生物基乙交酯及聚乙醇酸的制备与性能  

Preparation and properties of bio-based glycolide and polyglycolic acid

作　　者：李秀峥 白富栋 张雷 孙启梅[1,2,3] 白毓黎 刘来伍 王鹏翔 LI Xiuzheng;BAI Fudong;ZHANG Lei;SUN Qimei;BAI Yuli;LIU Laiwu;WANG Pengxiang(SINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co.,Ltd.,Dalian 116045,China;SINOPEC Key Laboratory of Research and Development and Application of Degradable Materials and Monomers,Dalian 116045,China;Dalian Key Laboratory of Degradable Polymer Materials,Dalian 116045,China)

机构地区：[1]中石化(大连)石油化工研究院有限公司,辽宁大连116045 [2]中国石化可降解材料及单体研发与应用重点实验室,辽宁大连116045 [3]大连市可降解高分子材料重点实验室,辽宁大连116045

出　　处：《工程塑料应用》2025年第3期16-23,共8页Engineering Plastics Application

摘　　要：聚乙醇酸(PGA)是一种可降解高分子材料,具有优良的生物相容性、力学性能、气体阻隔性及降解性能。为了实现由生物基原料出发制备PGA,首先以生物基原料微晶纤维素制备乙醇酸甲酯,并水解合成乙醇酸,进而制备乙交酯及PGA。介绍了纤维素制备乙醇酸甲酯的工艺流程,并对催化剂种类、纤维素用量、催化剂用量、反应温度、反应时间、初始反应压力进行了考察,得到了工艺条件对乙醇酸甲酯收率的影响规律。当纤维素用量为0.5 g、偏钨酸铵催化剂用量为0.15 g、甲醇用量为50 mL、反应温度为250℃、反应时间为2 h、初始反应压力为2 MPa时,乙醇酸甲酯收率最大,为33.0%。以乙醇酸甲酯为原料水解反应精馏制备乙醇酸,考察了水解催化剂、反应水酯比(水与乙醇酸甲酯物质的量比)、反应温度对乙醇酸甲酯转化率的影响。结果表明,当乙醇酸甲酯水解催化剂为D005-Ⅱ,水酯比为7∶1,反应温度为80~85℃时,乙醇酸甲酯转化率最高,达到98.2%。以乙醇酸为原料合成了乙交酯并进行精制,制备得到的乙交酯符合Q/PJIM 004-2021标准性能指标要求,可作为聚合级乙交酯使用。最后进行了乙交酯开环聚合实验得到了PGA,其熔点为221.4℃,玻璃化转变温度为37.2℃,特性黏度为0.45 dL/g。由生物基原料纤维素出发制备PGA,具有绿色低碳的优点。Polyglycolic acid(PGA)is a biodegradable polymer material that exhibits excellent biocompatibility,mechanical properties,gas barrier properties,and degradation performance.In order to prepare PGA from bio-based raw materials,methyl glycolate was prepared from bio-based raw material microcrystalline cellulose,and then was hydrolyzed to synthesize glycolic acid,at last,the glycolide and PGA were prepared.The technological process for the preparation of methyl glycolate from cellulose was presented.The types of catalysts,the amount of cellulose,the amount of catalyst,reaction temperature,reaction time,and initial reaction pressure were examined,and the influence of the process conditions on the yield of methyl glycolate was determined.Under the reaction conditions of 0.5 g cellulose,0.15 g ammonium metatungstate catalyst,50 mL methanol,reaction temperature of 250℃,reaction time of 2 h,and initial reaction pressure 2 MPa,the maximum yield of methyl glycolate is 33.0%.Hydrolysis reaction distillation was employed to prepare glycolic acid using methyl glycolate as the raw material.The effects of hydrolysis catalysts,the water-to-ester ratio(mole ratio of water to methyl ethanoate)in the reaction,and the reaction temperature on the conversion rate of methyl glycolate were investigated.The results show that,when the hydrolysis catalyst of methyl glycolate is D005-II,the water-toester ratio is 7∶1 and the reaction temperature is 80-85℃,the conversion rate of methyl glycolate is the highest and can reach 98.2%.Glycolic acid was used as raw material to synthesize and refine glycolide.The prepared glycolide can meet the performance indexes requirements of Q/PJIM 004-2021 standard and can be used as polymerization grade glycolide.Finally,the ring opening polymerization experiment of glycolide was conducted for preparing PGA.The melting point of PGA is 221.4℃,glass transition temperature is 37.2℃,and the intrinsic viscosity is 0.45 dL/g.The preparation of PGA from bio-based raw material cellulose has the advantages o

关 键 词：聚乙醇酸 乙交酯 乙醇酸甲酯 乙醇酸 纤维素 生物基 可降解 

分 类 号：TQ322.3[化学工程—合成树脂塑料工业]