高1,4-结构的双端多羟基液体聚丁二烯橡胶的制备  

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

作　　者：王卫鑫 赵文朋 董静 王凤 张学全 刘恒 Wei-xin Wang;Wen-peng Zhao;Jing Dong;Feng Wang;Xue-quan Zhang;Heng Liu(Key Laboratory of Rubber and Plastic Materials of Ministry of Education,Shandong Provincial College Laboratory of Rubber Material and Engineering,College of Polymer Science and Technology,Qingdao University of Science and Technology,Qingdao 266000;Lanzhou Petrochemical Research Center,Petrochemical Research Institute,PetroChina,Lanzhou 730060)

机构地区：[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

出　　处：《高分子学报》2025年第3期457-464,共8页Acta Polymerica Sinica

基　　金：国家重点研发计划(项目号2022YFC2104700);山东省泰山学者工程(项目号tsqn202211165)资助。

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(f),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.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 f 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：端羟基聚丁二烯 高1 4-结构含量 稀土 配位可逆链转移聚合 

分 类 号：TQ3[化学工程]