ABSTRACT:Radical polymerization of methyl methacrylate (MMA) initiated by diphenyldisulfide (DPDS) and CuC12 was carried out in a mixed solvent of 1,4-dioxane and water. Formerly, we reported 1 that lysozyme having four S-S linkages in a molecule could initiated the polymerization of methyl methacrylate (MMA) in an aqueous solution of CuC1 2 , and concluded that the initiation was consisted of three reactions, that is, (i) a normal "uncatalyzed polymerization" which is a reaction of polypeptide portion of lysozyme with Cu(II) ion, water and MMA, (ii) a generation of free radicals by the reaction of S-S bond with Cu(II) ion, and (iii) a thermal polymerization in MMA phase.The extent of our research indicates that the generation of free radicals by the reaction of S-S bond with Cu(II) ion in the dark is not known. Accordingly, it is necessary to ascertain whether a simple compound having S-S bond can initiate a radical polymerization of MMA in the dark and in the presence of Cu(II) ion. The present paper deals with this kind of polymerization. As a simple disulfide model, diphenyldisulfide (DPDS) was used.
The polymerization of vinyl monomer initiated by polyethyleneglycol (PEG) in aqueous solution was carried out at 85°C with shaking. Acrylonitrile (AN), methyl methacrylate (MMA), and methacrylic acid were polymerized by PEG–300 (M̄n = 300), whereas styrene was not. The effects of the amounts of monomer and PEG, the molecular weight of PEG, and the hydrophobic group at the end of PEG molecule on the polymerization were studied. The selectivity of vinyl monomer and the effect of the hydrophobic group are discussed according to “the concept of hard and soft hydrophobic areas and monomers.” The kinetics of the polymerization was investigated. The overall activation energy in the polymerization of AN was estimated as 37.9 kJ mol−1. The polymerization was effected by a radical mechanism.
The effect of polyethyleneglycol on the radical polymerization of methyl methacrylate initiated with an aqueous solution of sodium polystyrenesulfonate was studied. Under the definite condition, the conversion of methyl methacrylate raised from 6.6 to 100% by the addition of polyethyleneglycol. It was concluded that polyethyleneglycol acted only as a host of Na+, but not as a phase transfer catalyst.
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