通过直接酯化法,以2,5-噻吩二羧酸(TDCA)和乙二醇(EG)为原料,钛酸丁酯为催化剂,合成了新型的聚2,5-噻吩二羧酸乙二醇酯。采用红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)、差示扫描量热法(DSC)、热重分析(TGA)、电子单纤强力仪对制得的聚2,5-噻吩二羧酸乙二醇酯和纤维进行了测试。研究结果表明:2,5-噻吩二羧酸乙二醇酯的玻璃化转变温度为63.2℃,熔点为185.5℃,起始热分解温度(失重率2%条件下)为353.9℃,主要失重温度为412℃,具有良好的热稳定性;2,5-噻吩二羧酸乙二醇酯纤维的断裂强度最高可达2.92cN/dtex。
Novel poly(ethylene 2,5-thiophenedicarboxylate) was synthesized via direct esterification method based on 2,5-thiophenedicarboxylic acid and ethylene glycol.Tetrabutyl titanate was used as catalyst.The behaviour of polymer and fibers were studied by FT-IR,1H-NMR,DSC,TGA and single fiber strength tester.The results of DSC showed that the glass transition temperature(Tg) and the melting temperature (Tm) of polyester were 63.2 and 185.5℃,respectively.The initial thermal decomposition temperature (under a weight loss rate of 2%) was 353.9℃.Moreover,the maximum decomposition temperature was about 412℃,which indicated it also had good thermal stability.The fracture strength of polyester could reach to 2.92cN/dtex as the draw ratio rising.
[1]Ragauskas A J,Williams C K,Davison B H,et al.The path forward for biofuel sand biomaterials[J].Science,2006,311(5760):484-489.
[2]周佳栋,曹飞,余作龙,等.生物基聚酯单体2,5-呋喃二甲酸的制备及应用研究进展[J].高分子学报,2016(1):1-13.
[3]Knoop R J I,Vogelzang W,van Haveren J,et al.High molecular weight poly(ethylene-2,5-furanoate);critical aspects in synthesis and mechanical property determination[J].Journal of Polymer Science Part A Polymer Chemistry,2013,51(19):4191-4199.
[4]Ma J P,Yu X F,Xu J,et al.Synthesis and crystallinity of poly(butylene 2,5-furandicarboxylate)[J].Polymer,2012,53(19):4145-4151.
[5]Gomes M,Gandini A,Silvestre A J D,et al.Synthesis and characterization of poly(2,5-furan dicarboxylate)s based on a variety of diols[J].Journal of Polymer Science Part A Polymer Chemistry,2011,49(17):3759-3768.
[6]Ma J P,Pang Y,Wang M,et al.The copolymerization reactivity of diols with 2,5-furandicarboxylic acid for furan-based copolyester materials[J].Journal of Materials Chemistry,2012,22(8):3457-3461.
[7]Sousa A F,Matos M,Freire C S R,et al.New copolyesters derived from terephthalic and 2,5-furandicarboxylic acids:a step forward in the development of biobased polyesters[J].Polymer,2013,54(2):513-519.
[8]Mincheva R,Delangre A,Raquez J-M,et al.Biobased polyesters with composition-dependent thermomechanical properties:synthesis and characterization of poly(butylene succinate-co-butylene azelate)[J].Biomacromolecules,2013,14(3):890-899.
[9]Zhu J H,Cai J L,Xie W C,et al.Poly(butylene 2,5-furan dicarboxylate),a biobased alternative to PBT:synthesis,physical properties,and crystal structure[J].Macromolecules,2013,46(3):796-804.
[10]Munoz-Guerra S,Lavilla C,Japu C,et al.Chemlnform abstract:renewable terephthalate polyesters from carbohydrate-based bicylic monomers[J].Green Chemistry,2014,16(4):1716-1739.
[11]Roux M V,Temprado M,Jimenez P,et al.Thermochemistry of 2,5-thiophenedicarboxylic acid[J].Journal of Physical Chemistry A,2006,110(45):12477-12483.
[12]Gong Y,Wang T,Zhang M,et al.Synthesis,structure and property of metal thiophene-2,5-dicarboxylate:novel three dimensional coordination polymers[J].Journal of Molecular Structure,2007,833:1-7.
[13]丁为民,吴宝华,赵春山,等.噻吩-2,5-二羧酸合成方法的研究[J].化学工程师,2005,19(2):33-34.
[14]Li K X,Song X F,Zhang D.Molecular weight evalution of depolymerized poly(ethylene terephthalate) using intrinsic viscosity[J].Journal of Applied Polymer Science,2008,109(2):1294-1297.
[15]魏家瑞.热塑性聚酯及其应用[M].北京:化学工业出版社,2011,76-80.
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