环烯烃开环易位聚合物的合成  

Synthesis of ring-opening metathesis polymer from cycloolefin

作　　者：于明泉 张衡臣 杨雪娇 苑任旭 刘阳 方岩雄[1] Yu Mingquan;Zhang Hengchen;Yang Xuejiao;Yuan Renxu;Liu Yang;Fang Yanxion(School of Chemical Engineering and Light Industry,Guangdong University of Technology,Guangzhou 510000,Guangdong,China;Guangdong Xinhuayue Petrochemical Group Co.,Ltd.,Maoming 525000,Guangdong,China;Guangdong Provincial Key Laboratory of Optical Enterprises,Maoming 525000,Guangdong,China;Guangdong Provincial Key Laboratory of Port Safety Intelligent Testing,Dongguan 523000,Guangdong,China)

机构地区：[1]广东工业大学轻工化工学院,广东广州510000 [2]广东新华粤石化集团股份公司,广东茂名525000 [3]广东省光学品企业重点实验室,广东茂名525000 [4]广东省口岸安全智能化检测重点实验室,广东东莞523000

出　　处：《工业催化》2024年第3期75-79,共5页Industrial Catalysis

基　　金：广东省光学品企业重点实验室基金。

摘　　要：采用MoCl_(5)为核心的齐格勒-纳塔催化剂合成降冰片烯-四环十二烯的开环易位聚合物,实现稳定的100%单体转化率,凝胶率0%。并采用Al_(2)O_(3)负载的Ru催化剂和SiO 2/Al_(2)O_(3)负载的Ni金属催化剂对相同的降冰片烯-四环十二烯开环易位聚合物进行非均相加氢,可实现100%的加氢率,且简单过滤即可将催化剂与聚合物溶液完全分离。两种加氢催化剂的产品具有不同的性质,Ni负载催化剂最佳反应条件:催化剂含量10%、反应温度190℃、初始氢气压力4 MPa、反应时间2 h,加氢产物的熔融指数76 g·min^(-1),玻璃化转变温度126℃;Ru负载催化剂最佳反应条件:催化剂含量2%、反应温度180℃、初始氢气压力4 MPa、反应时间2 h,加氢产物的熔融指数10 g·min^(-1),玻璃化转变温度131℃。The ring-opening metathesis polymer of norbornene-tetracyclododecene was synthesized by using the Ziegler-Natta catalyst with MoCl_(5) as the core,and a stable monomer conversion of 100% and gel fraction of 0%were achieved.The polymers were heterogeneously hydrogenated by using Al_(2)O_(3) supported Ru metal catalyst and SiO_(2)/Al_(2)O_(3) supported Ni metal catalyst.A 100% hydrogenation efficiency could be achieved,and the catalyst could be completely separated from the polymer solution by simple filtration.The products of the two hydrogenation catalysts have different properties.The melt flow index of the hydrogenation product of Ni catalyst is more than 76 g·min^(-1) and the glass transition temperature is 126℃when mass of total solids feeding is 10%of polymer weight,190℃,4 MPa pressure of initial hydrogen and 2 h of reaction time,while the melt flow index of the hydrogenation product of Ru catalyst is 10 g·min^(-1) and the glass transition temperature is 131℃when mass of total solids feeding is 2%of polymer weight,180℃,4 MPa pressure of initial hydrogen and 2 h of reaction time.

关 键 词：精细化学工程 开环易位聚合 非均相加氢 环烯烃 环烯烃聚合物(COP) 氯化钼 钌 镍 

分 类 号：TQ426.94[化学工程] TQ316.3