Ring-Opening Metathesis Polymerization Using Alkenyl Sulfides as Chain-Transfer Agents: Efficient Routes to Unsymmetrical Poly(norbornene)-Based Macroinitiators Bearing a Terminal Hydroxy Group
作者:Hiroyuki Katayama、Yosuke Fukuse、Yuko Nobuto、Kensuke Akamatsu、Fumiyuki Ozawa
DOI:10.1021/ma034653m
日期:2003.9.1
hydroxy-terminated poly(norbornene)s (PNBEs) have been developed. Hydroboration of PNBEs bearing a terminal vinyl group with 9-BBN followed by oxidation with H2O2/NaOH forms hydroxy-terminated PNBEs in high yields. The parent PNBEs are prepared by ring-opening metathesis polymerization (ROMP) of norbornene using vinylic sulfides as chain-transfer agents (CTAs). On the other hand, ROMP of norbornene using (Z)-1-ph
已经开发了通往羟基封端的聚降冰片烯(PNBE)的便捷途径。带有9-BBN的带有末端乙烯基的PNBE进行硼氢化,然后用H 2 O 2 / NaOH氧化,可以高产率地形成羟基封端的PNBE。通过使用乙烯基硫化物作为链转移剂(CTA),降冰片烯的开环易位聚合(ROMP)来制备母体PNBE。另一方面,使用(Z)-1-苯硫基-1-丙烯-3-醇作为CTA的降冰片烯ROMP可以一步合成ω-羟基封端的PNBE,其中聚合物的分子量线性取决于CTA与单体的初始进料比。同样,使用(Z在苯基的对位上具有溴,氨基和4-(氯甲基)苯甲酰胺基取代基的CTA的-1--1-苯硫基-1-丙-3-醇可提供相应的α,ω-异二官能化(杂烯基)PNBE。所得的PNBE用作ε-己内酯的阴离子开环聚合(AROP)和苯乙烯的原子转移自由基聚合(ATRP)的大分子引发剂,从而得到AB型和ABC型嵌段共聚物。