Synthesis of Unimolecular Micelles with Incorporated Hyperbranched Boltorn H30 Polyester modified with Hyperbranched Helical Poly(phenyl isocyanide) Chains and their Enantioselective Crystallization Performance
Synthesis of Unimolecular Micelles with Incorporated Hyperbranched Boltorn H30 Polyester modified with Hyperbranched Helical Poly(phenyl isocyanide) Chains and their Enantioselective Crystallization Performance
复制标题
超支化螺旋聚异氰苯酯链改性超支化 Boltorn H30 聚酯单分子胶束的合成及其对映选择性结晶性能
DOI：
10.1002/marc.201700315
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发表时间：
2017
影响因子：
4.6
通讯作者：
Wu Zong Quan
中科院分区：
文献类型：
--
作者：
Zhang Zhi Huang;Qiao Chen Yang;Zhang Jian;Zhang Wen Ming;Yin Jun;Wu Zong Quan
在这里，报道了用螺旋聚合物链功能化的单分子胶束作为对映选择性结晶中的手性成核剂的制造。从分级超支化聚酯 (Boltorn H30) 开始，l-乳酸 (LLA) 的开环聚合和随后的端基修饰得到了炔烃-Pd(II) 锚定的超支化大分子引发剂 (H30-PLLA-Pd)。通过利用 Pd(II) 催化的手性侧链改性三苯基异氰化物 (PI) 单体的活性聚合，获得了接枝有一种主要螺旋方向的辐射螺旋 PPI 冠的明确手性单分子胶束 (H30-PLLA-PPI)。所得手性材料在水中外消旋苏氨酸的对映选择性结晶中表现出优异的应用，残留溶液的对映体过量值达到92%。据信，目前的概念和方法证明对于制备具有不同拓扑结构的新颖且通用的手性材料来说是简单而有力的，不仅适用于 PPI，而且适用于其他类型的聚合物。
Here, the fabrication of unimolecular micelles functionalized with helical polymeric chains as a chiral nucleating agent in enantioselective crystallization is reported. Starting from a fractionated hyperbranched polyester (Boltorn H30), the ring‐opening polymerization ofl‐lactic acid (LLA) and subsequent terminal‐group modification affords the alkyne‐Pd(II)‐anchored hyperbranched macroinitiator (H30‐PLLA‐Pd). By taking advantage of a Pd(II)‐catalyzed living polymerization of chiral pendant modifiedl‐ ord‐phenyl isocyanide (PI) monomers, well‐defined chiral unimolecular micelles (H30‐PLLA‐PPI) grafted with radiating helical PPI coronas of one predominant screw sense are obtained. The resultant chiral materials demonstrate excellent application in the enantioselective crystallization of racemic threonine in water, and a 92% enantiomeric excess value of the residual solution is obtained. It is believed this present proof of concept and methodology are facile and powerful for preparing novel and versatile chiral materials with different topological structures, not only applicable to PPI but also to other types of polymers.