Crystalline Three-Dimensional Polyhedron Nanoparticles from the Intramolecular Cyclization-Induced Self-Assembly of an Amorphous Poly(Amic Acid) in Water

IF 5.1 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-12-16 DOI:10.1021/acs.macromol.4c01878

Tao Wang, Yin Wang, Hui Sun

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Abstract

The controlled preparation of crystalline three-dimensional (3D) nanoparticles is attractive in polymer science due to the diverse topological structure and complicated chain folding mechanism of polymers. In this study, an intramolecular cyclization-induced self-assembly (ICISA) strategy is proposed to prepare water-dispersible crystalline 3D polyhedron nanoparticles taking advantage of the amorphous to crystalline transition during self-assembly promoted by the thermally triggered intramolecular cyclization reaction of an amorphous poly(amic acid) (PAA). Upon thermal treatment of the PAA in water, the rigid and crystalline polyimide (PI) blocks are generated in the backbone due to the unique intramolecular cyclization reaction feature of PAA, leading to the in situ flexible to rod-like chain and the amorphous to crystalline transition simultaneously, as well as the formation of crystalline polyhedron nanoparticles. Benifiting from the excellent stability of PI, the chain packing patterns of the polymer can be clearly observed by high-resolution transmission electron spectroscopy, which is further proved by computer simulations, demonstrating that the arrangement of polymer chains has a tilt angle of about 30° with a d spacing of 0.34 nm. This finding brings new insights into understanding the crystallization behavior of polymers and the facile preparation of crystalline 3D nanoparticles in water.

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由于高分子拓扑结构多样、链折叠机制复杂，可控制备结晶三维（3D）纳米粒子在高分子科学中具有很大的吸引力。本研究提出了一种分子内环化诱导自组装（ICISA）策略，利用无定形聚（amic acid）（PAA）的热触发分子内环化反应在自组装过程中促进的无定形到晶体的转变，制备水分散性结晶三维多面体纳米粒子。在水中对 PAA 进行热处理时，由于 PAA 独特的分子内环化反应特性，在骨架中生成了刚性和结晶性聚酰亚胺（PI）嵌段，从而实现了从柔性链到棒状链的原位转变和从无定形到结晶的同时转变，并形成了结晶性多面体纳米颗粒。利用 PI 的优异稳定性，高分辨率透射电子显微镜可以清晰地观察到聚合物的链堆积模式，计算机模拟也进一步证明了这一点，即聚合物链的排列具有约 30° 的倾斜角和 0.34 nm 的 d 间距。这一发现为理解聚合物的结晶行为以及在水中轻松制备结晶三维纳米粒子带来了新的启示。

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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.