催化剂循环使用合成聚甲基膦酸乙二醇酯
|
摘要
膦酸酯是一类优秀的阻燃剂,被广泛地应用在各种阻燃材料中。聚甲基膦酸乙二醇酯(PEMP)是其中的一种。对催化剂循环使用合成PEMP进行了研究,用傅里叶红外光谱(FTIR)和磷核磁共振光谱(31PNMR)跟踪了循环使用催化剂的合成过程。结果表明,催化剂可以循环使用三次,继续循环,由于产品黏度增高,催化剂与产品分离困难。根据31PNMR计算PEMP的聚合度发现,催化剂循环使用,可以提高产品的聚合度。催化剂第一次使用所得PEMP产品的聚合度为6.64,循环使用三次,产品聚合度能提高到19.62。循环使用催化剂,PEMP收率基本不变,维持在60%左右。
The phosphonate is a kind of excellent flame retardant which is widely applied in all kinds of flame retardant materials, and the poly(oxy-1,2-ethanediyl)methylphosphonate(PEMP)is one of them. The synthesis of PEMP with recycled catalyst is studied. The FTIR and31 PNMR is used to trace the process of synthesis with recycled catalyst. The results show that the catalyst can be reused for 3 times. If continue using, it will be too difficult to separate the catalyst with the product due to the viscosity enhanced with increasing recycling times. By calculating the degree of poly-merization of PEMP according to the31 PNMR, it is found that the recycling of catalyst can improve the degree of polymerization of PEMP. When the catalyst is first used, the degree of polymerization of PEMP is 6.64; and after 3 times of recycling of catalyst, the degree of polymerization of product can reach 19.62. The yield of PEMP essentially unchanged by the recycling of catalyst, remains about 60%.
The phosphonate is a kind of excellent flame retardant which is widely applied in all kinds of flame retardant materials, and the poly(oxy-1,2-ethanediyl)methylphosphonate(PEMP)is one of them. The synthesis of PEMP with recycled catalyst is studied. The FTIR and31 PNMR is used to trace the process of synthesis with recycled catalyst. The results show that the catalyst can be reused for 3 times. If continue using, it will be too difficult to separate the catalyst with the product due to the viscosity enhanced with increasing recycling times. By calculating the degree of poly-merization of PEMP according to the31 PNMR, it is found that the recycling of catalyst can improve the degree of polymerization of PEMP. When the catalyst is first used, the degree of polymerization of PEMP is 6.64; and after 3 times of recycling of catalyst, the degree of polymerization of product can reach 19.62. The yield of PEMP essentially unchanged by the recycling of catalyst, remains about 60%.
引文
[1]王玉忠,郑长义。聚苯基膦酸二苯砜酯的合成与表征[J].高分子材料科学与工程,1999(1):53~56.
[2] RANGANATHAN T, BEAULIEU M, ZILBERMAN J, et al. Thermal degradation of deoxybenzoin polymers studied by pyrolysisgas chromatography/mass spectrometry[J]. Polymer Degradation&Stability, 2008, 93(6):1059~1066.
[3] SILIESCU S, AVRAM E, VISA A, et al. New technique for the synthesis of polyphosphoesters[J]. Macromole Res,2011,19:1186~1191.
[4]马作广,陈明清.新型环状磷酸酯的合成及其阻燃性能研究[J].精细化工, 2018, 35(2):320~325.
[5]孙才英,董子琳,姜大伟.聚甲基膦酸乙二醇酯阻燃棉布的性能[J].精细化工, 2017, 34(9):1058~1062.
[6]董懿嘉.聚膦酸酯阻燃玉米秸秆粉复合聚氨酯材料研究[D].哈尔滨:东北林业大学,2018.
[7]丁思月,姚玥玮,方霁堃.反应型低聚有机膦酸酯阻燃剂的合成与应用[J].聚氨酯工业, 2012, 27(6):17~20.
[8]程超,孙才英.[Bmim]BF4/p-TSA催化合成聚甲基膦酸乙二醇酯[J].精细化工, 2013, 30(10):1155~1159.
[9]吴强,李乾文,于元浩,等.聚甲基膦酸乙二醇酯的催化合成与封端[J].化学与黏合, 2015, 37(4):278~281.
[10]张叶,于春红,杨锦飞.低聚有机膦酸酯阻燃剂的合成[J].南京师范大学学报:工程技术版, 2008, 8(2):56~58.
[11]卢涌泉,邓振华.实用红外光谱解析[M].北京:电子工业出版社,1989.
[2] RANGANATHAN T, BEAULIEU M, ZILBERMAN J, et al. Thermal degradation of deoxybenzoin polymers studied by pyrolysisgas chromatography/mass spectrometry[J]. Polymer Degradation&Stability, 2008, 93(6):1059~1066.
[3] SILIESCU S, AVRAM E, VISA A, et al. New technique for the synthesis of polyphosphoesters[J]. Macromole Res,2011,19:1186~1191.
[4]马作广,陈明清.新型环状磷酸酯的合成及其阻燃性能研究[J].精细化工, 2018, 35(2):320~325.
[5]孙才英,董子琳,姜大伟.聚甲基膦酸乙二醇酯阻燃棉布的性能[J].精细化工, 2017, 34(9):1058~1062.
[6]董懿嘉.聚膦酸酯阻燃玉米秸秆粉复合聚氨酯材料研究[D].哈尔滨:东北林业大学,2018.
[7]丁思月,姚玥玮,方霁堃.反应型低聚有机膦酸酯阻燃剂的合成与应用[J].聚氨酯工业, 2012, 27(6):17~20.
[8]程超,孙才英.[Bmim]BF4/p-TSA催化合成聚甲基膦酸乙二醇酯[J].精细化工, 2013, 30(10):1155~1159.
[9]吴强,李乾文,于元浩,等.聚甲基膦酸乙二醇酯的催化合成与封端[J].化学与黏合, 2015, 37(4):278~281.
[10]张叶,于春红,杨锦飞.低聚有机膦酸酯阻燃剂的合成[J].南京师范大学学报:工程技术版, 2008, 8(2):56~58.
[11]卢涌泉,邓振华.实用红外光谱解析[M].北京:电子工业出版社,1989.