ビニルエーテルのリビングカチオンポリマーと水との反応の再検討：アルデヒド端末およびヒドロキシ末端ポリビニルエーテルの合成

概要

論文の詳細を見る
The reaction of living cationic polymers of n-buty1 viny1 ether (NBVE;CH2=CH-O-nBu) with water was investigated to obtain the aldehyde-terminated poly(viny1 ether)s. The polymerizations of NBVE with 1,4-di(vinyloxy)butane-acetic acid adduct [1; CH3CH(OCOCH3)-O[CH2]4O-CH(OCOCH3)CH3]/Et1.5Alcl1.5/CH3COOEt system in toluene at 0 â and with the 2-acetoxyethy1 viny1 ether-hydrogen chloride adduct [2; CH3CH(Cl)-OCH2CH2CH2OCOCH3]/ZnCl2 system in toluene at -30 â produced bifunctional and monofunctional living polymers, respectively. The termination of these living polymers with aqueous ammonia gave the aldehyde polymer terminals (-CH2-CHO)quantitatively. In contrast, the termination with pure water under the same reaction conditions resulted in the formation of a small amount of the acetal polymer terminals [-CH2-CH-(OnBu)2]. 2-Methoxyethy1 viny1 ether (MOVE) was also polymerized with the 2/ZnCl2 system and treated with aqueous ammonia under the similar reaction condition to give the corresponding aldehyde-capped polymers. The reduction of the aldehyde groups of these polymers with NaBH4 or LiAlH4 afforded hydroxy-terminated telechelic poly(viny1 ethers)s.