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

张羽飞; 丁营利; 姜子豪; 黄冬; 吴昊洋; 潘莉; 李悦生

doi:10.11777/j.issn1000-3304.2024.24245

您当前的位置：

首页 >

文章列表页 >

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

研究论文 | 更新时间：2025-02-27

- 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
- 高分子学报 2025年56卷第3期页码：431-441
- 作者机构：
  
  天津大学材料科学与工程学院天津 300350
- 作者简介：
  
  E-mail: lilypan@tju.edu.cn
- 基金信息：
  
  国家自然科学基金面上项目(基金号 52373013)
- DOI：10.11777/j.issn1000-3304.2024.24245
  中图分类号：
- CSTR：32057.14.GFZXB.2024.7320
- 收稿日期：2024-09-26，
  
  录用日期：2024-11-05，
  
  网络出版日期：2025-01-26，
  
  纸质出版日期：2025-03-20
- 稿件说明：
移动端阅览
张羽飞, 丁营利, 姜子豪, 黄冬, 吴昊洋, 潘莉, 李悦生. 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. 高分子学报, 2025, 56(3), 431-441

Zhang, Y. F.; Ding, Y. L.; Jiang, Z. H.; Huang, D.; Wu, H. Y.; Pan, L.; Li, Y. S. Synthesis and properties of highly transparent cyclic olefin copolymers from dual-selective catalysts. Acta Polymerica Sinica, 2025, 56(3), 431-441
张羽飞, 丁营利, 姜子豪, 黄冬, 吴昊洋, 潘莉, 李悦生. 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. 高分子学报, 2025, 56(3), 431-441 DOI： 10.11777/j.issn1000-3304.2024.24245. CSTR： 32057.14.GFZXB.2024.7320.

Zhang, Y. F.; Ding, Y. L.; Jiang, Z. H.; Huang, D.; Wu, H. Y.; Pan, L.; Li, Y. S. Synthesis and properties of highly transparent cyclic olefin copolymers from dual-selective catalysts. Acta Polymerica Sinica, 2025, 56(3), 431-441 DOI： 10.11777/j.issn1000-3304.2024.24245. CSTR： 32057.14.GFZXB.2024.7320.

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.

Abstract

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

Keywords

references

许蔷 , 高玉李 , 王科峰 , 义建军 . 环烯烃共聚物研究进展 . 高分子通报 , 2019 ( 1 ), 64 - 74 . doi: 10.14028/j.cnki.1003-3726.2019.01.008 http://dx.doi.org/10.14028/j.cnki.1003-3726.2019.01.008

曲树璋 , 王伟 . 环烯烃共聚物材料应用的研究进展 . 石油化工 , 2022 , 51 ( 4 ), 477 - 484 . doi: 10.3969/j.issn.1000-8144.2022.04.015 http://dx.doi.org/10.3969/j.issn.1000-8144.2022.04.015

Limam . M; Tighzert L . Sorption of organic solvents by packaging materials : polyethylene terephthalate and TOPAS. Polym. Test. , 2005 , 24 , 395 - 402 . doi: 10.1016/j.polymertesting.2004.09.004 http://dx.doi.org/10.1016/j.polymertesting.2004.09.004

李贵生 , 张丕生 . 环烯烃材料应用于电容膜的研究进展 . 河南化工 , 2023 , 40 ( 2 ), 8 - 11 .

Kaminsky W. ; Bark A. ; Arndt M. New polymers by homogenous zirconocene/aluminoxane catalysts . Makromol. Chem. Macromol. Symp. , 1991 , 47 ( 1 ), 83 - 93 . doi: 10.1002/masy.19910470108 http://dx.doi.org/10.1002/masy.19910470108

Wang W. ; Qu S. Z. ; Li X. W. ; Chen J. Comparison of ethylene copolymerization with norbornene and 5-norbornene-2-methanol by using Ph2C(cp)(flu)ZrCl2/MAO. Macromol. Chem. Phys. , 2023 , 224 , 2300005 . doi: 10.1002/macp.202300005 http://dx.doi.org/10.1002/macp.202300005

Donner M. ; Fernandes M. ; Kaminsky W. Synthesis of copolymers with sterically hindered and polar monomers . Macromol. Symp. , 2006 , 236 ( 1 ), 193 - 202 . doi: 10.1002/masy.200690055 http://dx.doi.org/10.1002/masy.200690055

Goodall B. L. ; McIntosh , L. H. III , Rhodes L. F. New catalysts for the polymerization of cyclic olefins . Macromol. Symp. , 1995 , 89 ( 1 ), 421 - 432 . doi: 10.1002/masy.19950890139 http://dx.doi.org/10.1002/masy.19950890139

Tritto I. ; Boggioni L. ; Jansen J. C. ; Thorshaug K. ; Sacchi M. C. ; Ferro D. R. Ethylene-norbornene copolymers from metallocene-based catalysts: microstructure at tetrad level and reactivity ratios . Macromolecules , 2002 , 35 ( 3 ), 616 - 623 . doi: 10.1021/ma011365m http://dx.doi.org/10.1021/ma011365m

Tritto I. ; Marestin C. ; Boggioni L. ; Sacchi M. C. ; Brintzinger H. H. ; Ferro D. R. Stereoregular and stereoirregular alternating ethylene-norbornene copolymers . Macromolecules , 2001 , 34 ( 17 ), 5770 - 5777 . doi: 10.1021/ma010122r http://dx.doi.org/10.1021/ma010122r

McKnight A. L. ; Waymouth R. M. Ethylene/norbornene copolymerizations with titanium CpA catalysts . Macromolecules , 1999 , 32 ( 9 ), 2816 - 2825 . doi: 10.1021/ma981365v http://dx.doi.org/10.1021/ma981365v

Tang L. M. ; Hu T. ; Bo Y. J. ; Li Y. S. ; Hu N. H. Titanium complexes bearing aromatic-substituted β -enaminoketonato ligands: syntheses, structure and olefin polymerization behavior . J. Organomet. Chem. , 2005 , 690 ( 13 ), 3125 - 3133 . doi: 10.1016/j.jorganchem.2005.04.002 http://dx.doi.org/10.1016/j.jorganchem.2005.04.002

Pan L. ; Hong M. ; Liu J. Y. ; Ye W. P. ; Li Y. S. Living copolymerization of ethylene with dicyclopentadiene using titanium catalyst: formation of well-defined polyethylene-block-poly(ethylene- co -dicyclopentadiene)s and their transformation into novel polyolefin-block-(functional polyolefin)s . Macromolecules , 2009 , 42 ( 13 ), 4391 - 4393 . doi: 10.1021/ma9008548 http://dx.doi.org/10.1021/ma9008548

Gao H. Y. ; Liu Y. ; Li G. L. ; Xiao Z. F. ; Liang G. D. ; Wu Q. Catalytic synthesis of polyethylene-block-polynorbornene copolymers using a living polymerization nickel catalyst . Polym. Chem. , 2014 , 5 , 6012 - 6018 . doi: 10.1039/c4py00701h http://dx.doi.org/10.1039/c4py00701h

Gao H. ; Chen S. T. ; Du B. ; Dai Z. Y. ; Lu X. ; Zhang K. Y. ; Pan L. ; Li Y. ; Li Y. S. Cyclic olefin copolymers containing both linear polyethylene and poly(ethylene- co -norbornene) segments prepared from chain shuttling copolymerization of ethylene and norbornene . Polym. Chem. , 2022 , 13 ( 2 ), 245 - 257 . doi: 10.1039/d1py01251g http://dx.doi.org/10.1039/d1py01251g

刘炬阳 , 高欢 , 王菲 , 黄冬 , 潘莉 , 李悦生 . 链穿梭共聚合制备环烯烃多嵌段共聚物 . 高分子学报 , 2023 , 54 ( 11 ), 1708 - 1719 .

Qiu N. T. ; Sun Z. Q. ; Yu F. ; Wang K. Q. ; Long C. J. ; Dong Z. ; Li Y. Z. ; Cao K. ; Chen Z. R. Chain shuttling polymerization for cycloolefin block copolymers: from engineering plastics to thermoplastic elastomers . Macromolecules , 2024 , 57 ( 12 ), 5729 - 5738 . doi: 10.1021/acs.macromol.4c01029 http://dx.doi.org/10.1021/acs.macromol.4c01029

Wang F. ; Huang D. ; Gao H. ; Wang F. ; Pan L. ; Li Y. S. Synthesis of bimodal distributed cyclic olefin copolymers with improved tensile properties . Chinese J. Chem. , 2022 , 40 ( 16 ), 1931 - 1938 . doi: 10.1002/cjoc.202200186 http://dx.doi.org/10.1002/cjoc.202200186

Kiesewetter J. ; Arikan B. ; Kaminsky W. Copolymerization of ethene with norbornene using palladium(II) α -diimine catalysts: influence of feed composition, polymerization temperature, and ligand structure on copolymer properties and microstructure . Polymer , 2006 , 47 ( 10 ), 3302 - 3314 . doi: 10.1016/j.polymer.2006.03.020 http://dx.doi.org/10.1016/j.polymer.2006.03.020

Kaminsky W. ; Bark A. Copolymerization of ethene and dimethanooctahydronaphthalene with aluminoxane containing catalysts . Polym. Int. , 1992 , 28 ( 3 ), 251 - 253 . doi: 10.1002/pi.4990280312 http://dx.doi.org/10.1002/pi.4990280312

Zhao W. Z. ; Nomura K. Copolymerizations of norbornene and tetracyclododecene with α‍ -olefins by half-titanocene catalysts: efficient synthesis of highly transparent, thermal resistance polymers . Macromolecules , 2016 , 49 ( 1 ), 59 - 70 . doi: 10.1021/acs.macromol.5b02176 http://dx.doi.org/10.1021/acs.macromol.5b02176

Huang D. ; Lu X. ; Zhang K. Y. ; Wang Y. F. ; Wang F. ; Gao H. ; Ding Y. L. ; Pan L. ; Li Y. ; Li Y. S. Ultra-high-molecular weight cyclic olefin copolymers with excellent all-round performance prepared via highly effective quasi-living copolymerization . Chem. Eng. J. , 2024 , 494 , 153256 . doi: 10.1016/j.cej.2024.153256 http://dx.doi.org/10.1016/j.cej.2024.153256

Yuan H. B. ; Kida T. ; Kim H. ; Tanaka R. ; Cai Z. G. ; Nakayama Y. ; Shiono T. Synthesis and properties of gradient copolymers composed of norbornene and higher α‍-olefins using an ansa-fluorenylamidodimethyltitanium- [Ph 3 C ] [B(C 6 F 5 )4 ] systemcatalyst. Macromolecules , 2020 , 53 ( 11 ), 4323 - 4329 .

Kim E. C. ; Kim M. J. ; Thi Ho L. N. ; Lee W. ; Ka J. W. ; Kim D. G. ; Shin T. J. ; Huh K. M. ; Park S. ; Kim Y. S. Synthesis of vinyl-addition polynorbornene copolymers bearing pendant n-alkyl chains and systematic investigation of their properties . Macromolecules , 2021 , 54 ( 14 ), 6762 - 6771 . doi: 10.1021/acs.macromol.1c00858 http://dx.doi.org/10.1021/acs.macromol.1c00858

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

链穿梭共聚合制备环烯烃多嵌段共聚物