Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, PO Box 476, Florianópolis, SC, 88040-900, Brazil.
Appl Biochem Biotechnol. 2019 Nov;189(3):745-759. doi: 10.1007/s12010-019-03043-9. Epub 2019 May 21.
The total or partial substitution of fossil raw materials by biobased materials from renewable resources is one of the great challenges of our society. In this context, the reaction under mild condition as enzyme-catalyzed esterification was applied to investigate the esterification of the biobased 10-undecenoic acid with 2-hydroxyethyl methacrylate (HEMA) to obtain a new diene ester monomer. The environmentally friendly enzymatic reaction presented up to 100% of conversion; moreover, the production of possible by-products was minimized controlling reaction time and amount of enzyme. Furthermore, the presence of chloroform was evaluated during the enzymatic reactions and despite high conversions with higher enzyme concentration, the solvent-free system showed fast kinetics even with 1.13 U/g substrates. In addition, the commercial immobilized lipases Novozym 435 and NS 88011 could be applied for up to 10 cycles keeping conversions about 90%. The scale-up of the reaction was possible and a purification procedure was applied in order to isolate the diene ester monomer 2-(10-undecenoyloxy)ethyl methacrylate, preserving its double bonds, which could allow a potential use of this product in the synthesis of new renewable polymers through techniques as metathesis, thiol-ene, or free-radical polymerization.
用可再生资源的生物基材料替代全部或部分化石原料是我们社会的一大挑战。在此背景下，应用温和条件下的酶催化酯化反应来研究生物基 10-十一烯酸与 2-羟乙基甲基丙烯酸酯（HEMA）的酯化反应，以获得一种新的二烯酯单体。该环保酶促反应的转化率高达 100%；此外，通过控制反应时间和酶用量，最大限度地减少了可能副产物的生成。此外，还评估了在酶促反应过程中氯仿的存在，尽管在较高酶浓度下具有较高的转化率，但无溶剂体系表现出快速动力学，甚至在 1.13 U/g 底物时也是如此。此外，商业固定化脂肪酶 Novozym 435 和 NS 88011 可以重复使用 10 次，转化率保持在 90%左右。反应可以放大，并且应用了一种纯化程序来分离二烯酯单体 2-(10-十一烯酰氧基)乙基甲基丙烯酸酯，保留其双键，这可能允许通过例如复分解、硫醇-烯、或自由基聚合等技术将该产品用于合成新的可再生聚合物。
