Synthesis of Multi-hydroxyl Terminated Polybutadiene Liquid Rubber Featuring High 1,4-Content

Wei-xin Wang; Wen-peng Zhao; Jing Dong; Feng Wang; Xue-quan Zhang; Heng Liu

doi:10.11777/j.issn1000-3304.2024.24237

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Synthesis of Multi-hydroxyl Terminated Polybutadiene Liquid Rubber Featuring High 1,4-Content

Research Article | 更新时间：2025-02-27

- Synthesis of Multi-hydroxyl Terminated Polybutadiene Liquid Rubber Featuring High 1,4-Content
- Acta Polymerica Sinica Vol. 56, Issue 3, Pages: 457-464(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：
  
  Heng Liu, E-mail: hengliu@qust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24237
  CLC：
- CSTR：32057.14.GFZXB.2024.7315
- Received：13 September 2024，
  
  Accepted：2024-11-05，
  
  Published Online：10 January 2025，
  
  Published：20 March 2025
- 稿件说明：
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王卫鑫, 赵文朋, 董静, 王凤, 张学全, 刘恒. 高1,4-结构的双端多羟基液体聚丁二烯橡胶的制备. 高分子学报, 2025, 56(3), 457-464

Wang, W. X.; Zhao, W. P.; Dong, J.; Wang, F.; Zhang, X. Q.; Liu, H. Synthesis of multi-hydroxyl terminated polybutadiene liquid rubber featuring high 1,4-content. Acta Polymerica Sinica, 2025, 56(3), 457-464
王卫鑫, 赵文朋, 董静, 王凤, 张学全, 刘恒. 高1,4-结构的双端多羟基液体聚丁二烯橡胶的制备. 高分子学报, 2025, 56(3), 457-464 DOI： 10.11777/j.issn1000-3304.2024.24237. CSTR： 32057.14.GFZXB.2024.7315.

Wang, W. X.; Zhao, W. P.; Dong, J.; Wang, F.; Zhang, X. Q.; Liu, H. Synthesis of multi-hydroxyl terminated polybutadiene liquid rubber featuring high 1,4-content. Acta Polymerica Sinica, 2025, 56(3), 457-464 DOI： 10.11777/j.issn1000-3304.2024.24237. CSTR： 32057.14.GFZXB.2024.7315.

摘要

端羟基聚丁二烯(HTPB)是一种低分子量的遥爪液体橡胶，其性能主要受主链微观结构的影响，高1

4-结构含量的HTPB低温力学性能最佳，然而由于聚合机理的限制，合成高1

4-结构含量的HTPB的方法非常有限. 本研究利用钕系催化剂催化丁二烯单体配位可逆链转移聚合(CCTP)的特性，采用“三步法序贯聚合”策略，合成了一系列分子量可控、窄分布、高1

4-结构含量的端羟基聚丁二烯(HTPB)液体橡胶. 与传统的HTPB不同的是，此法得到的HTPB的羟基的平均官能度(

)，可通过调节羟基共聚单体Bd

OAl

的加入量得以实现，进而能够制备末端含多个羟基的端多羟基HTPB，羟基官能度最高达3.3，所得HTPB的分子量可通过改变单体比和铝比得以实现. 降低单体比或增加铝比，均能明显降低所得HTPB的分子量. 本工作所得HTPB分子量分布窄、分子量大范围可调，且羟基官能度可调，能够与传统阴离子/自由基型HTPB形成良好的互补性.

Abstract

Hydroxyl-terminated polybutadiene (HTPB)

a low-molecular-weight telechelic liquid rubber

is extensively utilized in various applications due to its distinctive attributes

including excellent transparency and low viscosity. The overall properties of HTPB are predominantly influenced by the microstructures of the main chain

with HTPB possessing a high 1

4-content exhibiting superior mechanical characteristics

particularly at low temperatures. However

the synthesis of such HTPB is challenging due to the inferior regioselectivity of current anionic or radical polymerization methods

which predominantly yield products with a high 1

2-content. In this study

we introduce a neodymium-based coordination polymerization system for the preparation of HTPB featuring high 1

‍4-content. This catalytic system exhibits unique coordinative chain transfer polymerization (CCTP) features

enabling the synthesis of HTPB with controlled molecular weight

narrow polydispersity

and very high 1

‍4-content. Furthermore

the average functionality (

‍f ‍

) of the hydroxyl groups in the synthesized HTPB can be readily adjusted by varying the molar ratio of the Bd

OAl

comonomer. The resulting

values can reach up to 3.3

which is significantly higher than those typically obtained from traditional HTPB synthesized

via

anionic or radical polymerization methods

which are usually below 2.0. In conclusion

the HTPB synthesized using the CCTP method presented in this study offers a complementary advantage over conventional HTPB

showcasing improved control over molecular architecture and functionality

which may have significant implications for the development of advanced materials in various industrial sectors.

关键词

Keywords

references

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