Block copolymer particles with tunable and robust internal nanostructures by combining hydrogen-bonding and crosslinking

Shuai Deng , Tinghao Yan , Mian Wang , Jingye Liu , Renhua Deng , Jintao Zhu
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Abstract

Nanostructured block copolymer (BCP) particles are attractive due to their ordered internal structures, unique shape and surface patterns; however, their structural integrity can be easily lost because of weak intermolecular interactions, which limits their practical applications. In this study, we present a simple and reliable method to fabricate nanostructured particles of polystyrene-block-poly(4-vinylpyridine) with tunable and robust nanostructures by employing hydrogen-bonding and cross-linking strategies. The key feature of poly(4-vinylpyridine) is the presence of reactive pyridyl moieties, which allow precise regulation of internal nanostructures via hydrogen bonds and locking of the structural integrity via quaternarization by feeding hydrogen bond donors and cross-linkers, respectively. The solvent resistance is well proven by immersing the particles in either selective solvents of the continuous phase or good solvent of the BCP. Furthermore, mesoporous BCP particles derived from the cross-linked particles are obtained simply by a swelling/deswelling treatment. This study provides a way to improve the structural robustness of BCP particles and could be a key step that advances the functionalization and subsequent applications of such nanostructured BCP colloidal particles.

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通过结合氢键和交联,嵌段共聚物颗粒具有可调和坚固的内部纳米结构
纳米结构嵌段共聚物(BCP)颗粒由于其有序的内部结构、独特的形状和表面图案而具有吸引力;然而,由于分子间相互作用较弱,它们的结构完整性很容易丧失,这限制了它们的实际应用。在本研究中,我们提出了一种简单可靠的方法,通过氢键和交联策略制备具有可调和坚固纳米结构的聚苯乙烯嵌段聚(4-乙烯基吡啶)纳米结构颗粒。聚(4-乙烯基吡啶)的关键特征是存在反应性吡啶基部分,其允许通过氢键精确调节内部纳米结构,并通过分别供给氢键供体和交联剂的季铵化锁定结构完整性。通过将颗粒浸入连续相的选择性溶剂或BCP的良好溶剂中,很好地证明了耐溶剂性。此外,由交联颗粒衍生的中孔BCP颗粒简单地通过溶胀/去溶胀处理获得。这项研究提供了一种提高BCP颗粒结构稳健性的方法,可能是推进这种纳米结构BCP胶体颗粒的功能化和后续应用的关键步骤。
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