多重响应性超支化星形聚合物的合成与组装以及控制释放研究

doi:10.6023/A12040167

化学学报 ›› 2012, Vol. 70 ›› Issue (16): 1690-1696.DOI: 10.6023/A12040167 上一篇下一篇

研究论文

多重响应性超支化星形聚合物的合成与组装以及控制释放研究

张文建, 范溦, 李敏, 洪春雁, 潘才元

中国科学院软物质化学重点实验室中国科学技术大学高分子科学与工程系合肥 230026

投稿日期:2012-05-05 发布日期:2012-06-19
通讯作者: 洪春雁
基金资助:
项目受国家自然科学基金(Nos. 20974103, 21074121, 21090354)资助.

Multi-responsive Hyperbranched Star Copolymer: Synthesis, Self-assembly and Controlled Release

Zhang Wenjian, Fan Wei, Li Min, Hong Chunyan, Pan Caiyuan

CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026

Received:2012-05-05 Published:2012-06-19
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 20974103, 21074121 and 21090354).

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1. 多重响应性超支化星形聚合物的合成与组装以及控制释放研究.PDF(148KB)

摘要/Abstract

含二硫键的自引发单体与2-(2-甲氧基乙氧基)乙基甲基丙烯酸酯(MEO₂MA)进行自缩合乙烯基共聚合得到超支化PMEO₂MA(H-PMEO₂MA). 以它作大分子引发剂, 引发二甲氨基乙基甲基丙烯酸酯(DMAEMA)进行原子转移自由基聚合, 合成了具有温度、pH以及氧化还原多重响应性的超支化星形聚合物H-PMEO₂MA-star-PDMAEMA. 证明了H-PMEO₂MA有低临界溶液温度(LCST); 研究了PDMAEMA 链段的长度和溶液的pH值对超支化星形聚合物的LCST的影响. 当H-PMEO₂MA-star-PDMAEMA水溶液温度从2 ℃升高至室温, H-PMEO₂MA变成疏水性而发生聚集, 形成以H-PMEO₂MA为核, PDMAEMA为壳的胶束. 在胶束形成过程中, 将尼罗红装载到这种聚合物胶束中, 形成释药系统, 研究了pH、氧化还原响应性释药性能.

关键词: 自缩合乙烯基聚合, 原子转移自由基聚合, 超支化星形聚合物, 多重响应性, 控制释放

Multi-responsive (temperature, pH and redox) hyperbranched star polymers, poly(2-(2-methoxyethoxy)ethyl methacrylate)-star-poly(dimethylaminoethyl methacrylate) (H-PMEO₂MA-star-PDMAEMA) have been successfully synthesized by self-condensing vinyl polymerization of disulfide-based inimer and MEO₂MA first, and subsequently atom transfer radical polymerization of DMAEMA with H-PMEO₂MA as macroinitiator. The M_n and M_w/M_n of the H-PMEO₂MA were 8300 g/mol and 2.61, respectively. H-PMEO₂MA-star-PDMAEMAs with different molecular weights were obtained by adjusting the polymerization time. The molecular weight of the hyperbranched star copolymer increased but the polydispersity index (PDI) decreased with increasing polymerization time. Since the PDI of the PDMAEMA formed by ATRP is low, with the molecular weight increase of the PDMAEMA, the relative amount of H-PMEO₂MA in the hyperbranched star copolymers becomes less; as a result, the influence of the core H-PMEO₂MA’s PDI on the hyperbranched star copolymers decreases. UV/Vis TU-1901 spectrophotometer was used to investigate the lower critical solution temperature (LCST) of the resultant polymer. The LCST of H-PMEO₂MA is relatively low (2—10 ℃). The effects of the compositions and pH of the solution on LCST of the hyperbranched star copolymers were studied. The LCST increased with the chain length increase of PDMAEMA. The pH of the solution has a significant impact on the LCST of the hyperbranched star copolymers. With decrease of the pH value, the protonation degree of PDMAEMA increased, the repulsion between the chain segments enhanced, making the aggregation of the H-PMEO₂MA-star-PDMAEMA molecules become difficult, and as a result, the water-solubility of the hyperbranched star copolymers enhanced. In addition, when temperature of the aqueous solution raised from 2 ℃ to room temperature, the spherical micelles with H-PMEO₂MA as core and PDMAEMA as shell were formed. During the formation of spherical micelles in the aqueous solution of H-PMEO₂MA-star-PDMAEMA and Nile Red, the Nile Red was successfully encapsulated in the micelles. The controlled release of this system, in which Nile Red was used as model drug, was investigated, the results showed that this system is pH and redox-responsive, and may have potential application in drug delivery.

Key words: self-condensing vinyl polymerization (SCVP), atom transfer radical polymerization (ATRP), hyperbranched star copolymer, multi-responsive, controlled release

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张文建, 范溦, 李敏, 洪春雁, 潘才元. 多重响应性超支化星形聚合物的合成与组装以及控制释放研究[J]. 化学学报, 2012, 70(16): 1690-1696.

Zhang Wenjian, Fan Wei, Li Min, Hong Chunyan, Pan Caiyuan. Multi-responsive Hyperbranched Star Copolymer: Synthesis, Self-assembly and Controlled Release[J]. Acta Chimica Sinica, 2012, 70(16): 1690-1696.

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多重响应性超支化星形聚合物的合成与组装以及控制释放研究

Multi-responsive Hyperbranched Star Copolymer: Synthesis, Self-assembly and Controlled Release

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