双催化剂体系制备高透明环烯烃共聚物及聚合物性能研究  

Synthesis and Properties of Highly Transparent Cyclic Olefin Copolymers from Dual-Selective Catalysts

作　　者：张羽飞 丁营利 姜子豪 黄冬 吴昊洋 潘莉 李悦生[1] Yu-fei Zhang;Ying-li Ding;Zi-hao Jiang;Dong Huang;Hao-yang Wu;Li Pan;Yue-sheng Li(School of Materials Science and Engineering,Tianjin University,Tianjin 300350)

机构地区：[1]天津大学材料科学与工程学院,天津300350

出　　处：《高分子学报》2025年第3期431-441,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金面上项目(基金号52373013)资助。

摘　　要：乙烯/二甲桥八氢萘共聚物(E/TCD)是一种具有高附加值的环烯烃共聚物(cyclic olefin copolymer,COC),但TCD单体价格十分昂贵且尚未实现国产化,导致相关共聚物产品价格过高.本研究中,我们优选了2种可分别得到具有不同TCD插入率、不同分子量的E/TCD共聚物选择性茂金属催化剂进行复合制备了一系列组成不同E/TCD共聚物混合物.通过改变两催化剂比例等,有效调控TCD平均插入率和聚合物分子量,进而实现共聚物热性能和力学性能的高效调节.研究发现,两催化剂比例为4:1时,所得共聚物的综合力学性能最优,拉伸强度为54.6 MPa,断裂伸长率提升为5.0%,相比于高插入率、高分子量的E/TCD共聚物,利用更低的TCD插入率实现了更优的综合力学性能.为了进一步提高其耐热性和韧性,本研究引入烷基降冰片烯作为第三单体,采用双催化剂体系制备了三元环烯烃共聚物.柔性烷基侧链的引入也可使聚合物的韧性得到明显提高.通过调节共聚物组成与结构,在保持E/TCD共聚物优秀的光学性能的同时降低TCD单体插入率,实现了该类COC性能优化并有效降低成本.Ethylene/tetracyclododecene(E/TCD)copolymers are high-value added cyclic olefin copolymers(COCs).However,the high price of TCD restricts the production and application of E/TCD copolymers with high TCD incorporation.In this study,copolymers with different TCD incorporations and molecular weights were prepared by two selective metallocene catalysts.A series of E/TCD copolymers were prepared with this dual catalyst system by adjusting the ratio of the two catalysts.Apparent TCD incorporation and polymer molecular weight could be effectively controlled and adjusted,thereby achieving satisfactory glass transition temperature and mechanical properties of the obtained COCs.When the ratio of two catalysts was 4:1,the obtained COC exhibited optimal tensile properties,with a tensile strength of 54.6 MPa and an elongation at break of 5.0%.Compared with E/TCD copolymers with high TCD incorporation and high-molecular weight,better tensile properties were achieved.To further improve heat resistance and toughness of the E/TCD copolymer,norbornene bearing soft alkyl tails was introduced as the third monomer to give E/TCD/nC-NB terpolymers by using the dual-catalyst system.The introduction of flexible alkyl side chains could improve the toughness of the polymer,with a 48%increase in elongation at break compared with E/TCD copolymer.By adjusting the composition and structure of the copolymer,the excellent optical properties of the E/TCD copolymer were maintained while reducing the incorporation of the TCD monomer,which realized the optimization of the performance of COC and effectively reduced the cost.

关 键 词：双催化剂体系 环烯烃共聚物 二甲桥八氢萘 烷基降冰片烯 

分 类 号：O631.5[理学—高分子化学] O643.36[理学—化学]