Side-Chain Architecture-Dependent Thermoresponsive Behaviors of Graft Polymers with Poly(N-isopropylacrylamide) Pendants

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-01-30 DOI:10.1021/acs.macromol.4c02611

Fujin Duan, Gege Liu, Jinqian Zhang, Xin Zhao, Qingqing Wang, Youliang Zhao

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Abstract

The variations of side-chain architecture can significantly affect the thermoresponsive behaviors of graft polymers. This study is aimed at designing linear graft polymers with linear or cyclic pendants (LGPLs/LGPCs) to elucidate the distinct thermostability of polymer solutions. Three pairs of poly(N-isopropylacrylamide) (PNIPAM)-bearing graft polymers with a weight-average graft number (N_g) up to 16 are synthesized by the combination of the ring-first method, fractionation, and topology transformation. The chain architecture and graft number can affect the thermostability and thermosensitivity of polymer aqueous solutions, in which thermo-induced maximal variations of transmittance, light scattering intensity, and fluorescence intensity ratio related to amide–water hydrogen bonding drastically decrease with the incorporation of cyclic pendants and an increase of N_g. LGPLs with pronounced chain entanglement can self-assemble into thermostable lamellae, while other polymer assemblies are subjected to thermo-induced sphere-to-vesicle or vesicle-to-lamella transitions. This research affords a promising method to construct graft polymers with variable architectural parameters to achieve topology-dependent thermoresponsive behaviors.

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聚n -异丙基丙烯酰胺接枝聚合物侧链结构相关的热响应行为

侧链结构的变化会显著影响接枝聚合物的热响应行为。本研究旨在设计具有线性或环状悬垂的线性接枝聚合物（LGPLs/LGPCs），以阐明聚合物溶液的不同热稳定性。采用环优先法、分馏法和拓扑变换相结合的方法合成了3对重量平均接枝数（Ng）达16的聚n -异丙基丙烯酰胺（PNIPAM）接枝聚合物。链结构和接枝数会影响聚合物水溶液的热稳定性和热敏性，其中热诱导的透过率、光散射强度和荧光强度比与酰胺-水氢键相关的最大变化随着环垂链的加入和Ng的增加而急剧降低。具有明显链缠结的lgpl可以自组装成热稳定的片层，而其他聚合物组装则受到热诱导的球体到囊泡或囊泡到片层的转变。该研究为构建具有可变结构参数的接枝聚合物以实现拓扑相关的热响应行为提供了一种有前途的方法。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.