茂型过渡金属化合物催化“活性”自由基聚合反应的研究.docx

南开大学博士论文 庄岩
摘要
本文旨在找到新型的稳定的茂型过渡金属有机化合物,并用于催化活性自由基聚合
的研究。
找到了全新活性自由基催化剂二茂钴:催化甲基丙烯酸甲酯自由基聚合可得到PDI ;催化苯乙烯自由基聚合可得到PDI 。通过对不同条件下二茂钴催化活性自由基聚合的考察,找到了聚合的最佳条件。
发现了二茂钴阳离子可以催化AIBN引发的MMA和苯乙烯反向1ATRP反应,并得
到活性聚合的结果。
考察了一系列非桥连和桥连环戊二烯基铁铁键化合物催化苯乙烯自由基聚合的结果,发现叔丁基环戊二烯四羰基二铁和碳硅桥连环戊二烯四羰基二铁可以催化苯乙烯活性自由基聚合,并讨论了催化活性与铁铁键键长的关系。
考察了一系列非桥连和桥连环戊二烯基钌钌键化合物催化苯乙烯自由基聚合的结果,发现叔丁基环戊二烯四羰基二钌是很好的苯乙烯活性自由基聚合催化剂。
考察了一系列带环戊二烯基的第六副族金属有机化合物,并发现CpMo(CO)3CH2Ph 可以作为引发剂引发MMA控制聚合,钼和钨的环戊二烯基金属键金属键化合物能在室温下就催化MMA聚合,。
关键词:活性自由基聚合,原子转移自由基聚合,反向原子转移自由基聚合、二茂
钴、二茂钴阳离子,环戊二烯基金属金属键化合物
南开大学博士论文庄岩
Abstract
In this dissertation,a lot plexes containing cyclopentadiene were synthesized and catalyzed MMA or styrene relationships between the structures ofcatalysts and activities ofliving radical polymerizations were studied.
A novel catalyst,cobaltocene,was used as catalyst of MMA and styrene atom transfer radical polymerizations(ATRP).The polymerizations were showed“living’'/controlled radical polymerization defined PMMA or PSt with narrow polydispersity (PDI~ and ,respectively),and with∞-bromine atom end groups was beRer polymerization conditions were found by discussing experiment results.
Cobalticinium(CpCoBr3)was used as catalyst of MMA and styrene reversed polymerizations proceeded in a‘‘living’'/controlled manner,and narrow polydispersity polymers were obtained.
The styrene polymerizations catalyzed by a series of cyclopentadienyl plex
、Ⅳcrc plex’[t-BuCpFe(CO)2]2 and(CMez)(SiMe2)[(rl 5-CsH3)Fe(CO)2]2 controlled the polymerization relationship between activities of living radical polymerizations and lengths of iron·iron bond were discussed.
The styrene polymerizations catalyzed by a series of cyclopentadienyl plex were plex,【t-BuCpRu(CO)2]2 was the best catalyst of styrene living radical polymerization.
The MMA polymerizations catalyzed by a series of plexes were was found t