TiO_2/SiO_2催化酯交换法合成PES的工艺
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摘要
采用凝胶–溶胶法合成TiO_2/SiO2催化剂(TSP–44),用于催化丁二酸二甲酯(DMS)和乙二醇(EG)酯交换法合成高分子量聚丁二酸乙二酯(PES)。采用FTIR和1H-NMR确定聚合物结构,系统考察了催化剂浓度、聚合反应温度和时间对聚合反应的影响。经常压酯交换后获得的预聚体在230℃条件下缩聚4.0h后,合成PES的特性黏数[η]可达到0.693dL/g,重均分子量(Mw)和数均分子量(Mn)分别可以达到91 546和52 015,分子量分布系数(PDI)为1.76。热稳定性测试结果显示,酯交换法合成PES失重1%的温度和最大热解速率的温度(Tmax)分别为310℃和398℃。
A TiO_2/SiO_2 catalyst was prepared by a sol-gel route and used to catalyze the transesteri?cation of dimethyl succinate(DMS) with ethylene glycol(EG) to high-molecular-weight poly(ethylene succinate)(PES). The structure of the obtained polymer was con?rmed by the result of FTIR and 1 H-NMR and the effect of catalyst amount,reaction temperature and time on the reaction performance were systematically discussed. It is found that the intrinsic viscosity([η]),weight average molecular weight(Mw)and number average molecular weight(Mn) for the obtained PES after polymerizing the prepolymer from atmospheric transesteri?cation at 230℃ for 4.0 h can achieve to 0.693 dL/g,91 546 and 52 015,respectively,with polymer dispersity index(PDI) value of1.76. The temperature at weightlessness 1% and maximum decomposition temperature(Tmax) are 310℃ and 398℃,respectively.
A TiO_2/SiO_2 catalyst was prepared by a sol-gel route and used to catalyze the transesteri?cation of dimethyl succinate(DMS) with ethylene glycol(EG) to high-molecular-weight poly(ethylene succinate)(PES). The structure of the obtained polymer was con?rmed by the result of FTIR and 1 H-NMR and the effect of catalyst amount,reaction temperature and time on the reaction performance were systematically discussed. It is found that the intrinsic viscosity([η]),weight average molecular weight(Mw)and number average molecular weight(Mn) for the obtained PES after polymerizing the prepolymer from atmospheric transesteri?cation at 230℃ for 4.0 h can achieve to 0.693 dL/g,91 546 and 52 015,respectively,with polymer dispersity index(PDI) value of1.76. The temperature at weightlessness 1% and maximum decomposition temperature(Tmax) are 310℃ and 398℃,respectively.
引文
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[19]Xue Peng,Qiu Zhaobin.Synthesis,thermal properties,and crystallization kinetics of novel biodegradable poly(ethylene succinateco-diethylene glycol succinate)copolyesters[J].Thermochimica Acta,2015,606:45-52.
[20]Li Xiaojing,Qiu Zhaobin.Synthesis and properties of novel poly(ethylenesuccinate-co-decamethylene succinate)copolymers[J].RSC Advances,2015,5:103 713-103 721.
[2]晋慧斌.聚乳酸改性及在包装领域的应用[J].工程塑料应用,2017,45(12):135-138,142.Jin Huibin.Modification of polylactic acid and its application in packaging[J].Engineering Plastics Application,2017,45(12):135-138,142.
[3]朱大勇,徐俊鹏,曹礼彬,等.PLA热稳定性和降解性能研究及其应用[J].工程塑料应用,2018,46(1):119-122.Zhu Dayong,Xu Junpeng,Cao Libin,et al.Thermal stability and the degradation performance of poly(lactic acid)and its application[J].Engineering Plastics Application,2018,46(1):119-122.
[4]唐文强,刘绍英,王公应.合成聚丁二酸乙二醇酯的催化剂及其工艺的研究进展[J].石油化工,2014,43(1):112-117.Tang Wenqiang,Liu Shaoying,Wang Gongying.Progress in catalysts and technics for synthesis of poly(ethylene succinate)[J].Petrochemical Technology,2014,43(1):112-117.
[5]刘伟,石峰晖,王进锋,等.高分子量生物可降解聚丁二酸乙二醇酯的合成与表征[J].高分子材料科学与工程,2009,25(4):8-11.Liu Wei,Shi Fenghui,Wang Jinfeng,et al.Synthesis and characterization of high molecular weight poly(ethylene succinate)biodegradable polyester[J].Polymer Materials Science&Engineering,2009,25(4):8-11.
[6]Seretoudi G,Bikiaris D N,Panayiotou C.Synthesis,characterization and biodegradability of poly(ethylene succinate)/poly(1-caprolactone)block copolymers[J].Polymer 2002,43:5 405-5 415.
[7]马楷,刘绍英,姚洁,等.金属醋酸盐催化合成聚丁二酸乙二醇酯预聚体和碳酸二甲酯[J].应用化学,2010,27(11):1 276-1 281.Ma Kai,Liu Shaoying,Yao Jie,et al.Simultaneous synthesis of poly(ethylene glycol succinate)oligomers and dimethyl carbonate using metal acetates as catalysts[J].Chinese Journal of Applied Chemistry,2010,27(11):1 276-1 281.
[8]马楷,张廷建,刘绍英,等.乙酰丙酮盐催化碳酸乙烯酯和丁二酸二甲酯的耦合反应[J].高分子材料科学与工程,2012,28(4):14-17.Ma Kai,Zhang Tingjian,Liu Shaoying,et al.Coupling reaction of ethylene carbonate and dimethyl succinate by using metal acetylacetone as catalysts[J].Polymer Materials Science&Engineering,2012,28(4):14-17.
[9]殷明,冯润财,李春成,等.基于Ti O2/SiO2溶胶的新型PET缩聚催化剂的合成[J].高等学校化学学报,2010,31(2):418-420.Yin Ming,Feng Runcai,Li Chuncheng,et al.Synthesis of novel catalyst based on TiO2/SiO2 for poly(ethylene terephthalate)[J].Chemical Journal of Chinese Universities,2010,31(2):418-420.
[10]刘峰,杨先贵,李建国,等.碳酸二苯酯与1,4-丁二醇熔融酯交换法合成聚(对亚丁基)碳酸酯的研究[J].高分子学报,2014(5):628-635.Liu Feng,Yang Xiangui,Li Jianguo,et al.Synthesis of poly(butylene carbonate)by melt transesterification of diphenyl carbonate and 1,4-butanediol[J].Acta Polymerica Sinica,2014(5):628-635.
[11]Wang Ziqing,Yang Xiangui,Liu Shaoying,et al.Magnesium acetate used as an effective catalyst for synthesizing aliphatic polycarbonates via melt transesterification process[J].Chem Res Chin Univ,2016,32(3):512-518.
[12]王自庆,杨先贵,刘绍英,等.聚乙烯吡咯烷酮固载卤化锌催化酯交换法合成脂肪族聚碳酸酯[J].高分子学报,2016(12):1 654-1 661.Wang Ziqing,Yang Xiagui,Liu Shaoying,et al.Synthesis of aliphatic polycarbonates by transesterification route with poly(vinylpyrrolidone)-immobilized zinc halide as catalysts[J].Acta Polymerica Sinica,2016(12):1 654-1 661.
[13]王田田,常雪松,田恒水.熔融酯交换法合成异山梨醇型聚碳酸酯[J].工程塑料应用,2016,44(5):39-42.Wang Tiantian,Chang Xuesong,Tian Hengshui.Synthesis of poly(isosobide carbonate)by melt-transesterification process[J].Engineering Plastics Application,2016,44(5):39-42.
[14]Wang J T,Zhu Q,Lu X L,et al,ZnGA-MMT catalyzed the copolymerization of carbon dioxide with propylene oxide[J].European Polymer Journal,2005,41:1 108-1 114.
[15]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):44-46,17.Liu Wei,Shi Fenghui,Ji Junhui,et al.Synthesis and degradability of poly(ethylene succinate)biodegradable polyester[J].Plastics,2008,37(4):44-46,17.
[16]唐文强,刘绍英,欧阳春,等.Zn-MOFs催化合成聚丁二酸乙二醇酯和碳酸二甲酯的研究[J].高分子学报,2016(5):628-636.Tang Wenqiang,Liu Shaoying,Ouyang Chun,et al.Simultaneous synthesis of poly(ethylene succinate)and dimethyl carbonate using Zn-MOFs as catalysts[J].Acta Polymerica Sinica,2016(5):628-636.
[17]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):173-175,211.Sun Jie,Xia Yunxia,Liu Junling,et al.Synthesis of poly(ethylenesuccinate)[J].Chinese Journal of Synthetic Chemistry,2007,15(2):173-175,211.
[18]Qiu Shoutian,Zhang Kangjing,Su Zhiqiang,et al.Thermal behavior,mechanical and rheological properties,and hydrolytic degradation of novel branched biodegradable poly(ethylene succinate)copolymers[J].Polymer Testing,2018,66:64-69.
[19]Xue Peng,Qiu Zhaobin.Synthesis,thermal properties,and crystallization kinetics of novel biodegradable poly(ethylene succinateco-diethylene glycol succinate)copolyesters[J].Thermochimica Acta,2015,606:45-52.
[20]Li Xiaojing,Qiu Zhaobin.Synthesis and properties of novel poly(ethylenesuccinate-co-decamethylene succinate)copolymers[J].RSC Advances,2015,5:103 713-103 721.