长链支化聚烯烃弹性体的合成、结构与性能研究

刘明; 杨小俊; 陈风涛; 董金勇

doi:10.11777/j.issn1000-3304.2025.25053

您当前的位置：

首页 >

文章列表页 >

长链支化聚烯烃弹性体的合成、结构与性能研究

研究论文 | 更新时间：2025-04-28

- 长链支化聚烯烃弹性体的合成、结构与性能研究
- Synthesis, Structures and Properties of Long-chain-branched Polyolefin Elastomers
- 高分子学报 2025年页码：1-13
- 作者机构：
  
  1.武汉工程大学化工与制药学院绿色化工过程教育部重点实验室武汉 430205
  2.中国科学院化学研究所工程塑料重点实验室北京 100190
  3.中国科学院大学北京 100049
- 作者简介：
  
  E-mail: yangxiaojun@wit.edu.cn
  chenfengtao@iccas.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52403018;52173013);52373015┫;中国科学院关键核心技术攻坚先导专项(XDC0270200)
- DOI：10.11777/j.issn1000-3304.2025.25053
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7395
- 收稿日期：2025-02-28，
  
  录用日期：2025-04-03，
  
  网络出版日期：2025-04-28，
- 稿件说明：
移动端阅览
刘明, 杨小俊, 陈风涛, 董金勇. 长链支化聚烯烃弹性体的合成、结构与性能研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25053

Liu, M.; Yang, X. J.; Chen, F. T.; Dong, J. Y. Synthesis, structures and properties of long-chain-branched polyolefin elastomers. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25053
刘明, 杨小俊, 陈风涛, 董金勇. 长链支化聚烯烃弹性体的合成、结构与性能研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25053 DOI： CSTR： 32057.14.GFZXB.2025.7395.

Liu, M.; Yang, X. J.; Chen, F. T.; Dong, J. Y. Synthesis, structures and properties of long-chain-branched polyolefin elastomers. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25053 DOI： CSTR： 32057.14.GFZXB.2025.7395.

摘要

聚烯烃弹性体(POE)作为高端的聚乙烯树脂，具有高抗冲击性、高弹性、高柔韧性以及与其他聚烯烃材料的优异相容性，但由于其本身缺乏长链支化结构，导致其在熔体加工过程中仍存在不足. 本研究采用两种策略，分别将

-烯烃基甲基二氯硅烷和非共轭

-双烯烃作为长链支化功能助剂，向POE分子链中引入H型长链支化结构，合成得到了同时具备高熔体强度、高透光率和优良力学性能的新型长链支化聚烯烃弹性体(LCB-POE). POE样品的傅里叶红外光谱(FITR)、凝胶渗透色谱(GPC)和熔体流变测试结果均证明了长链支化结构的存在. 对比两组样品的流变测试结果可知，使用

-烯烃基甲基二氯硅烷作为LCB助剂具有更高的长链支化结构生成效率.

Abstract

As a premium polyethylene resin

polyolefin elastomer (POE) demonstrates extensive applications in automotive components

photovoltaic encapsulation films

and wire/cable insulation systems owing to its remarkable impact resistance

superior elasticity

exceptional flexibility

and outstanding compatibility with other polyolefin materials. However

its inherent deficiency in long-chain-branching (LCB) structures results in multiple processing limitations during melt processing

significantly constraining broader industrial implementation. In this paper

two strategies were adopted to introduce H-shape LCB structures into the POE molecular chain by employing

-alkenylmethyldichlorosilane (hex-DCS) and nonconjugated

-diolefin (1

9-DD) as LCB functional additives

respectively. A new type of long-chain-branching polyolefin elastomer (LCB-POE) with both high melt strength

high light transmittance

and significantly enhanced mechanical properties was synthesized. Comprehensive characterization including Fourier transform infrared spectroscopy (FTIR)

gel permeation chromatography (GPC)

and melt rheological analysis conclusively demonstrated the successful incorporation of LCB structures

with the degree of LCB increasing proportionally to the concentration of LCB agents. Comparative rheological analysis revealed distinct structural evolution pathways: non-conjugated

-diolefins as LCB agents initially induced pendant short-chain branches on POE backbones at low concentrations

failing to transition into LC

B architectures. In contrast

-alkenylmethyldichlorosilane exhibited superior LCB formation efficiency

achieving effective long-chain branching at equivalent low loading levels through optimized topological connectivity.

关键词

Keywords

references

黄格省 , 师晓玉 , 丁文娟 , 王春娇 , 慕彦君 , 侯雨璇 . 光伏电池封装胶膜材料发展现状与前景分析 . 化工进展 , 2023 , 42 ( 10 ), 5037 - 5046 .

李伯耿 , 张明轩 , 刘伟峰 , 王文俊 . 聚烯烃类弹性体: 现状与进展 . 化工进展 , 2017 , 36 ( 9 ), 3135 - 3144 .

马师 . 聚烯烃弹性体POE工艺开发的难点分析 . 化工管理 , 2024 ( 35 ), 158 - 160 .

乔泽爽 , 邹发生 , 宋文波 , 白红伟 , 傅强 . 基于结晶调控制备低收缩聚丙烯 . 高分子学报 , 2023 , 54 ( 8 ), 1186 - 1195 . doi: 10.11777/j.issn1000-3304.2022.22450 http://dx.doi.org/10.11777/j.issn1000-3304.2022.22450

Gloor P. E. ; Tang Y. ; Kostanska A. E. ; Hamielec A. E. Chemical modification of polyolefins by free radical mechanisms: a modelling and experimental study of simultaneous random scission, branching and crosslinking . Polymer , 1994 , 35 ( 5 ), 1012 - 1030 . doi: 10.1016/0032-3861(94)90946-6 http://dx.doi.org/10.1016/0032-3861(94)90946-6

Karimkhani V. ; Afshar-Taromi F. ; Pourmahdian S. ; Stadler F. J. Revisiting the long-chain branch formation mechanism in metallocene catalyzed polyethylenes . Polym. Chem. , 2013 , 4 ( 13 ), 3774 - 3790 . doi: 10.1039/c3py00319a http://dx.doi.org/10.1039/c3py00319a

Kolodka E. ; Wang W. J. ; Zhu S. P. ; Hamielec A. E. Copolymerization of propylene with poly(ethylene- co -propylene) macromonomer and branch chain-length dependence of rheological properties . Macromolecules , 2002 , 35 ( 27 ), 10062 - 10070 . doi: 10.1021/ma021171m http://dx.doi.org/10.1021/ma021171m

Liu Y. ; Qin Y. W. ; Dong J. Y. Assessing 1,9-decadiene/propylene copolymerization with Ziegler-Natta catalysts to long-chain-branched polypropylene . Ind. Eng. Chem. Res. , 2020 , 59 ( 26 ), 12038 - 12047 . doi: 10.1021/acs.iecr.0c02087 http://dx.doi.org/10.1021/acs.iecr.0c02087

Majumdar B. ; Keskkula H. ; Paul D. R. Morphology development in toughened aliphatic polyamides . Polymer , 1994 , 35 ( 7 ), 1386 - 1398 . doi: 10.1016/0032-3861(94)90338-7 http://dx.doi.org/10.1016/0032-3861(94)90338-7

Moad G. The synthesis of polyolefin graft copolymers by reactive extrusion . Prog. Polym. Sci. , 1999 , 24 ( 1 ), 81 - 142 . doi: 10.1016/s0079-6700(98)00017-3 http://dx.doi.org/10.1016/s0079-6700(98)00017-3

Rahmatiyan S. ; Bahri-Laleh N. ; Hanifpour A. ; Nekoomanesh-Haghighi M. Different behaviors of metallocene and Ziegler-Natta catalysts in ethylene/1,5-hexadiene copolymerization . Polym. Int. , 2019 , 68 ( 1 ), 94 - 101 . doi: 10.1002/pi.5700 http://dx.doi.org/10.1002/pi.5700

Wang W. J. ; Yan D. J. ; Charpentier P. A. ; Zhu S. P. ; Hamielec A. E. ; Sayer B. G. Long chain branching in ethylene polymerization using constrained geometry metallocene catalyst . Macromol. Chem. Phys. , 1998 , 199 ( 11 ), 2409 - 2416 . doi: 10.1002/macp.1998.021991107 http://dx.doi.org/10.1002/macp.1998.021991107

Xu L. ; Nakajima H. ; Manias E. ; Krishnamoorti R. Tailored nanocomposites of polypropylene with layered silicates . Macromolecules , 2009 , 42 ( 11 ), 3795 - 3803 . doi: 10.1021/ma9002853 http://dx.doi.org/10.1021/ma9002853

Yang Q. ; Jensen M. D. ; McDaniel M. P. Alternative view of long chain branch formation by metallocene catalysts . Macromolecules , 2010 , 43 ( 21 ), 8836 - 8852 . doi: 10.1021/ma101469j http://dx.doi.org/10.1021/ma101469j

Yang X. ; Zhao H. ; Li C. Y. ; Zhao X. D. ; Yang J. M. ; Wang X. Improved wide-temperature-range insulation properties of block polypropylene by UV-irradiated cografting of maleic anhydride and 4- tert -butylstyrene . ACS Appl. Polym. Mater. , 2023 , 5 ( 1 ), 247 - 258 . doi: 10.1021/acsapm.2c01476 http://dx.doi.org/10.1021/acsapm.2c01476

Ye Z. B. ; AlObaidi F. ; Zhu S. P. Synthesis and rheological properties of long-chain-branched isotactic polypropylenes prepared by copolymerization of propylene and nonconjugated dienes . Ind. Eng. Chem. Res. , 2004 , 43 ( 11 ), 2860 - 2870 . doi: 10.1021/ie0499660 http://dx.doi.org/10.1021/ie0499660

Zhang M. ; Colby R. H. ; Milner S. T. ; Chung M. T. C. ; Huang T. Z. ; deGroot W. Synthesis and characterization of maleic anhydride grafted polypropylene with a well-defined molecular structure . Macromolecules , 2013 , 46 ( 11 ), 4313 - 4323 . doi: 10.1021/ma4006632 http://dx.doi.org/10.1021/ma4006632

Li K. ; Zhou H. S. ; Qin Y. W. ; Zhao Y. ; Wang D. J. ; Dong J. Y. ω -Alkenylmethyldichlorosilane-assisted propylene polymerization with Ziegler-Natta catalyst to long chain-branched polypropylene . Polymer , 2020 , 202 , 122737 . doi: 10.1016/j.polymer.2020.122737 http://dx.doi.org/10.1016/j.polymer.2020.122737

Liu X. M. ; Qin Y. W. ; Zhao S. M. ; Dong J. Y. In situ promotion of long-chain branching in polyethylene from ziegler-natta catalysts . ACS Appl. Polym. Mater. , 2021 , 3 ( 12 ), 6455 - 6467 . doi: 10.1021/acsapm.1c01197 http://dx.doi.org/10.1021/acsapm.1c01197

Wang Y. J. ; Qin Y. W. ; Dong J. Y. Trouble-free combination of ω-alkenylmethyldichlorosilane copolymerization-hydrolysis chemistry and metallocene catalyst system for highly effective and efficient direct synthesis of long-chain-branched polypropylene . Polymer , 2022 , 259 , 125327 . doi: 10.1016/j.polymer.2022.125327 http://dx.doi.org/10.1016/j.polymer.2022.125327

Zhang B. Y. ; Chen F. T. ; Dong J. Y. Industrial synthesis of linear low-density polyethylene with H-shape long-chain-branching structures using ziegler-natta catalysts . Macromol. React. Eng. , 2024 , 2400044 . doi: 10.1002/mren.202400044 http://dx.doi.org/10.1002/mren.202400044

Zhang Z. J. ; Yang K. ; Li J. Y. ; Dong J. Y. Simultaneous promotion of the mechanical flexibility and dielectric strength of impact polypropylene copolymers containing multifold H-shape long-chain-branching structures for recyclable power cable insulation application . ACS Appl. Polym. Mater. , 2024 , 6 ( 4 ), 2210 - 2222 . doi: 10.1021/acsapm.3c02755 http://dx.doi.org/10.1021/acsapm.3c02755

Zhang Z. J. ; Yang K. ; Li J. Y. ; Jing Z. H. ; Qin Y. W. ; Dong J. Y. Impact polypropylene copolymers containing multifold H-shape long-chain-branching structures: synthesis and properties . Polymer , 2022 , 252 , 124942 . doi: 10.1016/j.polymer.2022.124942 http://dx.doi.org/10.1016/j.polymer.2022.124942

刘秀明 , 杜杰 , 霍金兰 , 秦亚伟 , 赵松美 , 董金勇 . 基于Ziegler-Natta催化剂和 ω -烯烃基甲基二氯硅烷共聚-水解化学制备长链支化高密度聚乙烯 . 高分子学报 , 2021 , 52 ( 11 ), 1488 - 1497 .

张志箭 , 王莉 , 祖凤华 , 洪柳婷 , 秦亚伟 , 董金勇 . α -烯烃基甲基二氯硅烷调控丙烯多相共聚制备高熔体强度高抗冲聚丙烯 . 高分子学报 , 2020 , 51 ( 7 ), 744 - 753 . doi: 10.11777/j.issn1000-3304.2020.20017 http://dx.doi.org/10.11777/j.issn1000-3304.2020.20017

Wang W. ; Shao C. G. ; Zheng L. R. ; Wang B. ; Pan L. ; Ma G. Q. ; Li Y. S. ; Wang Y. M. ; Liu C. T. ; Ma Z. Stretching-induced phase transition of the butene-1/ethylene random copolymer: orientation and kinetics . J. Polym. Sci. Part B Polym. Phys. , 2019 , 57 ( 2 ), 116 - 126 . doi: 10.1002/polb.24764 http://dx.doi.org/10.1002/polb.24764

Klosin J. ; Kruper W. J. ; Nickias P. N. ; Roof G. R. ; De Waele P. ; Abboud K. A. Heteroatom-substituted constrained-geometry complexes. Dramatic substituent effect on catalyst efficiency and polymer molecular weight . Organometallics , 2001 , 20 ( 13 ), 2663 - 2665 . doi: 10.1021/om010016d http://dx.doi.org/10.1021/om010016d

Kimura K. ; Yuasa S. ; Maru Y. Carbon-13 nuclear magnetic resonance study of ethylene-1-octene and ethylene-4-methyl-1-pentene copolymers . Polymer , 1984 , 25 ( 4 ), 441 - 446 . doi: 10.1016/0032-3861(84)90199-x http://dx.doi.org/10.1016/0032-3861(84)90199-x

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

暂无数据