苯乙烯<strong>/</strong>异戊二烯渐变嵌段共聚物的负离子法合成和性能

doi:10.11901/1005.3093.2019.289

材料研究学报

2019, Vol. 33

Issue (11): 831-836 DOI: 10.11901/1005.3093.2019.289

研究论文

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苯乙烯/异戊二烯渐变嵌段共聚物的负离子法合成和性能

廖明义(

),徐晓川

大连海事大学交通运输工程学院材料科学与工程系大连 116026

Anionic Synthesis and Dynamic Mechanical Poperties of Styrene/Isoprene Copolymers with Gradient Blocks

LIAO Mingyi(

),XU Xiaochuan

Department of Materials Science and Engineering, College of Transportation Engineering, Dalian Maritime University, Dalian 116026, China

引用本文:

廖明义,徐晓川. 苯乙烯/异戊二烯渐变嵌段共聚物的负离子法合成和性能[J]. 材料研究学报, 2019, 33(11): 831-836.
Mingyi LIAO, Xiaochuan XU. Anionic Synthesis and Dynamic Mechanical Poperties of Styrene/Isoprene Copolymers with Gradient Blocks[J]. Chinese Journal of Materials Research, 2019, 33(11): 831-836.

全文: PDF(1671 KB) HTML

摘要:

一次加料延时加入极性结构调节剂四氢呋喃(THF)、以正丁基锂(n-BuLi)为引发剂、环己烷为溶剂，用活性负离子聚合技术合成了具有渐变嵌段结构的苯乙烯(St)/异戊二烯(Ip)共聚物(S/I)。使用核磁共振氢谱(¹H-NMR)和动态粘弹谱(DMA)等仪器表征共聚物的微观结构并测定共聚物的动态力学性能，研究了THF的加入时间和St含量对S/I共聚物微观结构和性能的影响。结果表明，加入THF的时间显著影响共聚物的微观结构、力学和动态力学性能。控制THF的加入时间能调控St和Ip单体的共聚合活性从而调控共聚物的微观结构和共聚物的组成及其分布，生成具有渐变嵌段结构的S/I共聚物，拓宽共聚物的玻璃化转变温度(T_g)区间。对S/I共聚物的结构和性能的变化过程也进行了理论分析。

关键词 ：有机高分子材料, 苯乙烯/异戊二烯共聚物, 负离子聚合, 合成, 渐变嵌段结构, 动态力学性能

Abstract：

The styrene (St)/isoprene (Ip) copolymers (S/I) with gradient blocks were synthesized by a one-step anionic polymerization technique with cyclohexane as solvent, n-butyl lithium (n-BuLi) as initiator and tetrahydrofuran (THF) as polar structure regulator. The microstructures and dynamic mechanical properties of synthesized S/I copolymers were characterized by ¹H-NMR and dynamic mechanic analysis (DMA), respectively. The effect of the time of THF addition and St content on the microstructure and the properties of S/I copolymers were investigated. The results show that the time of THF addition had a great effect on the microstructure, mechanical and dynamic properties of S/I copolymers, and the proper time of THF addition may be beneficial to modulate the copolymerization activity of St and Ip, and further modulate the microstructure and composition of the copolymers, therefore, S/I copolymers with gradient blocks could finally form, which possess broadened glass transition region and damping range. The evolution of structure and the properties of S/I copolymers were also analyzed theoretically.

Key words： organic polymer materials styrene/isoprene copolymers anionic polymerization synthesis gradient block structure dynamic mechanical properties

收稿日期: 2019-06-05

ZTFLH:

TQ333.99

作者简介: 廖明义，男，1962年生，博士，教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2019.289 或 https://www.cjmr.org/CN/Y2019/V33/I11/831

图1 S/I共聚物的1H-NMR谱图

表1 S/I共聚物的1H-NMR谱图归属

表2 调节剂加入时间对S/I共聚物微观结构含量的影响

表3 St含量对S/I共聚物微观结构含量的影响

表4 调节剂加入时间对S/I共聚物力学性能的影响

图2 调节剂的加入时间对S/I共聚物动态力学性能的影响

图3 调节剂的加入时间对S/I共聚物动态力学性能的影响

表5 St含量对S/I共聚物力学和动态力学性能的影响

图4 St含量对S/I共聚物动态力学性能的影响

图5 共聚物S/I链结构的示意图

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