Kiichi Takemoto

Vinyl Polymerization. CLXXXV. Polymerization of Methyl Methacrylate Initiated with Benzoic Anhydride and Dimethylaniline N-Oxide. Effects of Solvent and the Substituent of the Initiator

Abstract Studies on the rate of the reaction of substituted dimethylaniline N-oxide (DMAO) with substituted benzoic anhydride (Bz2O) and the rate of polymerization of methyl methacrylate (MMA) with their systems were made. The solvent effects on the rate of the reaction of DMAO with Bz2O and on the polymerization of MMA with the system were also studied.

Vinyl Polymerization. CLXVII. Vinyl Polymerization Initiated with p-Methoxy p′-nitrobenzoyl Peroxide

Abstract It was described in the literature that p-methoxy-p′-nitrobenzoyl peroxide decomposed homolytically in benzene, but heterolytically in acetone. However, in the present study the polymerizations of styrene and acrylonitrile were found to proceed always through radical mechanism in benzene, dimethylformamide, or acetone. And in the above various solvents, the rate of polymerization was found to be almost equal.

Vinyl Polymerization. 215. Decomposition of p-Methoxy-p′-nitrobenzoyl Peroxide in Monosubstituted Benzenes and Polymerization of Styrene Initiated with This Peroxide

Abstract The rate constant of decomposition of p-methoxy-p′-nitrobenzoyl peroxide (MN-BPO), k′d, in various monosubstituted benzenes was measured. The value of k′d seemed to increase with the polarity of the solvents. Activation energies and activation entropies of the decomposition were determined. When styrene was present, the rate constant of decomposition of MN-BPO, kd, increased markedly by three to five times, except in the case of cyano-and nitrobenzenes.

Acetoxylation of Polyvinyl Chloride.

ポリ塩化ビニルおよびその脱塩素体をテトラヒドロフラン中,60～65℃ において酢酸および無水酢酸の存在下,酢酸銀によるアセトキシル化反応を行ない,その反応はポリ塩化ビニル自体よりも脱塩素体の方がより平滑に進行すること,反応時間とともに生成物の極限粘度値が低下することを見出した。赤外線吸収スペクトルおよび元素分析,溶解性の検討を行ない,その結果から分子内にアセトキシル基の生成することを見出した。またポリ塩化ビニルの還元体についても同様の反応を行なった。酢酸銀のかわりに他の酢酸塩をもちいた場合には,反応はほとんど進行しなかった。さらに一部のアセトキシル化物について加水分解を行ない,生成物の検討を行なった。