Thermoresponsive Gelation and Phase Transition of PEG/Cation Random Terpolymer Micelles in Water in the Presence of Salts

IF 5.1 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-10-22 DOI:10.1021/acs.macromol.4c01677

Rikuto Kanno, Motoki Shibata, Mikihito Takenaka, Shin-ichi Takata, Kosuke Hiroi, Makoto Ouchi, Takaya Terashima

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Abstract

Amphiphilic random terpolymers bearing hydrophilic poly(ethylene glycol) (PEG) chains, quaternary ammonium cations, and hydrophobic dodecyl groups form size-controlled micelles in water. The terpolymer micelles show a lower critical solution temperature (LCST)-type solubility in water in the presence of salts. Focusing on the features, we herein investigated the thermoresponsive properties of the concentrated aqueous solutions of the PEG/cation random terpolymer micelles containing NaCl to find unique gelation and phase transition dependent on the PEG/cation composition. Upon heating, the PEG/cation (2/1, 1/1, and 1/2) terpolymer micelle solutions exhibited a two-step phase transition through transient gelation to viscous and turbid solutions via LCST-type phase separation. In contrast, a cation-rich PEG/cation (1/3) terpolymer micelle and a cation copolymer micelle formed gels in water at room temperature, where the former changed to a viscous and transparent solution upon heating. The rheological properties of the gels can be tuned by the PEG/cation ratio and degree of polymerization of the terpolymers. Small-angle neutron scattering measurements revealed that the transient gelation of the terpolymer micelle solutions occurred via the formation of intermicellar networks.

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盐类存在时 PEG/阳离子无规三元共聚物胶束在水中的热膨胀凝胶化和相变

含有亲水性聚乙二醇（PEG）链、季铵阳离子和疏水性十二烷基的两亲无规三元共聚物可在水中形成大小可控的胶束。三元共聚物胶束在盐存在的情况下，在水中显示出较低临界溶解温度（LCST）型溶解度。针对这一特点，我们在此研究了含有氯化钠的 PEG/阳离子无规三元共聚物胶束浓水溶液的热致伸缩特性，发现其独特的凝胶化和相变取决于 PEG/阳离子的组成。加热时，PEG/阳离子（2/1、1/1 和 1/2）三元共聚胶束溶液通过 LCST 型相分离表现出两步相变，即从瞬时凝胶化变为粘稠浑浊的溶液。相反，富含阳离子的 PEG/阳离子（1/3）三元共聚胶束和阳离子共聚胶束在室温下于水中形成凝胶，前者在加热后变为粘稠透明的溶液。凝胶的流变特性可通过 PEG/阳离子比率和三元共聚物的聚合度来调节。小角中子散射测量显示，三元共聚物胶束溶液的瞬时凝胶化是通过形成胶束间网络实现的。

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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.