Synthesis and thiol-responsive degradation of polylactide-based block copolymers having disulfide junctions using ATRP and ROP

Synthesis and thiol-responsive degradation of polylactide-based block copolymers having disulfide junctions using ATRP and ROP
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DOI:
10.1002/pola.26335
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发表时间:
2013-07-15
影响因子:
--
通讯作者:
Oh, Jung Kwon
Oh, Jung Kwon
中科院分区:
化学3区
文献类型:
--
作者:
Ko, Na Re;Yao, Kejian;Oh, Jung Kwon

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研究了一种新的方法来合成各种可控的聚乳酸(PLA)基嵌段共聚物(PLA-ss-PATRPs)在嵌段连接处具有二硫键。该方法使用开环聚合(ROP)和原子转移自由基聚合(ATRP)的组合,其引发具有末端OH和Br基团的新的二硫化物标记的双头引发剂(HO-ss-iBuBr)的合成。锡催化剂用量和聚合时间对HO-ss-iBuBr引发体系的ROP控制有显著影响。各种甲基丙烯酸酯以及丙烯酸酯和苯乙烯在所得PLA-ss-iBuBr大分子引发剂存在下的一系列ATRP以活性方式进行。使用差示扫描量热法和二硫键裂解后的硫醇响应性降解进一步表征这些良好控制的PLA-ss-PATRP的热性质。(c)2012 Wiley Periodicals,Inc. J Polym Sci Part A:Polym. 2013,51,3071-3080
A new method to synthesize a variety of well-controlled polylactide (PLA)-based block copolymers having disulfide linkages at block junctions (PLA-ss-PATRPs) was investigated. The method uses a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) that initiates the synthesis of a new disulfide-labeled double-head initiator having both terminal OH and Br groups (HO-ss-iBuBr). The amount of tin catalyst and polymerization time significantly influenced the control of ROP initiated with HO-ss-iBuBr. A series of ATRP of various methacrylates as well as acrylate and styrene in the presence of the resulting PLA-ss-iBuBr macroinitiators proceeded in a living manner. These well-controlled PLA-ss-PATRPs were further characterized for thermal properties using differential scanning calorimetry and thiol-responsive degradation upon the cleavage of disulfide linkages. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym. Chem. 2013, 51, 3071-3080