Citation: Zhi-feng Cai, Qing-yin Wang, Shao-ying Liu, Gong-ying Wang. Study of KF/Al₂O₃ Catalyst in Synthesis of Poly(ethylene terephthalate) by Esterification[J]. Acta Polymerica Sinica, ;2018, 0(9): 1184-1193. doi: 10.11777/j.issn1000-3304.2018.18014 shu

Study of KF/Al₂O₃ Catalyst in Synthesis of Poly(ethylene terephthalate) by Esterification

Zhi-feng Cai ^1,3 ,
Qing-yin Wang ^1,2 ,
Shao-ying Liu ^1,2,, ,
Gong-ying Wang ^1,2,,

3.
University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Shao-ying Liu, syliu@cioc.ac.cn Gong-ying Wang, gywang@cioc.ac.cn
Received Date: 15 January 2018
Revised Date: 8 March 2018
Available Online: 11 July 2018

A series of KF/Al₂O₃ solid base catalysts were prepared by a wet impregnation method and applied to the synthesis of poly(ethylene terephthalate) (PET) from 1,4-dicarboxybenzene and ethylene glycol. The effect of KF content and calcination temperature on the structure, active components and properties of the catalysts were investigated. The structure of KF/Al₂O₃ catalysts was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET. The basic strength and basicity of KF/Al₂O₃ catalysts were measured by Hammett indicator. The relationship between KF content, calcination temperature and the structure, basic strength and basicity of KF/Al₂O₃ catalyst was investigated. The relationship between the structure, basic strength and basicity of KF/Al₂O₃ catalysts and the catalytic activity in PET synthesis was also studied. The results showed that KF/Al₂O₃ catalysts could be used to synthesize high-molecular-weight PET. It was found that several types of basic centers such as K₃AlF₆, KAlO₂, K₂O and K₂CO₃ existed in the catalyst. The specific surface area of KF/Al₂O₃ was reduced with increasing KF content. The particle size of KF/Al₂O₃ increased with increasing KF content. The basic strength and basicity of KF/Al₂O₃ increased with increasing KF content and calcination temperature. The activity of KF/Al₂O₃ was related to the basic strength and basicity and was not really influenced by the specific surface area and particle size. Medium strength basic sites were responsible for the higher intrinsic viscosity, and strong basic sites could cause decomposition of the obtained polymer. Strong basic sites were mainly due to potassium carbonate, potassium aluminate and potassium oxide. The catalytic effect of 25-KF/Al₂O₃-400 was better than that of Sb₂O₃. It contained γ-Al₂O₃, K₃AlF₆ and a small amount of K₂CO₃. It had moderate basic strength, basicity and high activity. Based on the obtained results, the possible active site was K₃AlF₆. The intrinsic viscosity of 1.07 dL/g, with carboxyl end group content of 20.29 mol/t, DEG content of 2.85%, L value of 86.6 and b value of 4.6, was obtained with 0.1 wt% of catalyst concentration.
- KF/Al₂O₃,
- Basic strength and basicity,
- Structure-activity relationship,
- Poly(ethylene terephthalate)
1. [1]
2. [2]
  Ni L L, Xin J Y, Dong H X, Liu X M, Liu X M, Zhang S J. ChemSusChem, 2017, 10: 2394 − 2401
3. [3]
4. [4]
  Aharoni S M. Polym Eng Sci, 1998, (38): 1039 − 1047
5. [5]
  He M C, Yang J R. Sci Total Environ, 1999, 234(9): 149 − 155
6. [6]
  McClelland E, Harrogate. US patent, C08g, 3965071.1976-06-22
7. [7]
  Ronald A. Tershansy. US patent, C08g, 3907754.1975-09-23
8. [8]
  Neidel U, Eckert T. Chem Fibers Int, 1999, 49: 27 − 29
9. [9]
  Yin M, Li C C, Guan G H, Zhang D, Xiao Y N. J Appl Polym Sci, 2010, 115(4): 2470 − 2478
10. [10]
11. [11]
  Finelli L, Lorenzetti C, Messori M, Sisti L, Vannini M. J Appl Polym Sci, 2004, 92: 1887 − 1892
12. [12]
13. [13]
14. [14]
  Lin Q H, GuY Q, Chen D J. J Appl Polym Sci, 2013, 129(5): 2571 − 2579
15. [15]
  Xiao B, Wang L P, Mei R H, Wang G Y. Chinese Chem Lett, 2011, 22(6): 741 − 744
16. [16]
17. [17]
  Zheng X Y, Fan W M, Kong W P, Qi C. Kinet Catal, 2014, 55(5): 592 − 598
18. [18]
  Shahraki H, Entezari M H, Goharshadi E K. Ultrason Sonochem, 2015, 23: 266 − 274
19. [19]
  Xu B, Xiao G M, Cui L F, Wei R P, Gao L J. Energ Fuel, 2007, 21: 3109 − 3112
20. [20]
  Feng Y X, Yin N, Li Q F, Wang J W, Kang M Q, Wang X K. Catal Lett, 2008, 121: 97 − 102
21. [21]
  Serio M D, Tesser R, Ferrara A, Santacesaria E. J Mol Catal A-Chem, 2004, 212: 251 − 257
22. [22]
  Yan S L, Kim M, Salley S O, Simon S K Y. Appl Catal A-Gen, 2009, 360: 163 − 170
23. [23]
  Xie W L, Peng H, Chen L G. Appl Catal A-Gen, 2006, 300: 67 − 74
24. [24]
  Xu C L, Sun J, Zhao B B, Liu Q. Appl Catal B-Environ, 2010, 99: 111 − 117
25. [25]
  Qiu P, Yang B L, Yi C H, Qi S T. Catal Lett, 2010, 137: 232 − 238
26. [26]
  Liu Z M, Wang J W, Kang M Q, Yin N, Wang X K, Tan Y S, Zhu Y L. J Braz Chem Soc, 2014, 25: 152 − 160
27. [27]
  Liu Z M, Wang J W, Kang M Q, Yin N, Wang X K, Tan Y S, Zhu Y L. J Ind Eng Chem, 2015, 21: 394 − 399
28. [28]
  Wang S, Hao P F, Li S X, Zhang A L, Guan Y Y, Zhang L N. Appl Catal A-Gen, 2017, 542: 174 − 181
29. [29]
  Holland B J, Hay J N. Polymer, 2002, 43: 1835 − 1847
30. [30]
  Holland B J, Hay J N. Polymer, 2002, 43: 1797 − 1804
31. [31]
  Yang J H, Xia Z X, Kong F T, Ma X S. Polym Degrad Stab, 2010, 95: 53 − 58
32. [32]
  Hovenkamp S G, Munting J P. J Polym Sci, Part B: Polym Chem, 1970, 8: 679 − 682
33. [33]
  Wang Z Q, Yang X G, Li J G, Liu S Y, Wang G Y. J Mol Catal A-Chem, 2016, 424: 77 − 84
34. [34]
  Jung J H, Moonhor R, Heesoo K. Catal Today, 2006, 115: 283 − 287
35. [35]
  Dimitris N B, George P K. Polym Degrad Stab, 1999, 63: 213 − 218
36. [36]
  Zimmerman H, Kim N T. Polym Eng Sci, 1980, 20: 680 − 683
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Study of KF/Al₂O₃ Catalyst in Synthesis of Poly(ethylene terephthalate) by Esterification