固定化脂肪酶催化合成生物基增塑剂2,5-呋喃二甲酸正丁酯

Synthesis of bio-based plasticizer dibutylfuran-2,5-dicarboxylate catalyzed by immobilized lipase

摘要:

2,5-呋喃二甲酸正丁酯（DBF）因其具有类似邻苯二甲酸酯的化学结构和理化性质、良好的生物相容性、并且能够通过代谢进入人体内的三羧酸循环等特点，有望成为一种可替代石油基邻苯二甲酸酯的新型绿色环保型增塑剂。本文研究了生物基增塑剂2,5-呋喃二甲酸正丁酯的酶法合成工艺，以脂肪酶为催化剂，在甲苯体系中催化2,5-呋喃二甲酸二甲酯与正丁醇转酯化反应制备2,5-呋喃二甲酸正丁酯，对酶促合成2,5-呋喃二甲酸正丁酯的工艺进行优化，并探讨了糖类物质和吸附剂作为添加剂对酶法转酯化收率的影响。结果表明在2,5-呋喃二甲酸二甲酯与正丁醇底物摩尔比为1∶5，固定化脂肪酶Novozym435添加量为0.005 g/mL（925U）的10 mL甲苯溶液中，45 ℃、180 r/min反应28 h后，2,5-呋喃二甲酸正丁酯的产率达到最大。在反应体系中添加4A型分子筛能明显促进DBF的生成，海藻糖的加入也增强了反应体系中脂肪酶的催化能力，反应体系中加入0.2 g/mL的4A型分子筛和酶用量15%的海藻糖，45 ℃反应14 h后2,5-呋喃二甲酸正丁酯的产率达到了87%。

Abstract:

Dibutylfuran-2,5-dicarboxylate (DBF) was expected to be a new substitute for petroleum phthalate green plasticizer because of its chemical structure and physical properties similar to phthalate esters, good biocompatibility, and metabolism to human tricarboxylic acid cycle. In this study, the enzymatic synthesis process of bio-based plasticizer dibutylfuran-2,5-dicarboxylate was introduced. In toluene system, dimethyl 2,5-furandicarboxylate was esterified with butanol under the catalysis of lipase, and dibutyl 2,5-dicarboxylate was prepared. The synthesis process of dibutylfuran-2,5-dicarboxylate was optimized, and the effects of sugars and adsorbents as additives on the yield of enzymatic transesterification were discussed. The results showed that when the molar ratio of substrate was 1: 5, the dosage of Novozym435 was 0.005 g/ml, the reaction conditions was 45 ℃,180 r/min in 10 ml toluene solution, and the reaction time was 30 h, the yield of dibutylfuran-2,5-dicarboxylate was the highest. The addition of 4A molecular sieve could obviously promote the formation of dibutylfuran-2,5-dicarboxylate, and the addition of trehalose can also enhance the catalytic ability of lipase. The yield of dibutylfuran-2,5-dicarboxylate reached 87% after adding 0.2 g/ml 4A molecular sieve and 15% trehalose into the reaction system and reacting at 45℃ for 14 h.