene, methyl methacrylate, and i-butyl methacrylate were polymerized, whereas acrylonitrile and vinyl acetate were not. The effects of the amounts of vinyl monomer, Q-PVBAC1, and water on the conversion of vinyl monomer were studied. The overall activation energy in the polymerization of styrene was estimated as 79.1 kJ mol-'. The polymerization proceeded through a radical mechanism. The selectivity of vinyl monomer was discussed by "a concept of hard and soft hydrophobic areas and monomers." ANAL. Calcd for --fC12HlgNCl j12~fCgHgCl juo+CgHg&-: C, 68.80%; H, 8.02%; N,
ABSTRACT:The polymerization of methyl methacrylate with Micrococcus lysodeiplicus was carried out in water, and the reaction was found to proceed through a radical mechanism. The effects of the quantity of reagent on the rate of polymerization and selectivity of vinyl monomer were studied. The change in the sectional view of the polymerization system was observed with a transmission electron microscope.
KEY WORDSMicrococcus lysodeiplicus I Radical Polymerization I Methyl Methacrylate I Transmission Electron Microscope I Recently, it was reported 1 • 2 that the cells of yeast, Saccharomyces cerevisiae, could initiate the polymerization of methyl methacrylate (MMA) in the presence of Cu(II) ion. Polymerization was found to proceed in the exterior and interior of the cell, particularly in the cell wall. The present paper deals with polymerization by the cells of bacteria, Micrococcus lysodeiplicus (abbreviated as Me 1). The possibility of radical polymerization, the effects of the quantity of reactant on the conversion of MMA and the selectivity of the vinyl monomer are studied. Moreover, the traits of the cells before and after polymerization, were observed with a transmission electron microscope.
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