茂锆金属催化体系下环烯烃共聚物的制备  

Synthesis of Cycloolefin Copolymers with Zirconium Metallocene Catalytic System

作　　者：王超亚 何广湘[1] 杨索和[1] 靳海波[1] 刘若凡 金玉顺[2] 伍一波[2] Chaoya Wang;Guangxiang He;Suohe Yang;Haibo Jin;Ruofan Liu;Yushun Jin;Yibo Wu(Beijing Key Laboratory of Fuel Cleanliness and Efficient Catalytic Emission Reduction Technology,College of New Materials and Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China;Beijing Key Laboratory of Special Elastomer Composite Materials,College of New Materials and Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China)

机构地区：[1]北京石油化工学院新材料与化工学院燃料清洁化及高效催化减排技术北京重点实验室,北京102617 [2]北京石油化工学院新材料与化工学院特种弹性体复合材料北京重点实验室,北京102617

出　　处：《高分子材料科学与工程》2024年第10期11-20,共10页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(91634101);北京市属高等学校高层次人才引进与培养计划项目(IDHT20180508)。

摘　　要：环烯烃共聚物(COC)具有优良的光学性能,广泛地应用于镜头及液晶显示屏用导光板等方面,因此,研究COC树脂的合成工艺条件是十分必要的。文中采用茂锆金属催化体系以加成聚合方式催化制备了COC树脂,考察了乙烯进气速率、反应时间、铝锆摩尔比(Al/Zr)、茂锆金属催化剂浓度、反应温度对制备COC树脂的影响,并对COC树脂的分子结构使用核磁共振(^(13)C-NMR)、傅里叶变换红外光谱仪(FT-IR)进行了分析,对COC树脂的热性能、光学性能、力学性能使用差示扫描量热仪、热重分析仪、紫外分光光度计和拉伸测试机进行了表征。结果表明,控制通入乙烯流速为3mL/min、反应时间为30min、Al/Zr为1500、茂锆金属催化剂浓度为6×10^(-5)mol/L、反应温度为70℃时,所得COC树脂的玻璃化转变温度(Tg)约为135℃,在可见光范围内透过率约为92%,与市售高端COC树脂产品相近。Cycloolefin copolymer(COC)has excellent optical properties and is widely used in lenses and light guides plates for liquid crystal display.Therefore,it is necessary to study the synthesis process conditions of COC resin.The effects of ethylene gas inlet rate,reaction time,mole ratio of aluminum-zirconium(Al/Zr),concentration of zircon metal catalyst and reaction temperature on the preparation of COC resin were investigated.And the molecular structure of the prepared COC resins was analyzed by ^(13)C-NMR and FT-IR spectra.The thermal,optical and mechanical properties of the prepared COC resins were analyzed by differential scanning calorimetry,thermogravimetric analyzer,UV spectrophotometer,tensile tester.The results show that when the control flow rate of ethylene is 3 mL/min,reaction time is 30 min,mole ratio of Al/Zr is 1500,and the concentration of zirconium metallocene catalyst is 6×10^(-5) mol/L,the reaction temperature is 70℃,the glass transition temperature(Tg)of the obtained COC resin is about 135℃,and its transmittance in visible light range is about 92%,which is similar to that of high-end COC resin products on the market.

关 键 词：环烯烃共聚物 降冰片烯 乙烯 茂锆催化剂 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业]