以二硫键连接的两嵌段共聚物的制备新方法

doi:10.7503/cjcu20150570

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (1): 161.doi: 10.7503/cjcu20150570

以二硫键连接的两嵌段共聚物的制备新方法

张丽鑫¹, 王金涛², 杨永芳¹, 赵汉英²()

1. 河北工业大学化工学院高分子科学与工程系, 天津 300130
2. 南开大学化学学院, 天津 300071

收稿日期:2015-07-22 出版日期:2016-01-10 发布日期:2015-12-20
基金资助:
国家自然科学基金(批准号: 51473079)资助

Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points^†

ZHANG Lixin¹, WANG Jintao², YANG Yongfang¹, ZHAO Hanying^2,^*()

1. Institute of Polymer Science and Engineering, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
2. College of Chemistry, Nankai University, Tianjin 300071, China

Received:2015-07-22 Online:2016-01-10 Published:2015-12-20
Contact: ZHAO Hanying E-mail:hyzhao@nankai.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51473079)

摘要/Abstract

摘要：

报道了一种制备二硫键连接的两嵌段共聚物的新方法. 以可逆加成-断裂链转移自由基聚合(RAFT)制备聚苯乙烯大分子链转移剂(PS-RAFT), 经伯胺还原得到巯基封端的PS(PS-SH). PS-SH与原子转移自由基聚合(ATRP)引发剂2-溴-2-甲基丙酸-2-(2-吡啶基二硫)乙酯发生交换反应, 得到含有二硫键的聚苯乙烯大分子ATRP引发剂(PS-S-S-Br). 以PS-S-S-Br引发甲基丙烯酸-2-羟基乙酯(HEMA)的ATRP聚合反应, 合成了由二硫键连接的两嵌段共聚物PS-S-S-PHEMA. 将PS-S-S-PHEMA可在甲醇中自组装形成以PS为核, PHEMA为壳的球形聚合物胶束, 为制备新型含二硫键聚合物提供了新的合成方法.

关键词: 二硫键, 嵌段聚合物, 自组装, 可逆加成-断裂链转移自由基聚合, 原子转移自由基聚合

Abstract:

Synthesis of diblock copolymers containing disulfides at the junction points was reported. Rever-sible addition-fragmentation chain transfer(RAFT) polymerization of styrene was employed to prepare polystyrene marco RAFT agent(PS-RAFT). The terminal RAFT agents of PS were reduced to sulfhydryl groups(PS-SH) in the presence of primary amine, and the atom transfer radical polymerization(ATRP) macroinitiator(PS-S-S-ATRP) was prepared by an exchange reaction between PS-SH and an ATRP initiator containing disulfide bonds. PS-S-S-ATRP was used to initiate the polymerization of 2-hydroxyethyl methacrylate(HEMA) and PS-S-S-PHEMA diblock copolymers with disulfides at the junction points were obtained. The structures and molecular weights of the diblock copolymers were characterized by proton nuclear magnetic resonance(¹H NMR) and gel permeation chromatography(GPC). Kinetics study of ATRP of HEMA shows the characteristic of living polymerization. In methanol, the diblock copolymer self-assembles into polymeric micelle with PS cores and PHEMA coronae. Transmission electron microscopy and dynamic light scattering were used to study the morphology changes of the micelles after cleavage of the disulfide bonds. The result shows a new methd to prepare block copolymers with disulfide bonds at the junction points. The self-assenbly strecture of the copolymers will have a wide application in drug release and biological imaging techniques.

Key words: Disulfide bond, Diblock copolymer, Self-assembly, Reversible addition-fragmentation chain transfer polymerization, Atom transfer radical polymerization

中图分类号:

O633.3

TrendMD:

张丽鑫, 王金涛, 杨永芳, 赵汉英. 以二硫键连接的两嵌段共聚物的制备新方法. 高等学校化学学报, 2016, 37(1): 161.

ZHANG Lixin, WANG Jintao, YANG Yongfang, ZHAO Hanying. Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points^†. Chem. J. Chinese Universities, 2016, 37(1): 161.

图/表 9

Scheme 1 Schematic illustration for the preparation of PS-S-S-PHEMA

Fig.1 1H NMR spectra of PS-RAFT(a), PS-SH(b) and PS-S-S-Br(c)

Fig.2 UV-Vis Spectra of PS-SH(a), PySSPy(b) and mixture of PS-SH and Py-SS-Py(c)

Fig.3 1H NMR spectra of PS-S-S-PHEMA

Fig.4 GPC curves of PS-RAFT(a), PS-S-S-Br(b), PS-S-S-PHEMA(c) and block copo-lymer after DTT treatment(d)^Mobile phase is DMF.

Fig.5 GPC curves of PS-S-S-PHEMA at different polymerization time(A) and dependence of Mn and PDI on polymerization time(B)

Fig.6 DLS curves of PS-S-S-PHEMA micelles in methanol(a), PS-S-S-PHZMA micelles treated with DTT for 6 h(b) and 24 h(c)

Fig.7 TEM image of PS-S-S-PHEMA micelle in methanol^Inset: tyndall effect of PS-S-S-PHEM micelle in methanol.

Fig.8 TEM image of PS-S-S-PHEMA micelle in methanol after DTT treatment^Inset: photograph of precipitation of PS-S-S-PHEMA.

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以二硫键连接的两嵌段共聚物的制备新方法

Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points^†

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以二硫键连接的两嵌段共聚物的制备新方法

Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points†

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Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points^†