Page 102 - 《精细化工》2023年第5期

第 40 卷第 5 期 精 细 化 工 Vol.40, No.5
20 23 年 5 月 FINE CHEMICALS May 2023

功能材料
2,2-二(5-甲基-2-四氢呋喃基)丙烷在丁二烯-苯乙烯

阴离子聚合中的结构调节能力

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于志娟，武敬翔，蒋景阳，张春庆
（大连理工大学 化工学院，辽宁 大连 116024）

摘要：以正丁基锂（n-BuLi）为引发剂，2,2-二(5-甲基-2-四氢呋喃基)丙烷（BMTFP）、乙基四氢糠基醚（ETE）、
双四氢糠丙烷（DTHFP）为极性调节剂，在不同调节剂用量及聚合温度下进行丁二烯-苯乙烯的阴离子共聚合反
1
应。利用 HNMR 和 GPC 对丁苯共聚物的微观结构、相对分子质量及其分布进行了表征和测试。结果表明，BMTFP
聚合体系中无副反应发生，共聚物相对分子质量分布较窄，符合活性阴离子聚合的特点；BMTFP 对丁苯共聚物
具有较强的微观结构调节能力，在聚合温度为 50 ℃、n(BMTFP)∶n(n-BuLi)=2.0∶1.0 时，丁苯共聚物中 1,2-
结构相对含量可以达到 69.7%，苯乙烯微嵌段含量趋近于 0。且在相同条件下，BMTFP 与 ETE、DTHFP 对丁苯
共聚物微观结构的调节能力处于同一水平，但 BMTFP 的合成中所需的主要原料来源于生物基平台化合物，从
环境保护、能源安全以及潜在的经济价值等方面考虑，BMTFP 在制备高乙烯基溶聚丁苯橡胶方面具有良好的发
展前景。
关键词：活性阴离子聚合；丁苯共聚物；2,2-二(5-甲基-2-四氢呋喃基)丙烷；生物基调节剂；微观结构；功能材料
中图分类号：TB34；TQ316.324 文献标识码：A 文章编号：1003-5214 (2023) 05-1022-07

Structure regulation ability of 2,2-bis(5-methyl-2-tetrahydrofuranyl)propane
in anionic polymerization of butadiene-styrene

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YU Zhijuan, WU Jingxiang, JIANG Jingyang, ZHANG Chunqing
（School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China）

Abstract: Anionic copolymerization of butadiene and styrene with n-butyllithium (n-BuLi) as initiator,
2,2-bis(5-methyl-2-tetrahydrofuranyl)propane (BMTFP), ethyl tetrahydrofurfuryl ether (ETE) and
ditetrahydrofuranyl propane (DTHFP) as polar regulators was carried out under different dosage of
regulator and polymerization temperatures, respectively. The microstructure, relative molecular mass and its
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distribution of styrene-butadiene copolymer produced were then characterized and analyzed by HNMR and
GPC. The results showed that there was no side reaction in BMTFP polymerization system, while the
relative molecular mass distribution of copolymer was narrow, which was consistent with the characteristics
of living anionic polymerization. Moreover, BMTFP exhibited strong capacity in regulating the
microstructure of styrene-butadiene copolymer. When the polymerization temperature was 50 ℃ and
n(BMTFP)∶n(n-BuLi)=2.0∶1.0, the relative content of 1,2-structure in styrene-butadiene copolymer
reached 69.7%, and the content of styrene microblock approached zero. Though BMTFP, ETE and DTHFP
displayed the same level in terms of their ability in regulating the microstructure of styrene butadiene
copolymers under the same experimental conditions, the raw materials required for BMTFP synthesis were
bio-based platform compounds, indicating BMTFP had great development potential in the preparation of
solution styrene butadiene rubber with high vinyl content considering the aspects of environmental
protection, energy security and potential economic value.
Key words: living anionic polymerization; styrene-butadiene copolymer; 2,2-bis(5-methyl-2-tetrahydrofuran)propane;
bio-based regulator; microstructure; functional materials

收稿日期：2022-08-28; 定用日期：2022-11-10; DOI: 10.13550/j.jxhg.20220805
作者简介：于志娟（1997—），女，硕士生，E-mail：18340876832@163.com。联系人：张春庆（1970—），男，副教授，E-mail：zhangchq@
dlut.edu.cn。