This invention relates catalysis and concerns production of catalyst for dicyclopentadiene (DCPD) ring-opening metathesis polymerization.
Catalyst for metathesis polymerization has the formula:
where L is a substituent selected from the group:
Several methods of the catalyst preparation were developed:
Method of preparing catalyst having the following formula
where L
where the second generation Grubbs catalyst is subject to interaction with (N,N-dialkyl-(2-vinylbenzyl)amine or 1-(2- vinylbenzyl)pyrrolidine or 4-(2- vinylbenzyl)morpholine in inert atmosphere at temperatures of 60-85 °C in the presence of a solvent, with dialkyl- being methylethyl- or methyl(2-metoxyethyl).
Method of preparing catalyst having the following formula
where L is a substituent selected from the group:
where triphenylphosphine complex of ruthenium is subject to interaction with 1,1-diphenyl-2-propyne-1-ol in tetrahydrofuran at the temperature of solvent boiling in inert atmosphere, and then with tricyclohexylphosphine at room temperature in inert atmosphere; indenylidene complex of ruthenium formed is recovered and then step by step, in one reactor, it is subject to interaction with 1,3-Bis(2,4,6-trimethylphenyl)-2-(trichloromethyl)imidazolidine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl) pyrrolidine HJIH 4-(2- vinylbenzyl)morpholine in toluene with heating at 60-70°C in inert atmosphere, with dialkyl- being dimethyl, diethyl-, or methylethyl- or methyl(2-metoxyethyl)-.
Method of metathesis polymerization of dicyclopentadiene has been also developed where polymerization is carried out with the catalyst of item 1 with mole ratio of substrate to catalyst of 70000:1 to 200000:1.
Invention allows increasing of the catalyst yield and simplifies schemes of synthesis through reducing number of stages, as well as preparing polydicyclopentadiene with high application properties.
本发明与催化有关,涉及双
环戊二烯(DCPD)开环偏聚催化剂的生产。
元合成聚合催化剂的
化学式为
其中 L 是选自以下组别的取代基:
已开发出几种催化剂制备方法:
制备下式催化剂的方法
其中 L
第二代 Grubbs 催化剂与 N,N-二烷基-(2-
乙烯基苄基)胺或 1-(2-
乙烯基苄基)
吡咯烷或 4-(2-
乙烯基苄基)吗啉在惰性气氛中于 60-85 ℃温度下在溶剂存在下发生作用,其中二烷基为甲基乙基或甲基(2-甲氧基乙基)。
制备下式催化剂的方法
其中 L 是选自以下组别的取代基:
其中
钌的
三苯基膦络合物在溶剂沸腾温度和惰性气氛下与
四氢呋喃中的
1,1-二苯基-2-丙炔-1-醇作用,然后在室温和惰性气氛下与
三环己基膦作用;回收形成的
钌的亚
茚基络合物,然后在一个反应器中逐步与 1,3-双(2,4,6-三甲基苯基)-2-(三
氯甲基)
咪唑烷和 2-(N、N-二烷基
氨基甲基)
苯乙烯或 1-(2-
乙烯基苄基)
吡咯烷 HJIH 4-(2-
乙烯基苄基)吗啉在
甲苯中发生作用,在 60-70°C 的惰性气氛中加热,二烷基为二甲基、
二乙基或甲基乙基或甲基(2-甲氧基乙基)。
此外,还开发了二
环戊二烯的偏合成聚合方法,使用第 1 项催化剂进行聚合时,底物与催化剂的摩尔比为 70000:1 至 200000:1。
本发明通过减少阶段数量,提高了催化剂产量,简化了合成方案,并制备出具有高应用特性的聚二
环戊二烯。