Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl6-based Catalyst System  

作　　者：Yi-Ran Zhang Ji-Xing Yang Li Pan Yue-Sheng Li 

机构地区：[1]Tianjin Key Laboratory of Composite and Functional Materials,School of Materials Science and Engineering,Tianjin University,Tianjin 300350,China [2]Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300072,China

出　　处：《Chinese Journal of Polymer Science》2018年第2期214-221,共8页高分子科学（英文版）

基　　金：financial support by the National Natural Science Foundation of China(Nos.21234006 and U1510124)

摘　　要：Cyclic olefin polymers（COPs） with high glass transition temperature, high transparency（higher than 80%） in the visible light range, excellent thermal stability and outstanding mechanical properties have been synthesized by effective ring opening metathesis polymerization（ROMP） of exo-1,4,4 a,9,9 a,10-hexahydro-9,10（1′,2′）-benzeno-l,4-methanoanthracene（HBM） and dicyclopentadiene（DCPD） or norbornene（NBE） using WCl6/i-Bu3Al/ethanol/1-hexene catalyst system, followed by hydrogenation of double bonds. 1-Hexene acted as a molecular weight controller in the polymerization reaction, tuning the number-average molecular weight（Mn） of P-HBM from 5.8 × 10^4 to 41.1 × 10^4. The monomer composition and thermal properties of the copolymers were characterized by nuclear magnetic resonance（NMR）, differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA）. The saturated polymers exhibited high decomposition temperatures（Td） around 340 ℃ and glass transition temperatures（Tg） in the range from 117.5 ℃ to 219.7 ℃. What is more, tensile tests indicated that the mechanical properties of the COPs could be effectively tuned in a wide range by introducing varying amount of small cyclic olefin such as DCPD or NBE.Cyclic olefin polymers（COPs） with high glass transition temperature, high transparency（higher than 80%） in the visible light range, excellent thermal stability and outstanding mechanical properties have been synthesized by effective ring opening metathesis polymerization（ROMP） of exo-1,4,4 a,9,9 a,10-hexahydro-9,10（1′,2′）-benzeno-l,4-methanoanthracene（HBM） and dicyclopentadiene（DCPD） or norbornene（NBE） using WCl6/i-Bu3Al/ethanol/1-hexene catalyst system, followed by hydrogenation of double bonds. 1-Hexene acted as a molecular weight controller in the polymerization reaction, tuning the number-average molecular weight（Mn） of P-HBM from 5.8 × 10^4 to 41.1 × 10^4. The monomer composition and thermal properties of the copolymers were characterized by nuclear magnetic resonance（NMR）, differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA）. The saturated polymers exhibited high decomposition temperatures（Td） around 340 ℃ and glass transition temperatures（Tg） in the range from 117.5 ℃ to 219.7 ℃. What is more, tensile tests indicated that the mechanical properties of the COPs could be effectively tuned in a wide range by introducing varying amount of small cyclic olefin such as DCPD or NBE.

关 键 词：Ring-opening metathesis polymerization HYDROGENATION Cyclic olefin polymers Glass transition temperature Mechanical properties 

分 类 号：O632.12[理学—高分子化学] O643.36[理学—化学]