碘代化合物存在下光引发的可逆-休眠自由基聚合研究进展

doi:10.16085/j.issn.1000-6613.2019-2031

摘要/Abstract

摘要：

碘代化合物存在下光引发的可逆-休眠自由基聚合（reversible deactivation radical polymerization, RDRP）具有体系组成简单、适用光源波长范围宽等优点，近年来受到广泛关注。本文主要介绍了最近几年碘代化合物存在下光引发的可逆-休眠自由基聚合的研究进展，以及该聚合方法与其他研究方向的交叉应用。具体包括：光引发的碘转移聚合、光引发的可逆络合聚合以及这些聚合方法在其它研究方向的应用。概述了聚合机理、聚合适用的光源，以及上述聚合方法作为工具实现聚合物“刷”的制备和诱导自组装（polymerization-induced self-Assembly，PISA），实现了不同聚合物形貌的设计。

关键词: 可逆-休眠自由基聚合, 光引发的碘转移聚合, 光引发的可逆络合聚合

Abstract:

Photoinduced reversible deactivation radical polymerization in the presence of alkyl iodidie has many attractive features such as simple system composition, wide range wavelengths of light source. This paper summarized the photoinduced RDRP with iodocompounds and cross applications of this polymerization method in recent years, including photoinduced iodine transfer polymerization, photoinduced reversible complexation mediated polymerization. This paper gave a review of the basic mechanism of polymerization, applicability to different-wavelength light sources. Moreover, the preparation of polymer “brush” and polymerization induced self-assembly by photoinduced reversible complexation mediated polymerization were also discussd.

Key words: reversible deactivation radical polymerization (RDRP), photoinduced iodine transfer polymerization, photoinduced reversible complexation mediated polymerization

中图分类号:

张旭, 陈珂龙. 碘代化合物存在下光引发的可逆-休眠自由基聚合研究进展[J]. 化工进展, 2020, 39(S1): 1-11.

Xu ZHANG, Kelong CHEN. Research progress of photoinduced reversible deactivation radical polymerization in the presence of alkyliodidie[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 1-11.

图/表 17

图1 可逆-失活自由基聚合

图2 光开关调控异丁酸正丁酯碘转移聚合的聚合机理

图3 可逆络合聚合（RCMP）聚合机理

图4 可见光条件下MMA的可逆络合聚合

图5 小分子有机胺的结构示意图

图6 紫外光谱图与核磁共振谱图

图7 可见光条件下溴碘转化可逆络合聚合

图8 溴代化合物转化为碘代化合物的核磁谱图

图9 不同溶剂的聚合体系的红外谱图（包括MMA的本体聚合）

图10 聚合体系的聚合机理

图11 可见光蓝光条件下碘单质以及聚合体系在水中不同时刻的红外谱图

图12 两亲性聚合物的透射电镜图

图13 MMA和 δ-戊内酯嵌段聚合物的制备

图14 二元聚合物刷制备示意图

图15 合成PMAA-PMMA嵌段聚合物流程图

图16 PPEGMA- b-PbnMA嵌段聚合物制备流程图

图17 不同亲水段和亲油段长度对应的透射电镜图(a～e)及不同亲油段和亲水段两亲性聚合物粒径分布图(f)

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