Synthesis and Characterization of Methacrylated Eugenol as a Sustainable Reactive Diluent for a Maleinated Acrylated Epoxidized Soybean Oil Resin
Synthesis and Characterization of Methacrylated Eugenol as a Sustainable Reactive Diluent for a Maleinated Acrylated Epoxidized Soybean Oil Resin
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DOI：
10.1021/acssuschemeng.7b01673
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发表时间：
2017-10-01
影响因子：
8.4
通讯作者：
Kessler, Michael R.
中科院分区：
文献类型：
--
作者：
Zhang, Yuehong;Li, Yuzhan;Kessler, Michael R.
以丁香酚和甲基丙烯酸酐为原料，通过Steglich酯化反应，合成了一种可再生的芳香单体--甲基丙烯酸丁香酚(ME)。随后将得到的ME用作活性稀释剂，与商业马来酸酯化环氧化大豆油(MAESO)树脂共聚，形成可再生的MAESO ME热固性树脂。考察了ME的挥发性，分析了MAESO ME混合物的粘度和固化行为。系统研究了不同ME含量(0%、20%、40%、60%、80%和100%)的MAESO ME热固性树脂的固化动力学、热机械性能和热稳定性。结果表明，ME单体具有极低的挥发率(在30℃等温放置10h后，质量损失小于3%)、高生物基碳含量(BBC，71.4%)和低粘度(25℃时为17.6CP)。与MAESO树脂一起使用时，体系的粘度显著降低。与按当量MAESO相比，ME稀释体系表现出更高的反应活性，从而改善了MAESO-ME体系的固化程度和交联度。随着ME含量从0%增加到100%，MAESO-ME热固性树脂的玻璃化转变温度(T-g)从61.1℃提高到139.3℃。总体而言，开发的基于生物的ME单体被证明是一种有效的、可持续的活性稀释剂，可以取代苯乙烯用于商业上可获得的MAESO树脂。
This work presents a solvent-free, facile synthesis of a renewable, aromatic monomer, methacrylated eugenol (ME), from eugenol and methacrylic anhydride by the Steglich esterification reaction. The resulting ME was subsequently used as a reactive diluent to copolymerize with a commercial maleinated acrylated epoxidized soybean oil (MAESO) resin to form renewable MAESO ME thermosets. The volatility of ME was examined, along with an analysis of viscosity and curing behavior of the MAESO ME mixtures. The curing kinetics, thermo-mechanical properties, and thermal stabilities of the fully cured MAESO ME thermosets with different ME proportions (0%, 20%, 40%, 60%, 80%, and 100%) were systematically investigated. The results indicated that ME monomer exhibited extremely low volatility (less than 3% mass loss after being held isothermally at 30 degrees C for 10 h), high biobased carbon content (BBC, 71.4%), and low viscosity (17.6 cP at 25 degrees C). Upon use with MAESO resin, viscosity of the system was considerably decreased. Compared with per equivalent of MAESO, ME-diluted systems exhibited higher reactivity, which resulted in improved curing extent and higher cross-link density of the MAESO-ME systems. The glass transition temperature (T-g) of MAESO-ME thermosets greatly improved from 61.1 to 139.3 degrees C with increasing ME loading from 0% to 100%. Overall, the developed biobased ME monomer is shown to be an effective, sustainable reactive diluent to replace styrene for commercially available MAESO resin.