乙醇酸低聚物解聚催化剂的筛选及催化热解动力学研究.docVIP

乙醇酸低聚物解聚催化剂的筛选及动力学研究 姜海建，崔爱军，尹芳华，韦梅峻，何明阳，陈群* （常州大学 江苏省绿色催化材料与技术重点实验室，江苏 常州 213164） 摘要：通过解聚乙醇酸低聚物（PGA），乙酰丙酮锌催化可以明显降低反应体系的解聚温度，能够减轻乙交酯制备过程中的结焦现象，提高乙交酯的收率，进一步将其应用于PGA的溶剂共沸解聚工艺中，可以防止共沸溶剂在较高的温度下发生热劣化现象。对乙酰丙酮锌与传统金属氧化物在催化机理上进行了探讨，并且利用热重分析对PGA低聚物的降解过程进行了动力学分析。实验研究结果表明，乙酰丙酮锌作为催化剂反应体系的解聚温度仅为200℃，加入量为低聚物质量的0.4%，乙交酯收率最高可达95%，且PGA低聚物在其催化作用下与传统催化剂三氧化二锑相比其所需的活化能更低，裂解更容易进行。 关键词：乙醇酸；乙交酯；溶剂共沸解聚；乙酰丙酮锌 中图分类号：TQ316 文献标志码：A 文章编号： earch on the catalyst selection and thermal kinetics for the process of oligomeric PGA depolymerization JIANG Hai-jian, CUI Ai-jun, YIN Fang-hua , WEI Mei-Jun ,HE Ming-yang, CHEN Qun* (Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology Changzhou 213164，Jiangsu，China)Abstract： metal oxides and salts as catalysts were investigated in the depolymerization of polyglyolic acid (PGA) oligomers. It was found that the temperature of depolymerization reaction decreased obviously under the catalyst of Zn(acac)2, and the coking was reduced in the process of preparing glycolide with the improved yield of glycolide. Then Zn(acac)2 was applied in the solution depolymerization of PGA, and thermal degradation of the azeotropic solvent was prevented in high temperature. It proves that Zn(acac)2 can enhance the efficiency of depolymerization and the higher catalytic activity was thought to be related to the coordination?insertion mechanism. The experimental results showed that, PGA oligomer was depolymerized in lower temperature of 200℃ under Zn(acac)2 catalyst with a mass fraction of 0.4%, and the yield of glycolide reach 95%, As the chain length of the oligomeric PGA is shortened to the extent purely random degradation. The activation energy value in process of oligomer depolymerization was lower in the presence of Zn(acac)2 than the other catalysts, and this could enhance the efficiency of depolymerization. Key words: glycolic acid；glycolide；solution –phase depolymerization；Zinc(II) Acetylacetonate 聚乙交酯（PGA）作为优良的生物可降解材料之一，近些年来成为聚合物领域研究的重点[-3]。高分子量PGA