氢键构筑的刚柔型嵌段共聚物的自组装结构调控

doi:10.12141/j.issn.1000-565X.260004

摘要/Abstract

摘要：

嵌段共聚物可自组装形成丰富的纳米有序结构，是构建纳米模板和纳米多孔材料的理想软物质体系。将刚性链引入嵌段共聚物中，可以增强嵌段间的不相容性，从而有望利用所得刚柔嵌段共聚物构建小尺寸的有序结构。但是，单体的刚性结构不利于低分散嵌段共聚物的精确合成，而借助氢键等非共价相互作用、利用低分散度柔柔嵌段共聚物前体来构筑刚柔嵌段共聚物则更便捷。本工作中，以小分子羧酸配体6TP以及不同组成和分子量的聚苯乙烯-b-聚(4-乙烯基吡啶)（PS-b-P4VP）分别作为氢键给体和聚合物前体，构筑了一系列超分子型嵌段共聚物PS-b-P4VP(6TP)_x，并通过控制小分子配体与聚合物前体中吡啶的复合比例，实现了对氢键复合物的组装结构调控，获得了层状相（LAM）、双连续相（GYR）、六方柱状相（HEX）、球状相（BCC）等有序纳米结构。通过探究复合比例对组装结构的影响，发现接近等当量的复合比例有助于形成GYR结构。随后，以乙醇为选择性溶剂，尝试除去小分子配体6TP来制备GYR结构的纳米多孔材料，发现虽然刻蚀后GYR结构可以保持，但其周期尺寸减小，说明基于氢键的动态自组装结构发生了一定程度的塌缩。这一工作为利用氢键复合物来构筑小尺寸多孔网络结构奠定了基础。

关键词: 氢键, 刚柔型嵌段共聚物, 自组装, 双连续相

Abstract:

Block copolymers (BCPs) can assemble into various ordered nanostructures, making them ideal soft materials for constructing nanotemplates and nanoporous materials. The introduction of rod chains into BCPs would enhance incompatibility between blocks, rendering the possibility of obtaining small-sized ordered structures from rod-coil BCPs. However, it is difficult to the precise synthesis of narrowly dispersed BCPs from monomers with rigid structures. On the other hand, it is a facile method to construct rod-coil BCPs through non-covalent interactions such as hydrogen bonding using narrowly dispersed coil-coil BCP precursors. In this work, by using a small-molecule ligand 6TP that contains carboxylic acid and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with different compositions and molecular weights as hydrogen bonding donors and acceptors, respectively, a series of supramolecular rod-coil BCPs PS-b-P4VP(6TP)_x were prepared. By controlling the molar complex ratio between 6TP and pyridine in P4VP, we were able to control the ordered nanostructures of the hydrogen-bonding complexes, and lamellar phase (LAM), bicontinuous double gyroid phase (GYR), hexagonally packed cylindrical phase (HEX), and body-centered cubic phase (BCC) were obtained. By exploring the effect of complex ratio on the self-assembled structure, we found that the molar ratio being close to 1 would be helpful in the formation of the GYR structure. Afterwards, ethanol was chosen as the etching solvent to remove 6TP to construct nanoporous materials with the bicontinuous GYR structure. However, although the GYR structure could be maintained after etching, its periodic size decreased, indicating that the dynamic self-assembled structure based on hydrogen bonding underwent collapsing to a certain degree. This work lays the foundation for the application of constructing small-sized porous networks using hydrogen-bonding complexes.

Key words: hydrogen bonding, rod-coil block copolymers, self-assembly, double gyroid phase

刘赟, 王鸿飞, 杨世楚, 等. 氢键构筑的刚柔型嵌段共聚物的自组装结构调控[J]. 华南理工大学学报(自然科学版), doi: 10.12141/j.issn.1000-565X.260004.

Liu Yun, Wang Hongfei, Yang Shichu, et al. Controlling the Self-Assembled Structure of a Rod-Coil Block Copolymer Constructed by Hydrogen Bonding[J]. Journal of South China University of Technology(Natural Science Edition), doi: 10.12141/j.issn.1000-565X.260004.

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氢键构筑的刚柔型嵌段共聚物的自组装结构调控

Controlling the Self-Assembled Structure of a Rod-Coil Block Copolymer Constructed by Hydrogen Bonding

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