Kinetics of the Mono-esterification Between Terephthalic Acid and 1,4-Butanediol

Abstract

Abstract: The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)₄] were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)₄ were measured at a series of initial concentrations of BDO(or TPA) with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)₄ respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.

Key words: esterification, 1,4-butanediol, terephthalic acid, kinetics

摘要： The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)₄] were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)₄ were measured at a series of initial concentrations of BDO(or TPA) with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)₄ respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.

关键词: esterification, 1,4-butanediol, terephthalic acid, kinetics

TIAN Wenyu, ZENG Zuoxiang, XUE Weilan, LI Yingbin, ZHANG Tianyu. Kinetics of the Mono-esterification Between Terephthalic Acid and 1,4-Butanediol[J]. , 2010, 18(3): 391-396.

田文玉, 曾作祥, 薛为岚, 李应宾, 章添钰. Kinetics of the Mono-esterification Between Terephthalic Acid and 1,4-Butanediol[J]. , 2010, 18(3): 391-396.

References

1 Khairullin, I.I., Aleksashin, V.M., Petrova, A.P., “Use of thermal analysis techniques for studying a hot-melt adhesive”, Polymer, 49, 84-85(2007).
2 Petrova, A.P., Adhesive Materials Handbook, Kauchuk i Rezina, Moscow, 57-63(2002).
3 Corrado, B., Maurizio, F., Laura, S., “Synthesis of poly(butylene terephtahlate) nanocomposites using anionic clays”, Eur. Polym. J., 45, 70-78(2009).
4 Colonna, M., Banach, T.E., Berti, C., Fiorini, M., Marianucci, E., Messori, M., Pilati, F., Toselli, M., “New catalysts for poly(butylene terephthalate) synthesis(III) Effect of phosphate co-catalysts”, Polymer, 44, 4773-4779(2003).
5 Omota, F., Dimian A.C., Bliek, A., “Fatty acid esterification by reactive distillation(II) Kinetics-based design for sulphated zirconia catalysts”, Chem. Eng. Sci., 58, 3175-3185(2003).
6 Pilati, F., Comprehensive Polymer Science, Pergamon, Oxford, 231-233(1989).
7 Whinfield, J.R., Dickson, J.T., “Polymeric linear terephthalic esters”, US Pat., 2465319(1949).
8 Iida, H., Azuma, K., Hayashi, M., “Method for producing polybutylene terephthalate”, US Pat., 4656241(1987).
9 Ohme, H., Hiratsuka, M., Nogami, K., “Method for producing polybutylene terephthalate”, US Pat., 6060579(2000).
10 Blagov, S., Parada, S., Bailer, O., Moritz, P., Lam, D., Weinand, R., Hasse, H., “Influence of ion-exchange resin catalysts on the reactions of the esterification of n-Butanol with acetic acid”, Chem. Eng. Sci., 61, 753-765(2006).
11 Pilati, F., Munari, A., Fortunato, B., Manaresi, P., Passalacqua, V., “Formation of poly(butylene terephthalate):Secondary reactions studied by model molecules”, Polymer, 22, 1566-1570(1981).
12 El-Kinawy, O.S., Megahed, O.A., Zaher, F.A., “Kinetics of esterification of various saturated fatty acids with isobutanol”, Modell. Meas. Control C, 63, 27-38(2002).
13 Kulawska, M., Sadlowski, J.Z., Skrzypek, J., “Kinetics of the esterification of maleic anhydride with octyl, decyl or dodecyl alcohol over dowex catalyst”, React. Kinet. Catal. Lett., 85, 51-56(2005).
14 Tesser, R., Diserio, M., Nastasi, M., Santacesaria, E., “Kinetics of oleic acid esterification with methanol in the presence of triglycerides”, Ind. Eng. Chem. Res., 44, 7978-7982(2005).
15 Banach, T.E., Colonna, M., “New catalysts for poly(butylene terephthalate) synthesis(II) Kinetic comparison using model compounds”, Polymer, 42, 7517-7522(2001).
16 Padias, A.B., Hall, H.K., “Oligomeric bishydroxybutyl terephthalates from terephthalic acid”, J. Polym. Sci. A Polym. Chem., 19, 1021-1032(1981).
17 Baranova, T.L., Kremer, E.B., “Solution of terephthalic acid in the reaction system terephthalic acid-ethylene glycol-esterification products”, Fibre Chem., 9, 333-334(1978).
18 Patel, H., Feix, G., Schomacker, R., “Modeling of semibatch esterification process for poly(ethylene terephthalate) synthesis”, Macromol. React. Eng., 1, 502-503(2007).
19 Yamada, T., Imamura, Y., Makimura, O., “A mathematical model for computer simulation of a direct continuous esterification process between terephthalic acid and ethylene glycol(I) Model development”, Polym. Eng. Sci., 25, 788-795(1985).
20 Pilati, F., Manaresi, P., Fortunato, B., Munari, A., Passalacqua, V., “Formation of poly(butylene terephthalate):Growing reactions studied by model molecules”, Polymer, 22, 799-803(1981).
21 Pilati, F., Manaresi, P., Fortunato, B., Munari, A., Monari, P., “Models for the formation of poly(butylene terephthalate):Kinetics of the titanium tetrabutylate-catalysed reactions:2”, Polymer, 24, 1479-1483(1983).

[1]	Xiaolin Guo, Zhaoyang Zhang, Pengfei Xing, Shuai Wang, Yibing Guo, Yanxin Zhuang. Kinetic mechanism of copper extraction from methylchlorosilane slurry residue using hydrogen peroxide as oxidant [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 228-234.
[2]	Xun Tao, Fan Zhou, Xinlei Yu, Songling Guo, Yunfei Gao, Lu Ding, Guangsuo Yu, Zhenghua Dai, Fuchen Wang. Effect of carbon dioxide on oxy-fuel combustion of hydrogen sulfide: An experimental and kinetic modeling [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 105-117.
[3]	Junyang Liu, Luming Wang, Yuhang Bian, Chunshan Li, Zengxi Li, Jie Li. Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 1-10.
[4]	Wei Wang, Romain Lemaire, Ammar Bensakhria, Denis Luart. Thermogravimetric analysis and kinetic modeling of the co-pyrolysis of a bituminous coal and poplar wood [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 53-68.
[5]	Bing Liu, Yingjiao Li, Moses Arowo, Guangwen Chu, Yong Luo, Liangliang Zhang, Haikui Zou, Baochang Sun. Sulfonation of 1, 4-diaminoanthraquinone leuco by chlorosulfonic acid: Kinetics and process intensification [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 163-169.
[6]	Xinyu Liu, Hongliang Sheng, Song He, Chunhua Du, Yuansheng Ma, Chichi Ruan, Chunxiang He, Huaming Dai, Yajun Huang, Yuelei Pan. Insight into pyrolysis of hydrophobic silica aerogels: Kinetics, reaction mechanism and effect on the aerogels [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 266-281.
[7]	Guangyuan Chen, Tong Zhou, Meng Zhang, Zhongxiang Ding, Zhikun Zhou, Yuanhui Ji, Haiying Tang, Changsong Wang. Effects of heavy metal ions Cu²⁺/Pb²⁺/Zn²⁺ on kinetic rate constants of struvite crystallization [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 10-16.
[8]	Shujun Peng, Song Lei, Sisi Wen, Jian Xue, Haihui Wang. A Ruddlesden–Popper oxide as a carbon dioxide tolerant cathode for solid oxide fuel cells that operate at intermediate temperatures [J]. Chinese Journal of Chemical Engineering, 2023, 56(4): 25-32.
[9]	Zhiwei Wang, Yu Zhang, Zhi Zhang, Daowei Zhou, Zhikai Cao, Yong Sha. Investigation on catalytic distillation for ethyl acetate production with different catalytic packing structures [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 63-72.
[10]	Monique Juna L. Leite, Ingrid Ramalho Marques, Mariane Carolina Proner, Pedro H.H. Araújo, Alan Ambrosi, Marco Di Luccio. Catalytically active membranes for esterification: A review [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 142-154.
[11]	Tengjie Wang, Wenkai Li, Xuehui Ge, Ting Qiu, Xiaoda Wang. Kinetics measurement of ethylene-carbonate synthesis via a fast transesterification by microreactors [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 243-250.
[12]	Yingjie Song, Shuqi Zhong, Yingjiao Li, Kun Dong, Yong Luo, Guangwen Chu, Haikui Zou, Baochang Sun. Study on the catalytic degradation of sodium lignosulfonate to aromatic aldehydes over nano-CuO: Process optimization and reaction kinetics [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 300-309.
[13]	Xuan Gao, Zhihui Li, Dongsheng Zhang, Xinqiang Zhao, Yanji Wang. Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 310-316.
[14]	Kechang Gao, Shengjuan Shao, Zhixing Li, Jiaxin Jing, Weizhou Jiao, Youzhi Liu. Kinetics of the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 317-323.
[15]	Hongbo Song, Wei Wang, Jiachen Sun, Xianhui Wang, Xianhua Zhang, Sai Chen, Chunlei Pei, Zhi-Jian Zhao. Chemical looping oxidative propane dehydrogenation controlled by oxygen bulk diffusion over FeVO₄ oxygen carrier pellets [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 409-420.