Fan Bin, Liu Lei, Li Jun-Huan, Ke Xi-Xian, Xu Jun-Ting, Du Bin-Yang, Fan Zhi-Qiang
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science & Engineering, Zhejiang University, Hangzhou 310027, China.
Soft Matter. 2016 Jan 7;12(1):67-76. doi: 10.1039/c5sm02226f.
Crystallization-driven self-assembly of polyethylene-b-poly(tert-butylacrylate) (PE-b-PtBA) block copolymers (BCPs) in N,N-dimethyl formamide (DMF) was studied. It is found that all three PE-b-PtBA BCPs used in this work can self-assemble into one-dimensional crystalline cylindrical micelles. When the BCP solution is cooled to crystallization temperature (Tc) from 130 °C, the seed micelles may be produced via two competitive processes in the initial period: stepwise micellization/crystallization and simultaneous crystallization/micellization. Subsequently, the seed micelles can undergo growth driven by the epitaxial crystallization of the unimers. The lengths of both the seed micelles and the grown micelles are longer for the BCP with a longer PtBA block at a higher Tc. Quasi-living growth of the PE-b-PtBA crystalline cylindrical micelles is achieved at a higher Tc. A longer PtBA block evidently retards the attachment of unimers to the crystalline micelles, leading to a slower growth rate.
研究了聚乙烯 -b-聚（丙烯酸叔丁酯）（PE-b-PtBA）嵌段共聚物（BCP）在N，N-二甲基甲酰胺（DMF）中由结晶驱动的自组装。结果发现，本研究中使用的所有三种PE-b-PtBA BCP都能自组装成一维结晶圆柱形胶束。当BCP溶液从130°C冷却到结晶温度（Tc）时，在初始阶段，种子胶束可能通过两个竞争过程产生：逐步胶束化/结晶和同时结晶/胶束化。随后，种子胶束可以在单体的外延结晶驱动下生长。在较高的Tc下，对于具有较长PtBA嵌段的BCP，种子胶束和生长后的胶束长度都更长。在较高的Tc下实现了PE-b-PtBA结晶圆柱形胶束的准活性生长。较长的PtBA嵌段明显阻碍单体附着到结晶胶束上，导致生长速率较慢。
