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《合成橡胶工业》[ISSN:1000-1255/CN:62-1036/TQ]

期数:

2025年1期

页码:

16-22

栏目:

出版日期:

1900-01-01

文章信息/Info

Title:

Synthesis and photochromic behavior of spiro-pyran functionalized styrene-butadiene block copolymer

文章编号:

1000-1255（2025）01-0016-07

作者:

王 博; 张瑞雪; 赖 萌; 马红卫?鄢; 韩 丽?鄢; 李 杨

大连理工大学 精细化工国家重点实验室/辽宁省高分子科学与工程重点实验室，辽宁 大连 116024

Author(s):

WANG Bo;  ZHANG Rui-xue;  LAI Meng;  MA Hong-wei;  HAN Li;  LI Yang

State Key Laboratory of Fine Chemicals/Liaoning Provincial Key Laboratory of Polymer Science and Engineering, Dalian University of Technology, Dalian 116024, China

关键词:

丁苯嵌段共聚物; 活性负离子溶液聚合; 螺吡喃; 光致变色行为; 功能化

Keywords:

styrene-butadiene block copolymer;  living anionic solution polymerization;  spiro-pyran;  photochromic behavior;  functionalization

分类号:

TQ 333.1

DOI:

DOI:10.19908/j.cnki.ISSN1000-1255.2025.01.0016

文献标识码:

A

摘要:

利用活性负离子溶液聚合技术，通过分布加料法制备了含有硅氢基团功能化的聚苯乙烯（PVPDMS）与聚丁二烯（PB）组成的丁苯嵌段共聚物，即PVPDMS-b-PB。采用凝胶渗透色谱分析其数均分子量和分子量分布，结果显示，PVPDMS-b-PB呈现出单峰窄分布的特征且分子量可控；在PVPDMS-b-PB中，PVPDMS嵌段的分子量不变，PB嵌段的分子量逐渐增大。进一步设计合成了炔基官能化的螺吡喃单体（SP-Yne），在室温下通过SP-Yne与PVPDMS-b-PB（数均分子量10.4 kg/mol）的硅氢加成反应，制备了结构可控的螺吡喃（SP）功能化丁苯嵌段共聚物，即（PVPDMS-g-SP）-b-PB。采用核磁共振波谱仪对上述单体和聚合物进行结构分析，结果表明，在室温下，硅氢基团与炔基和双键的硅氢加成反应具有选择性，PVPDMS嵌段的硅氢基团能够与SP-Yne的炔基基团反应，而不与PB嵌段的双键反应，从而避免了PVPDMS嵌段中硅氢基团与PB嵌段中双键的硅氢加成反应而产生的自交联，成功将SP定向引入到PVPDMS嵌段中。采用紫外光谱仪对SP-Yne和（PVPDMS-g-SP）-b-PB的光致变色行为进行了分析，结果表明，在三氯甲烷、四氢呋喃和甲苯溶液中，365 nm紫外光照射下，SP-Yne和（PVPDMS-g-SP）-b-PB均出现明显的光致变色行为，其最大吸收波长与溶液的极性存在显著关系。

Abstract:

Using active anionic solution polyme-rization technology, a styrene-butadiene block copolymer (PVPDMS-b-PB) functionalized with silicon-hydride groups was synthesized via feed distribution method. Gel permeation chromatography was employed to analyze the number-average molecular weight and polydispersity index, revealing that PVPDMS-b-PB exhibited a unimodal, narrow distribution with a controllable molecular weight. In PVPDMS-b-PB, the molecular weight of the PVPDMS block remained constant, while the mole-cular weight of the PB block gradually increased. Further, an alkyne-functionalized spiro-pyran monomer (SP-Yne) was designed and synthesized. At room temperature, the silicon-hydride addition reaction between SP-Yne and PVPDMS-b-PB (number-average molecular weight 10.4 kg/mol) resulted in the formation of a structurally controlled spiro-pyran (SP)-functionalized styrene-butadiene block copolymer, namely (PVPDMS-g-SP)-b-PB. Structural ana-lysis of the monomer and polymer was carried out using nuclear magnetic resonance spectroscopy. The results showed that at room temperature, the silicon-hydride addition reaction between the silicon-hydride groups and the alkyne or double bonds was selective. The silicon-hydride groups in the PVPDMS block reacted with the alkyne groups in SP-Yne, avoiding reactions with the double bonds in the PB block, thereby preventing self-crosslinking between the silicon-hydride groups in PVPDMS and the double bonds in PB. UV spectroscopy was used to analyze the photochromic behavior of SP-Yne and (PVPDMS-g-SP)-b-PB, and the results showed significant photochromic behavior under 365 nm UV irradiation in chloroform, tetrahydrofuran, and toluene solutions. The maximum absorption wavelength exhibited a significant correlation with the polarity of the solution.

参考文献/References

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备注/Memo

备注/Memo:

中央高校基本科研业务费资助项目（DUT 21 LAB 129）。

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更新日期/Last Update: 1900-01-01