采用Grubbs催化剂的双环戊二烯开环移位聚合速率调控  

Reaction Rate Control in Ring Opening Metathesis Polymerization of Dicyclopentadiene with Grubbs Catalyst

作　　者：孙春水[1] 谢家明[1] 傅建松[1] 周立武[2] 姚臻[2] 曹堃[2] 

机构地区：[1]中国石油化工股份有限公司上海石化化工研究所,上海200540 [2]化学工程联合国家重点实验室,浙江大学化工系聚合与聚合物工程研究所,浙江杭州310027

出　　处：《化学反应工程与工艺》2011年第3期252-256,共5页Chemical Reaction Engineering and Technology

摘　　要：以双环戊二烯的反应注塑成型工艺为目的,研究了采用Grubbs催化剂的双环戊二烯开环移位聚合速率调控手段,详细考察了反应气氛、聚合温度、催化剂浓度及调聚剂三苯基膦含量对聚合过程的影响。结果表明,该体系可在少量氧存在的条件下聚合。即使反应温度较低(35℃),凝胶时间仍可小于10 min,且单体转化率接近100%。催化剂浓度对聚合速度影响较大,当催化剂浓度降低至单体的4.17×10^(-6)时,聚合体系凝胶时间可增加到70 min。调聚剂三苯基膦的含量存在一临界点,高于临界点体系不凝胶,单体转化率低;低于临界点反应迅速,单体转化率高。基于上述结果,成功设计并实施了一种两股物料的反应注塑成型工艺路线,各股物料储存时间均大于70min,两者混合后14min凝胶,单体转化率为99.5%。Aimed at the application of reaction injection moulding （RIM） of dicyclopentadiene （DCPD）, the methods for controlling polymerization rate in the ring opening metathesis of DCPD using Grubbs catalyst were studied. The effects of reaction atmosphere, temperature and catalyst concentration as well as the content of tripbenyl phosphine were thoroughly investigated. It has been found that the Grubbs catalyst was not sensitive to oxygen. At low temperature of 35 ℃, the system still could gel in 10 min, and the monomer conversion could reach nearly 100%. The concentration of catalyst has significant effect on the reaction rate, as the gel time could be extended to 70 rain when molar ratio of catalyst to monomer was reduced to 1/240 000. The content of triphenyl phosphine showed a critical point, above which the system could not gel and the conversion was very low. One the other hand, when triphenyl phosphine content was lower than the critical point, gelation occurred very quickly with nearly 100% monomer conversion. Based on these results, a new route for the RIM of DCPD was successfully designed and applied. Two feeds of monomer mixture were employed, both of which could be independently stored more than 70 min. After mixing these two feeds, the system gels in 14 min and the monomer conversion is 99.5%.

关 键 词：开环移位聚合 双环戊二烯 Grubbs催化剂 反应注塑 

分 类 号：TQ316.2[化学工程—高聚物工业]