Efficient synthesis of PMMA in green solvents of choline chloride and glycerol-based deep eutectic solvents

IF 5.4 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers Pub Date : 2026-02-01 Epub Date: 2025-11-28 DOI:10.1016/j.reactfunctpolym.2025.106581

Rawda Maen Sunoqrot , Putri Nur Amelina Muhammad Shamsudin Ng , Amjad Abedelqader , Hesham Ali Metwally Ali El-enshasy , Mohamad Hamdi Zainal Abidin , Chen Qian , Naharullah Jamaluddin

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引用次数: 0

Abstract

Polymethyl methacrylate (PMMA) is a widely utilized thermoplastic in electronic applications, packaging, and biomedical devices. However, conventional PMMA is synthesized in volatile organic solvents such as toluene, significantly impacting the environment. This issue needs an urgent alternative to minimize the toxicity of organic solvents. Herein, this study reports the synthesis of PMMA in choline chloride and Glycerol-based DES (ChCl/Gly DES) via free radical polymerization (FRP), as there is significantly less work done using fashionable and environmentally friendly DESs in the synthesis of PMMA. This DES enhances the polymerization performance through stabilizing the monomer and initiator via hydrogen bonding. A 50:50 wt% ratio of MMA to DES with 0.5 wt% APS at 60 °C for 6 h yielded the highest monomer conversion of 99.5 %. A comprehensive characterization using ¹H NMR, FTIR, DSC, TGA, and GPC was conducted to evaluate the polymer performance. Results revealed a high molecular weight polymer of 246,518 g/mol with a notably high glass transition (T_g) of 123.2 °C. FTIR confirmed the hydrogen bonding formed between PMMA and DES, contributing to the high thermal stability and reduced brittleness. The involvement of DES lowered activation energy (Ea = 23.3 kJ/mol) compared to the conventional solvents, and exhibited a higher apparent rate constant (0.883 h⁻¹). These findings highlight ChCl/Gly DES as a green alternative to organic solvents and also its capability in producing an efficient PMMA-DES.

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在氯化胆碱和甘油基深共晶绿色溶剂中高效合成PMMA

聚甲基丙烯酸甲酯（PMMA）是一种广泛应用于电子应用、包装和生物医学设备的热塑性塑料。然而，传统的PMMA是在甲苯等挥发性有机溶剂中合成的，对环境影响很大。这个问题迫切需要一个替代方案，以尽量减少有机溶剂的毒性。在此，本研究报告了在氯化胆碱和甘油基DES （ChCl/Gly DES）中通过自由基聚合（FRP）合成PMMA，因为使用时尚且环保的DES合成PMMA的工作要少得多。该DES通过氢键稳定单体和引发剂，提高了聚合性能。MMA与DES质量比为50:50，APS质量比为0.5 wt%，温度为60℃，反应时间为6 h，单体转化率最高，为99.5%。采用1H NMR、FTIR、DSC、TGA、GPC等手段对聚合物进行了综合表征。结果表明，聚合物的分子量为246,518 g/mol，玻璃化转变（Tg）温度高达123.2℃。FTIR证实了PMMA和DES之间形成的氢键，有助于高热稳定性和降低脆性。与传统溶剂相比，DES的加入降低了反应的活化能（Ea = 23.3 kJ/mol），并表现出较高的表观速率常数（0.883 h−1）。这些发现突出了ChCl/Gly DES作为有机溶剂的绿色替代品，以及它在生产高效PMMA-DES方面的能力。

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来源期刊

Reactive & Functional Polymers 工程技术-高分子科学

CiteScore

8.90

自引率

5.90%

发文量

259

审稿时长

27 days

期刊介绍： Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers. Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.