POM-ILs的制备及其在聚混合二元酸乙二醇酯合成中的应用  

Preparation of POM-ILs and their application in synthesis of polyglycol mixed dibasic acid ester

作　　者：王雪健 徐铁军[1] 郭立颖[1] 孙营晰 WANG Xuejian;XU Tiejun;GUO Liying;SUN Yingxi(School of Petrochemical Engineering,Shenyang University of Technology,Liaoyang 111003,Liaoning,China)

机构地区：[1]沈阳工业大学石油化工学院,辽宁辽阳111003

出　　处：《精细化工》2024年第8期1737-1744,共8页Fine Chemicals

基　　金：国家自然科学基金项目(22278271)。

摘　　要：制备了以Sn、Fe、Ti、Zn为配位金属的Keggin型单取代多金属氧酸盐离子液体(POM-ILs)催化剂,利用FTIR、XRD、SEM、EDS及TGA对催化剂进行了表征和测试,将其用于催化混合二元酸二甲酯(DBE)与碳酸乙烯酯(EC)反应合成聚混合二元酸乙二醇酯(PDBE),考察了不同配位金属对POM-ILs催化活性的影响。采用FTIR、GPC、TGA、DSC和微机控制电子万能试验机对PDBE进行了测试,并对PDBE的酶降解性能进行了测试。结果表明,Sn单取代的锌钨酸盐离子液体[Bmim]_(6)ZnW_(11)SnO_(39)(H_(2)O)的催化性能最优,在n(EC)∶n(DBE)=1.5∶1、反应时间5 h、温度215℃、催化剂用量为总原料质量的1.1%的条件下,PDBE预聚物选择性为57.85%,收率为54.76%。在反应时间3.5 h、反应温度220℃的最佳条件下,制备的PDBE特性黏数达到0.591dL/g,拉伸强度为33.4 MPa,断裂伸长率为17.9%;数均相对分子质量为14433,重均相对分子质量为33429,平均相对分子质量为70859,多分散性指数(PDI)为2.3161。当添加质量浓度为1.2 g/L固化脂肪酶435的磷酸盐缓冲溶液降解至质量剩余率为2%~3%时,PDBE需28 d,而聚丁二酸乙二醇酯需30 d。Mono-substituted polyoxometalate ionic liquids(POM-ILs)catalysts of Keggin-type with Sn,Fe,Ti and Zn as coordination metals were prepared,characterized and analyzed by FTIR,XRD,SEM,EDS and TGA.The POM-ILs were then applied to catalyze the synthesis of polyglycol mixed dibasic acid ester(PDBE)from dimethyl dibasic acid(DBE)and ethylene carbonate(EC),with the influence of different coordination metals on their catalytic activity evaluated.Product PDBE was further characterized by FTIR,GPC,TGA,DSC and microcomputer control electronic universal testing machine,and assessed for its enzymatic degradation performance.The results showed that Sn mono-substituted zinc tungstate ionic liquid[Bmim]_(6)ZnW_(11)SnO_(39)(H_(2)O)exhibited the best catalytic performance.Under the optimum conditions of n(EC)∶n(DBE)=1.5∶1,reaction time 5 h,reaction temperature 215℃,catalyst dosage being 1.1%of the total mass of raw materials,the selectivity and yield of PDBE prepolymer were 57.85%and 54.76%.Under the optimum polycondensation conditions of reaction time 3.5 h,reaction temperature 220℃,the PDBE obtained showed an intrinsic viscosity of 0.591 dL/g,a tensile strength of 33.4 MPa,an elongation at break of 17.9%,a relative number-average molecular mass of 14433,a relative weight-average molecular mass of 33429,an average relative molecular mass of 70859,and a polydispersity index(PDI)of 2.3161.When the phosphate buffer solution of Novozymes immobilized lipase 435 with a mass concentration of 1.2g/L was added to degrade to a mass residual rate of 2%~3%,PDBE took 28 d,while poly(ethylene succinate)(PES)took 30 d.

关 键 词：多金属氧酸盐 离子液体 催化剂 尼龙酸 聚混合二元酸乙二醇酯 生物可降解聚酯 功能材料 

分 类 号：TQ323.4[化学工程—合成树脂塑料工业]