可降解脂肪族聚酯的合成及酶解性能研究
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摘要
采用溶液缩聚法合成了3种不同的脂肪族聚酯——聚琥珀酸乙二醇酯、聚琥珀酸丁二醇酯和聚琥珀酸己二醇酯。利用傅里叶变换红外光谱仪、核磁共振氢谱仪、差示扫描量热仪、热重分析仪、接触角测量仪、X射线衍射仪和力学拉伸仪对合成的聚酯进行分析表征,并研究了三者的酶解性能。实验结果表明:3种脂肪族聚酯综合性能较优,拉伸强度均超过30MPa,断裂伸长率均大于300%;3种聚酯的热分解温度高于294℃,热稳定性良好;酶解实验表明,降解12h时3种聚酯的降解率均超过95%,可降解性良好。其中,聚琥珀酸己二醇酯表现出最优力学性能、热稳定性和可降解性,其拉伸强度为33.4MPa,断裂伸长率为798.3%,热分解温度达到314℃,且在降解4h时失重率高达88.1%,11h可实现完全降解。
Three different aliphatic polyesters,poly(ethylene glycol succinate)(PES),poly(butylene succinate)(PBS),and poly(hexamethylene succinate)(PHS),were synthesized by solution polycondensation.The synthesized polyesters were characterized by FT-IR,1 H-NMR,DSC,TG,WCA,XRD and mechanical extensors.The enzymatic properties of composites were also studied.The results showed that the tensile strength of three polyesters was above30 MPa and the elongation break was more than 300%.The thermal decomposition temperature was higher than 294℃,and the thermal stability was well.At the same time,the degradation rate was more than 95% at 12 h,and the biodegradability was excellent.Among these polymers,PHS showed the optimal mechanical properties and degradability.That was,the tensile strength reached 33.4 MPa,the elongation at break of 798.3%,and the decomposition temperature of 314℃.The enzymatic experiment showed that the degradation rate of PHS was as high as88.1% at 4 h,and it was completely degraded at 11 h.
Three different aliphatic polyesters,poly(ethylene glycol succinate)(PES),poly(butylene succinate)(PBS),and poly(hexamethylene succinate)(PHS),were synthesized by solution polycondensation.The synthesized polyesters were characterized by FT-IR,1 H-NMR,DSC,TG,WCA,XRD and mechanical extensors.The enzymatic properties of composites were also studied.The results showed that the tensile strength of three polyesters was above30 MPa and the elongation break was more than 300%.The thermal decomposition temperature was higher than 294℃,and the thermal stability was well.At the same time,the degradation rate was more than 95% at 12 h,and the biodegradability was excellent.Among these polymers,PHS showed the optimal mechanical properties and degradability.That was,the tensile strength reached 33.4 MPa,the elongation at break of 798.3%,and the decomposition temperature of 314℃.The enzymatic experiment showed that the degradation rate of PHS was as high as88.1% at 4 h,and it was completely degraded at 11 h.
引文
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[2]Bikiaris D N,Papageorgiou G Z,Achilias D S.Synthesis and comparative biodegradability studies of three poly(alkylene succinate)s[J].Polymer Degradation and Stability,2006,91(1):31-43.
[3]Ye H M,Liu P,Wang C X,et al.Polymorphism regulation in poly(hexamethylene succinate-co-hexamethylene fumarate):altering the hydrogen bonds in crystalline lattice[J].Polymer,2017,108:272-280.
[4]Fujimaki T.Processability and properties of aliphatic polyesters,‘BIONOLLE’,synthesized by polycondensation reaction[J].Polymer Degradation and Stability,1998,59(1):209-214.
[5]刘伟,石峰晖,季君晖,等.生物可降解聚丁二酸乙二醇酯的合成与降解性能研究[J].塑料,2008,37(4):44-47.
[6]何金欢.PBS及P(BS-co-1,2-PS)的二元酰氯扩链合成及其生物降解研究[D].西安:陕西科技大学,2012.
[7]吴梓新,李铮,陶震.酯交换合成PBS用催化剂的研究[J].塑料工业,2012,40(1):9-2.
[8]Hoftyzer P J.Properties of polymers:correlations with chemical structure[M].Amsterdam:Elsevier Publishing Company,1972:130-168.
[9]Wang S G,Bo Q.Polycaprolactone-poly(ethylene glycol)block copolymer,Ⅰ:synthesis and degradability in vitro[J].Polymers for Advanced Technologies,1993,4(6):363-366.
[10]孙杰,廖肃然,陆铭,等.脂肪族聚酯的热稳定性研究[J].高分子材料科学与工程,2007,23(6):144-147.
[11]曾建,王苓.热处理对高密度聚乙烯结晶度及力学性能的影响[J].塑料制造,2016(5):48-52.
[12]孙杰,夏云霞,刘俊玲,等.聚丁二酸乙二醇酯的合成[J].合成化学,2007,15(2):173-175.
[13]张昌辉,张敏,赵霞.高相对分子质量可生物降解聚丁二酸丁二醇酯的合成[J].石油化工,2009,38(2):185-188.
[14]Shirahama H,Kawaguchi Y,Aludin M S,et al.Synthesis and enzymatic degradation of high molecular weight aliphatic polyesters[J].Journal of Applied Polymer Science,2001,80(3):340-347.
[15]胡洁,李东风,臧红霞,等.PBS降解塑料降解性能的研究[J].化工新型材料,2016,44(3):175-177.
[16]Fields R D,Rodriguez F,Finn R K.Microbial degradation of polyesters:polycaprolactone degraded by P.pullulans[J].Journal of Applied Polymer Science,1974,18(12):3571-3579.