ヒドロキシ末端テレケリックポリ（2-アダマンチルビニルエーテル)の合成

摘要

ジビニルエーテルの酢酸付加体(1)とEt_(1.5)AlCl_(1.5)を組合せた開始剤を用い，酢酸ェチルの存在下，トルエン中，0℃の重合条件下で合成したリビングポリ(2-アダマンチルビニルエーテル)[ポリ(2-AdVE)]の成長末端変換反応を停止剤に水を用いて行い，アルデヒド末端テレケリックポリ(2-AdVE)(Polymer1)を合成した.%Aldehyde-terminated telechelic poly(2-adamantyl vinyl ether)s [poly(2-AdVE)s] were synthesized by water-based end-capping reaction of living poly(2-AdVE) with the bifunctional initiating system 1 [CH_3CH(OCOCH_3)-0(CH_2)_4OCH(OCOCH_3)CH_3]/Et_(1.5)AlCl_(1.5) in the presence of ethyl acetate in toluene at 0℃. The hydroxy-terminated telechelic poly(2-AdVE)s were synthesized by reduction of the terminal aldehyde groups with NaBH_4. The obtained hydroxy-terminated telechelic polymers possess controlled molecular weights and narrow molecular weight distributions (sample Ⅰ; M_n = 1,500, M_w/M_n= 1.47, sample Ⅱ; M_n = 3,200, M_w/M_n =1.48). ~1H NMR analysis showed that the resulting telechelic poly(2-AdVE)s had quantitative attachment of hydroxy terminals. Subsequent end-group transformation of hydroxy groups into acetate or urethane groups was possible.