文献类型：期刊文献

英文题名：Living Crystallization-Driven Self-Assembly of Linear and V-Shaped Oligo(p-phenylene ethynylene)-Containing Block Copolymers: Architecture Effect of π-Conjugated Crystalline Segment

作者：Nie, Jiucheng[1,2];Huang, Xiaoyu[1,2];Lu, Guolin[1];Winnik, Mitchell A.[4,5];Feng, Chun[1,3]

机构：[1]Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Chinese Acad Sci, Key Lab Synthet & Self Assembly Chem Organ Funct, Shanghai 200032, Peoples R China;[2]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China;[3]East China Univ Sci & Technol, Shanghai Key Lab Adv Polymer Mat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[4]Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada;[5]Univ Toronto, Dept Chem Engn & Appl Chem, Toronto, ON M5S 3E2, Canada

年份：2022

卷号：55

期号：17

起止页码：7856

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20223712702995);WOS:【SCI-EXPANDED(收录号:WOS:000861046400001)】；

基金：The authors are thankful for financial support from the National Science Foundation for Distinguished Young Scholars (51825304), the National Natural Science Foundation of China (52122314, 51873229, and 51961145103), the project of Bureau of International Cooperation, CAS (121731KYSB20200006), the Youth Innovation Promotion Association of CAS (Y2020062), the Shanghai Scientific and Technological Innovation Project (19590750400, 20JC1415400, 21520780100, and 22ZR1475400), the Innovation Program of Shanghai Municipal Education Commission (2019-01-07-00-05-E00012), and the East China University of Science and Technology (SLD13223004). M.A.W. thanks NSERC Canada for its financial support. The authors thank Dr. Kun Cui for his assistance in TEM measurements.

语种：英文

外文关键词：Acrylic monomers - Aggregates - Amides - Architecture - Aromatic compounds - Block copolymers - Self assembly

摘要：Diblock copolymers (BCPs) with a pi-conjugated block and an appropriate block ratio can undergo crystallizationdriven self-assembly (CDSA) to form fiber-like micelles of uniform width and length. Almost all examples in the literature involve BCPs with a linear pi-conjugated block. We are interested in exploring the influence of the architecture of the pi-conjugated block on (living) CDSA of oligo(p-phenylene ethynylene) (OPE) BCPs with a common block length and the same corona-forming block. Herein, we designed and synthesized three OPE7-b-PNIPAM(22) BCPs with seven repeats in the OPE block, PNIPAM = poly(N-isopropylacrylamide), with a mean degree of polymerization of 22 which differed only in the architecture of the OPE block. One sample, the reference, had a linear OPE7 block. A second sample had a V-shaped OPE7 with PNIPAM(22) attached in the middle (mV-OPE7), and the third sample was V-shaped with PNIPAM(22) attached at one end (tV-OPE7). Self-assembly experiments in ethanol/ water mixtures led to micelle-like aggregates. The variation of architecture of OPE7 backbone of OPE7-b-PNIPAM(22) led into distinct packing modes and different morphologies of the resulting aggregates. Self-seeding experiments with L-OPE7-b-PNIPAM(22) gave monodisperse fiber-like micelles of uniform width and tunable length, whereas irregular aggregates or polydisperse ribbon-like micelles were formed by tV-OPE7-b-PNIPAM(22) and mV-OPE7-b-PNIPAM(22). Important differences were also found in seeded growth experiments designed to form block comicelles with a heterogeneous core junction. L-OPE7-b-PNIPAM(22) could efficiently deposit onto the L-OPE9 core of L-OPE9-b-P2VP(56) seed micelles (P2VP = poly(2-vinylpyridine) to form triblock comicelles. In contrast, neither mV-OPE7-b-PNIPAM(22) nor tV-OPE7-b-PNIPAM(22) was able to grow micelles from the ends of the L-OPE9-b-P2VP(56) seed micelles. Instead, they formed polydisperse micelles by a self-nucleation and growth process. This work provides instructive information about how the architecture of pi-conjugated blocks affects the CDSA of BCPs with a p-conjugated-polymer block, especially under especially self-seeding and heterogeneous seeded growth protocols.