Synthesis and Performance Study of High-molecular-weight Amide End-functionalized <italic style="font-style: italic">cis</italic>-Polybutadiene Rubber

Xiu-hui Zhang; Jing Dong; Wei-tian Li; Xu Li; Feng Wang; Heng Liu; Xue-quan Zhang

doi:10.11777/j.issn1000-3304.2025.25104

您当前的位置：

首页 >

文章列表页 >

Synthesis and Performance Study of High-molecular-weight Amide End-functionalized cis-Polybutadiene Rubber

Research Article | 更新时间：2025-08-28

- Synthesis and Performance Study of High-molecular-weight Amide End-functionalized cis-Polybutadiene Rubber
- Acta Polymerica Sinica Vol. 56, Issue 9, Pages: 1633-1643(2025)
- 作者机构：
  
  1.青岛科技大学高分子科学与工程学院橡塑材料与工程教育部重点实验室山东省橡胶材料科学与工程高校实验室青岛 266000
  2.中国石油石油化工研究院兰州化工研究中心兰州 730060
- 作者简介：
  
  Feng Wang, E-mail: fengwang@qust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25104
  CLC：
- CSTR：32057.14.GFZXB.2025.7429
- Received：17 April 2025，
  
  Accepted：27 May 2025，
  
  Published Online：01 August 2025，
  
  Published：20 September 2025
- 稿件说明：
移动端阅览
张秀慧, 董静, 李伟天, 李旭, 王凤, 刘恒, 张学全. 高分子量端酰胺官能化顺丁橡胶的合成与性能研究. 高分子学报, 2025, 56(9), 1633-1643

Zhang, X. H.; Dong, J.; Li, W. T.; Li, X.; Wang, F.; Liu, H.; Zhang, X. Q. Synthesis and performance study of high-molecular-weight amide end-functionalized cis-polybutadiene rubber. Acta Polymerica Sinica, 2025, 56(9), 1633-1643
张秀慧, 董静, 李伟天, 李旭, 王凤, 刘恒, 张学全. 高分子量端酰胺官能化顺丁橡胶的合成与性能研究. 高分子学报, 2025, 56(9), 1633-1643 DOI： 10.11777/j.issn1000-3304.2025.25104. CSTR： 32057.14.GFZXB.2025.7429.

Zhang, X. H.; Dong, J.; Li, W. T.; Li, X.; Wang, F.; Liu, H.; Zhang, X. Q. Synthesis and performance study of high-molecular-weight amide end-functionalized cis-polybutadiene rubber. Acta Polymerica Sinica, 2025, 56(9), 1633-1643 DOI： 10.11777/j.issn1000-3304.2025.25104. CSTR： 32057.14.GFZXB.2025.7429.

摘要

采用具有可控配位链转移聚合特征的催化体系Nd(vers)

/Al(

Bu)

H/Al

引发丁二烯聚合，利用聚合体系快速可逆的链转移反应及Al-Polymer键较高的反应活性，在分子链末端高效地引入了酰胺基团，实现了高分子量顺丁橡胶原位官能化的高效制备. 通过凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)表征了聚合物的结构，结果表明酰胺的引入使得聚合物链间产生了氢键作用. 与顺丁橡胶相比，在分子量和分子量分布基本一致的情况下，官能化顺丁橡胶的表面能和门尼黏度均有明显提升. 极性基团的引入使得填料

在顺丁橡胶基体中的分散性改善，硫化胶的交联密度、强度和韧性均有提升，拉伸强度由19.6 MPa提高到了22.2 MPa. 本研究为原位合成官能化高分子量、高顺式-1

4含量的顺丁橡胶提供了一种简捷高效的策略，为顺丁橡胶的官能化及高值化应用提供了理论依据.

Abstract

Butadiene polymerization mediated by neodymium-based catalytic system with characteristics of controllable coordination chain transfer polymerization (CCTP) is reported herein. Due to the inherent nature of rapid and reversible chain transfer during the BD polymerization

polymer-Al bonds were able to be generated during the end of the polymerization

allowing amide groups inserting efficiently in to the

-end of the polymer chain

and thus achieving

in situ

functionalization of high molecular weight

cis

-polybutadiene rubber. The structure of the polymer was well characterized by GPC

FTIR and DSC. It was demonstrated that the introduction of amide groups led to the formation of hydrogen bonding interactions between the polymer chains. When comparing with the unfunctionalized counterpart

both the surface energy and Mooney viscosity were significantly increased. More importantly

significantly improved dispersity of fillers was demonstrated

which further resulted in enhanced crosslink density

tensile strength (from 19.6 MPa to 22.2 MPa) and toughness of the vulcanizate. Overall

this study provides a simple and efficient strategy for the

in situ

functionalization of high molecular weight

cis

-polybutadiene rubber while maintaining the high

cis

-1

4 content and high regularity of the mainchain

showing a great potential for large-scale industrialization.

关键词

Keywords

references

侯森垚 , 郝修歌 , 姜辉 , 郝新奇 , 宋毛平‍ . 铁、钴金属配合物催化1,3-二烯烃聚合研究进展‍ . 高分子学报 , 2023 ( 2 ), 186 - 205 .

Zhang X. H. ; Li X. F. ; Zhu W. B. ; Xie X. Z. ; Ji H. ; Bi J. F. Effect of dilution on the crystallization kinetics of neodymium-based rare earth polybutadiene rubber . Polymers , 2023 , 16 ( 1 ), 35 . doi: 10.3390/polym16010035 http://dx.doi.org/10.3390/polym16010035

荣钢 . 稀土顺丁橡胶在电动汽车轮胎中的应用 . 石油化工 , 2024 , 53 ( 7 ), 999 - 1005 . doi: 10.3969/j.issn.1000-8144.2024.07.013 http://dx.doi.org/10.3969/j.issn.1000-8144.2024.07.013

Medalia A. I. Filler aggregates and their effect on reinforcement . Rubber Chem. Technol. , 1974 , 47 ( 2 ), 411 - 433 . doi: 10.5254/1.3540450 http://dx.doi.org/10.5254/1.3540450

Wu J. ; Chen L. ; Su B. L. ; Wang Y. S. Evolution of Payne effect of silica-filled natural rubber in curing process . J. Rubber Res. , 2019 , 22 ( 3 ), 127 - 132 . doi: 10.1007/s42464-019-00018-7 http://dx.doi.org/10.1007/s42464-019-00018-7

Yang K. ; Zhong S. ; Tang S. Y. ; Zhou X. M. ; Wang R. Y. ; Ma K. ; Song L. ; Yue H. R. ; Liang B. Fabrication of SiO 2/Al2O3 composite-coated TiO2 by pulsed chemical vapor deposition and its applications. Ind. Eng. Chem. Res. , 2022 , 61 ( 34 ), 12590 - 12599 . doi: 10.1021/acs.iecr.2c01876 http://dx.doi.org/10.1021/acs.iecr.2c01876

Ying W. L. ; Pan W. J. ; Gan Q. ; Jia X. Y. ; Grassi A. ; Gong D. R. Preparation and property investigation of chain end functionalized cis -1,4 polybutadienes via de-polymerization and cross metathesis of cis -1,4 polybutadienes . Polym. Chem. , 2019 , 10 ( 25 ), 3525 - 3534 . doi: 10.1039/c9py00485h http://dx.doi.org/10.1039/c9py00485h

Zhang X. H. ; Ma L. S. ; Dong J. ; Li W. T. ; Li X. ; Liu H. ; Zhang X. Q. ; Wang F. Facile and efficient in situ end-functionalization of neodymium-based polybutadiene by isocyanate via a coordinative chain transfer polymerization strategy . Polymer , 2024 , 305 , 127166 . doi: 10.1016/j.polymer.2024.127166 http://dx.doi.org/10.1016/j.polymer.2024.127166

Wang W. X. ; Zhao W. P. ; Dong J. ; Zhang H. Q. ; Wang F. ; Liu H. ; Zhang X. Q. Polyisoprene bearing dual functionalized mini-blocky chain-ends prepared from neodymium-mediated coordinative chain transfer polymerizations . Chinese J. Polym. Sci. , 2023 , 41 ( 5 ), 720 - 727 . doi: 10.1007/s10118-023-2953-z http://dx.doi.org/10.1007/s10118-023-2953-z

汪骐远 , 黄建铭 , 李世辉 , 崔冬梅 . 羟基功能化高顺1,4-共轭双烯橡胶的合成 . 高分子学报 , 2022 , 53 ( 5 ), 474 - 481 . doi: 10.11777/j.issn1000-3304.2021.21312 http://dx.doi.org/10.11777/j.issn1000-3304.2021.21312

黄立贤 , 桑丽鹏 , 苏高攀 , 郭翔 , 李世辉 . 羟基功能化3,4-聚2-芳基-1,3-丁二烯的合成 . 高分子学报 , 2024 , 55 ( 2 ), 153 - 160 .

Leicht H. ; Bauer J. ; Göttker-Schnetmann I. ; Mecking S. Heterotelechelic and in-chain polar functionalized stereoregular poly(dienes) . Macromolecules , 2018 , 51 ( 3 ), 763 - 770 . doi: 10.1021/acs.macromol.7b02006 http://dx.doi.org/10.1021/acs.macromol.7b02006

Zheng Y. Y. ; Zhu H. ; Huang X. C. ; Wu Y. X. Amphiphilic silicon hydroxyl-functionalized cis -polybutadiene: Synthesis, characterization, and properties . Macromolecules , 2021 , 54 ( 5 ), 2427 - 2438 . doi: 10.1021/acs.macromol.0c02697 http://dx.doi.org/10.1021/acs.macromol.0c02697

Fan C. L. ; Bai C. X. ; Cai H. G. ; Dai Q. Q. ; Zhang X. Q. ; Wang F. S. Preparation of high cis-1 , 4 polyisoprene with narrow molecular weight distribution via coordinative chain transfer polymerization . J. Polym. Sci. Part A Polym. Chem., 2010, 48 ( 21 ), 4768 - 4774 . doi: 10.1002/pola.24268 http://dx.doi.org/10.1002/pola.24268

Wang F. ; Liu H. ; Zheng W. J. ; Guo J. ; Zhang C. Y. ; Zhao L. P. ; Zhang H. X. ; Hu Y. M. ; Bai C. X. ; Zhang X. Q. Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems . Polymer , 2013 , 54 ( 25 ), 6716 - 6724 . doi: 10.1016/j.polymer.2013.10.031 http://dx.doi.org/10.1016/j.polymer.2013.10.031

Abhilash G. ; Sabharwal S. ; Dubey A. ; Paul J. ; John H. ; Joseph R. Preparation of low-protein natural rubber latex: effect of polyethylene glycol . J. Appl. Polym. Sci. , 2009 , 114 ( 2 ), 806 - 810 . doi: 10.1002/app.30491 http://dx.doi.org/10.1002/app.30491

曾建 , 李世其 , 黄光速 , 徐云祥 . 端基四肽聚异戊二烯的合成表征及流变性能 . 高分子材料科学与工程 , 2017 , 33 ( 7 ), 1 - 5 . doi: 10.16865/j.cnki.1000-7555.2017.07.001 http://dx.doi.org/10.16865/j.cnki.1000-7555.2017.07.001

He Y. ; Xu R. ; Zhang R. ; Wang C. C. ; Li S. Q. ; Cao J. ; Tang M. Z. ; Xu Y. X. Promoted comprehensive properties of polyisoprene rubber with extremely high fatigue resistance enabled by oligopeptide aggregates . Chinese J. Polym. Sci. , 2023 , 41 ( 8 ), 1250 - 1260 . doi: 10.1007/s10118-023-2933-3 http://dx.doi.org/10.1007/s10118-023-2933-3

许蔷 , 胡雁鸣 , 李杨 , 史正海 , 王艳色 , 王玉荣 . 用甲基铝氧烷活化的氯化稀土催化剂合成高顺式窄分布聚丁二烯 . 高分子学报 , 2013 , 44 ( 1 ), 36 - 42 .

杨瑞宁 , 吴丝竹 , 祝静 , 尹超 , 赵秀英 . 受阻酚/丁腈橡胶体系的阻尼性能及分子动力学模拟 . 高分子材料科学与工程 , 2018 , 34 ( 12 ), 36 - 44 . doi: 10.16865/j.cnki.1000-7555.2018.12.007 http://dx.doi.org/10.16865/j.cnki.1000-7555.2018.12.007

Zheng Y. ; Pan L. ; Li Y. G. ; Li Y. S. Synthesis and characterisation of novel functional polyolefin containing sulfonic acid groups . Eur. Polym. J. , 2008 , 44 ( 2 ), 475 - 482 . doi: 10.1016/j.eurpolymj.2007.11.017 http://dx.doi.org/10.1016/j.eurpolymj.2007.11.017

Hagihara H. ; Tsuchihara K. ; Takeuchi K. ; Murata M. ; Ozaki H. ; Shiono T. Copolymerization of ethylene or propylene with α-olefins containing hydroxyl groups with zirconocene/methylaluminoxane catalyst . J. Polym. Sci., Part A: Polym. Chem. , 2004 , 42 ( 1 ), 52 - 58 . doi: 10.1002/pola.10989 http://dx.doi.org/10.1002/pola.10989

漆宗能 . 高聚物化学结构与玻璃化转变温度间的关系 . 化学通报 , 1965 , 28 ( 5 ), 1 - 8 .

Hassanabadi M. ; Najafi M. ; Hashemi Motlagh G. ; Saeedi Garakani S. Synthesis and characterization of end-functionalized solution polymerized styrene-butadiene rubber and study the impact of silica dispersion improvement on the wear behavior of the composite . Polym. Test. , 2020 , 85 , 106431 . doi: 10.1016/j.polymertesting.2020.106431 http://dx.doi.org/10.1016/j.polymertesting.2020.106431

于同隐 , 卜海山 . 塑料和橡胶复合物的韧性 . 塑料工业 , 1979 , 7 ( 3 ), 45 - 52 .

Wu W. X. ; Feng H. J. ; Xie L. L. ; Zhang A. Y. ; Liu F. ; Liu Z. H. ; Zheng N. ; Xie T. Reprocessable and ultratough epoxy thermosetting plastic . Nat. Sustain. , 2024 , 7 ( 6 ), 804 - 811 . doi: 10.1038/s41893-024-01331-9 http://dx.doi.org/10.1038/s41893-024-01331-9

Wang Y. X. ; Wu Y. P. ; Li W. J. ; Zhang L. Q. Influence of filler type on wet skid resistance of SSBR/BR composites: effects from roughness and micro-hardness of rubber surface . Appl. Surf. Sci. , 2011 , 257 ( 6 ), 2058 - 2065 . doi: 10.1016/j.apsusc.2010.08.129 http://dx.doi.org/10.1016/j.apsusc.2010.08.129

刘涛 , 陈亚薇 , 刘东 , 杜爱华 . 填充橡胶的Payne效应 . 特种橡胶制品 , 2015 , 36 ( 6 ), 76 - 81 .

Views

131

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Synthesis of High cis-1,4 Polybutadiene with Narrow Molecular Weight Distribution Catalyzed by a Half-sandwich Scandium Catalyst (C5H5)Sc(CH2C6H4NMe2-o)2

Synthesis of Highly Efficient Bidentate Polar Modifiers Featuring Dual Heteroatoms and Their Application in Butadiene Anionic Polymerization

Effects of Microstructure on Properties of Neodymium-based Cis Polybutadiene Rubber

Preparation of Hydroxyl Functionalized Cis-1,4 Polydienes

Related Author

Xue-quan Zang

Zheng-hai Shi

Rui Meng

Fang Guo

Qiang Xu

Ting-ting Li

Yang Li

Yu-rong Wang

Related Institution

State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology

College of Polymer Science and Engineering, Qingdao University of Science and Technology

Sinopec Beijing Yanshan Company

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology

School of Applied Chemistry and Engineering, University of Science and Technology of China

AI脑图

AI问答

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰

Synthesis and Performance Study of High-molecular-weight Amide End-functionalized cis-Polybutadiene Rubber

DOI：10.11777/j.issn1000-3304.2025.25104

摘要

Abstract

关键词

Keywords

references