Expanding the Scope of Self-Assembly: Heat-Induced Self-Assembly of Block Copolymers with High Solids

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-04-18 DOI:10.1021/acs.macromol.4c02808

Jingwei Zhang, Boyang Shi, Xiaoxiao Wu, Xiaotong Fang, Xinyue Liang, Zhou Peng, Guowei Wang

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引用次数: 0

Abstract

Polymerization-induced self-assembly (PISA) has gained widespread recognition as a potent tool for accessing nano-objects with diverse morphologies. To facilitate its practical application, further development of the self-assembly method is still urgent and challenging. We herein report an innovative self-assembly approach termed heat-induced self-assembly (HISA), enabling the preparation of nano-objects with abundant morphologies by direct thermal dissolution of solid block copolymers (BCPs) in selective solvents at elevated concentration (20% w/w). The BCPs of polyisoprene-b-polystyrene (PI-b-PS), polyisoprene-b-poly(methyl methacrylate) (PI-b-PMMA), and polyisoprene-b-poly(4-vinylpyridine) (PI-b-P4VP) were prepared by living anionic polymerization (LAP) for HISA investigation. Furthermore, this methodology was extended to heat-induced cooperative assembly (HICA) comprising PI-b-PS_m/PS_n (AB_m/B_n) and PI-b-PS_m/PI-b-PS_n (AB_m/AB_n), where B represented the PS core-forming block. The feasibility of HISA and HICA processes was investigated, and a library of morphologies, including spheres, worms, vesicles, nanotubes, and sponges, were collected. The pseudophase diagrams were constructed for both AB_m/B_n and AB_m/AB_n systems to provide guiding principles for the tailored morphologies. To evaluate the universality of HISA and HICA techniques, the AC_m/C_n and AB_m/AC_n systems (C represented PMMA or P4VP core-forming block) were further investigated. The corresponding glass transition temperatures (T_gs) of BCPs in both dry and solvated states were analyzed to gain further insights into the HISA and HICA techniques. These high-concentration assembly strategies including HISA and HICA combined operational simplicity with morphological diversity, showing significant potential in practical applications.

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扩展自组装的范围：高固体嵌段共聚物的热诱导自组装

聚合诱导自组装（PISA）作为一种获取具有不同形态的纳米物体的有效工具已经得到了广泛的认可。为了促进其实际应用，进一步发展自组装方法仍然是迫切和具有挑战性的。本文报道了一种称为热诱导自组装（HISA）的创新自组装方法，通过将固体嵌段共聚物（bcp）在高浓度（20% w/w）的选择性溶剂中直接热溶解，制备出具有丰富形貌的纳米物体。采用活阴离子聚合（LAP）法制备了聚异戊二烯-b-聚苯乙烯（PI-b-PS）、聚异戊二烯-b-聚甲基丙烯酸甲酯（PI-b-PMMA）和聚异戊二烯-b-聚4-乙烯基吡啶（PI-b-P4VP）的bcp，用于HISA研究。此外，将该方法扩展到由PI-b-PSm/PSn （ABm/Bn）和PI-b-PSm/PI-b-PSn （ABm/ABn）组成的热诱导协同组装（HICA），其中B代表PS成核块。研究了HISA和HICA工艺的可行性，并收集了包括球体、蠕虫、囊泡、纳米管和海绵在内的形态学文库。构建了ABm/Bn和ABm/ABn系统的伪相图，为定制形貌提供指导原则。为了评估HISA和HICA技术的通用性，我们进一步研究了ACm/Cn和ABm/ACn系统（C代表PMMA或P4VP成芯块）。分析了bcp在干燥和溶剂化状态下相应的玻璃化转变温度（Tgs），以进一步了解HISA和HICA技术。这些包括HISA和HICA在内的高浓度组装策略结合了操作的简单性和形态的多样性，显示出巨大的实际应用潜力。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.