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Synthesis of novel cyclic olefin copolymer (COC) with high performance via effective copolymerization of ethylene with bulky cyclic olefin

机译:通过乙烯与大体积环烯烃的有效共聚合成高性能的新型环烯烃共聚物(COC)

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摘要

Novel cyclic olefin copolymer (COC) with high glass transition temperature, good mechanical performance, high transparency, and excellent film forming ability has been achieved in this work by effective copolymerization of ethylene and exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l,4- methanoanthracene (HBMN). This bulky cyclic olefin comonomer can be simply prepared in good yield via Diels-Alder reaction. By utilizing constrained geometry catalyst (CGC) activated with Al(~iBu) _3/[Ph _3C][B(C _6F _5) _4], ethylene/HBMN copolymer can be obtained with excellent production, high molecular weight, and a wide range of HBMN incorporation. ~(13)C NMR (DEPT) spectra reveal alternating ethylene-HBMN sequence can be detected at high HBMN incorporation. The glass transition temperature (T _g) of resulted copolymer enhances with increasing HBMN incorporation. A high T _g up to 207.0 °C is attainable at low comonomer incorporation of 30.4 mol %, which is 61 °C higher than that of commercial norbornene (NB)-derived COC (54 mol %). The tensile test indicates that the ethylene/HBMN copolymer has good mechanical performance which is more flexible than ethylene/NB copolymer and the previously reported COC even at a higher T _g level.
机译:通过有效地乙烯与exo-1,4,4a,9,9a,10的有效共聚,获得了具有高玻璃化转变温度,良好的机械性能,高透明性和优异的成膜能力的新型环状烯烃共聚物(COC)。 -六氢-9,10(1',2')-苯并-1,4-甲基蒽(HBMN)。可以通过Diels-Alder反应以高收率简单地制备这种大体积的环状烯烃共聚单体。通过利用以Al(〜iBu)_3 / [Ph _3C] [B(C _6F _5)_4]活化的约束几何催化剂(CGC),可以生产出具有优异产量,高分子量和宽范围的乙烯/ HBMN共聚物。 HBMN合并。 〜(13)C NMR(DEPT)光谱显示在高HBMN掺入下可以检测到交替的乙烯-HBMN序列。所得共聚物的玻璃化转变温度(T_g)随着HBMN掺入量的增加而提高。在低共聚单体含量为30.4 mol%的情况下,可以获得高达207.0°C的高T_g,这比市售降冰片烯(NB)衍生的COC(54 mol%)高61°C。拉伸试验表明,乙烯/ HBMN共聚物具有良好的机械性能,甚至在较高的T_g水平下也比乙烯/ NB共聚物和先前报道的COC具有更大的柔韧性。

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