Conformational energy inversion in PMMA crystals prepared via thermal quenching with entropy diluents

IF 4.5 2区化学 Q2 POLYMER SCIENCE Polymer Pub Date : 2025-03-26 DOI:10.1016/j.polymer.2025.128318

Thanh Van Vu , Jae Hyun Sim , Jinwoo Choi , Hokyeong Jeong , Seungjoo Park , Sangho Kim , Sangeun Baek , Hyunmin Lee , Youngjong Kang

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Abstract

This study investigates the conformational structure of hypocrystalline poly(methyl methacrylate) (PMMA) films (hc-PMMAs) prepared via thermal quenching with benzoic acid (BA) as an entropy diluent. FT-IR spectroscopy revealed a significant increase in the trans-gauche (tg) conformation in hc-PMMAs compared to their solution-cast PMMA counterparts. The presence of BA stretched the polymer chains, promoting crystallization. Conformational energy calculations showed that the tg conformation became more stable than the trans-trans (tt) form, contrary to natural PMMA, due to chain stress from the quenching process. Thermal analysis demonstrated a unique tg plateau below the glass transition temperature (T_g), followed by relaxation to tt above T_g. These findings highlight the potential for manipulating polymer conformation and crystallinity using entropy diluents.

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熵稀释剂热猝灭制备PMMA晶体的构象能反转

研究了苯甲酸（BA）作为熵稀释剂，通过热猝灭法制备的聚甲基丙烯酸甲酯（PMMA）薄膜（hc-PMMA）的构象结构。FT-IR光谱显示，与溶液型PMMA相比，hc-PMMA的反式间扭式（tg）构象显著增加。BA的存在拉伸了聚合物链，促进了结晶。构象能计算表明，与天然PMMA相反，由于淬火过程中的链应力，tg构象比trans-trans （tt）构象更稳定。热分析表明，在玻璃化转变温度（tg）以下有一个独特的tg平台，然后在tg以上松弛到tt。这些发现突出了利用熵稀释剂操纵聚合物构象和结晶度的潜力。

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来源期刊

Polymer 化学-高分子科学

CiteScore

7.90

自引率

8.70%

发文量

959

审稿时长

32 days

期刊介绍： Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.