1. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China; 2. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 3. Research Institute of Qilu Branch Co., SINOPEC, Zibo 255400, China
Although an important industrial catalyst for producing high density polyethylene, the SiO2-supported organosilyl chromate UCC S-2 catalyst has not been fully investigated compared with the SiO2-supported oxo chromium Phillips catalyst. In this work, gas phase ethylene polymerization by S-2 catalysts (Cat-1, Cat-2, and Cat-3) was carried out in a high-speed stirred-autoclave reactor. The effects of temperature, time, and pressure on kinetics, activity, and product properties were studied. All kinetics were typical built-up types with slow decay. Compared to the simple physical mixtures of Cat-1 and Cat-2, Cat-3 showed higher activity and its product had a broader molecular weight distribution, indicating new active species induced during blending of Cat-1 and Cat-2 in n-hexane. The innovation by a simple catalyst technology created a new application to meet market demands.
Corresponding Author(s):
HAO Aiyou,Email:haoay@sdu.edu.cn; LIU Boping,Email:boping@ecust.edu.cn
引用本文:
. Gas phase ethylene polymerization over SiO2-supported organosilyl chromate UCC S-2 catalyst using a high-speed stirred-autoclave reactor[J]. Frontiers of Chemical Science and Engineering, 2011, 5(1): 89-95.
Liuzhong LI, Aiyou HAO, Ruihua CHENG, Boping LIU. Gas phase ethylene polymerization over SiO2-supported organosilyl chromate UCC S-2 catalyst using a high-speed stirred-autoclave reactor. Front Chem Sci Eng, 2011, 5(1): 89-95.
Chen Y P, Fan Z Q, Liao J H, Liao S Q. Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3. Journal of Applied Polymer Science , 2006, 102(2): 1768–1772 doi: 10.1002/app.24443
3
McDaniel M P. Supported chromium catalysts for ethylene polymerization. Advances in Catalysis , 1985, 33: 47–98 doi: 10.1016/S0360-0564(08)60258-8
4
Groppo E, Lamberti C, Bordiga S, Spoto G, Zecchina A. The structure of active centers and the ethylene polymerization mechanism on the Cr/SiO2 catalyst: a frontier for the characterization methods. Chemical Reviews , 2005, 105(1): 115–184 doi: 10.1021/cr040083s
5
Carrick W L, Turbett R J, Karol F J, Karapinka G L, Fox A S, Johnson R N. Ethylene polymerization with supported bis(triphenylsilyl) chromate catalysts. J Polym Sci Part A-1: Polym Chem , 1972, 10(9): 2609–2620 doi: 10.1002/pol.1972.150100909
6
Baker L M, Carrick W L. Bistriphenylsilyl chromate. Oxidation of olefins and use in ethylene polymerization. Journal of Organic Chemistry , 1970, 35(3): 774–776 doi: 10.1021/jo00828a051
7
Cann K, Apecetche M, Zhang M. Comparison of silyl chromate and chromium oxide based olefin polymerization catalysts. Macromolecular Symposia , 2004, 213(1): 29–36 doi: 10.1002/masy.200450904
8
Wang Q, Tang Y, Bi L, Li Y, Hu J, Shi J. Study on HDPE specialty resin for twin-wall corrugated pipe with large diameter. China Synthetic Resin and Plastic , 2005, 22: 1–4 (in Chinese)
9
Tang Y, Wang Q, Shi J, Xie J, Qi S, Bi L. Development of PE specialty resin PE 100 for tubing. China Synthetic Resin and Plastic , 2005, 22: 5–8 (in Chinese)
10
Xie T Y, McAuley K B, Hsu J C C, Bacon D W. Gas phase ethylene polymerization: production processes, polymer properties, and reactor modeling. Industrial & Engineering Chemistry Research , 1994, 33(3): 449–479 doi: 10.1021/ie00027a001
11
Samson J J C, van Middelkoop B, Weickert G, Westerterp K R. Gas-phase polymerization of propylene with a highly active ziegler-natta catalyst. AIChE Journal , 1999, 45(7): 1548–1558 doi: 10.1002/aic.690450716
12
Tannous K, Soares J B P. Gas-phase polymerization of ethylene using supported metallocene catalysts: Study of polymerization conditions. Macromolecular Chemistry and Physics , 2002, 203(13): 1895–1905 doi: 10.1002/1521-3935(200209)203:13<1895::AID-MACP1895>3.0.CO;2-C
13
Liu B, Fang Y, Nakatani H, Terano M. Surface physico-chemical state of CO-prereduced Phillips CrOx/SiO2 catalyst and unique polymerization Behavior in the presence of Al-alkyl cocatalyst. Macromolecular Symposia , 2004, 213(1): 37–46 doi: 10.1002/masy.200450905
14
Liu B, Sindelar P, Fang Y, Hasebe K, Terano M. Correlation of oxidation states of surface chromium species with ethylene polymerization activity for Phillips CrOx/SiO2 catalysts modified by Al-alkyl cocatalyst. Journal of Molecular Catalysis A Chemical , 2005, 238(1-2): 142–150 doi: 10.1016/j.molcata.2005.05.015
15
Fang Y, Liu B, Hasebe K, Terano M. Ethylene and 1-hexene copolymerization with CO-prereduced Phillips CrOx/SiO2 catalyst in the presence of Al-alkyl cocatalyst. Journal of Polymer Science. Part A: Polymer Chemistry , 2005, 43(19): 4632–4641 doi: 10.1002/pola.20935
16
Xia W, Liu B, Fang Y, Hasebe K, Terano M. Unique polymerization kinetics obtained from simultaneous interaction of Phillips Cr(VI)Ox/SiO2 catalyst with Al-alkyl cocatalyst and ethylene monomer. Journal of Molecular Catalysis A Chemical , 2006, 256(1-2): 301–308 doi: 10.1016/j.molcata.2006.05.007
17
Xia W, Tonosaki K, Taniike T, Terano M, Fujitani T, Liu B. Copolymerization of ethylene and cyclopentene with the Phillips CrOx/SiO2 catalyst in the presence of an aluminum alkyl cocatalyst. Journal of Applied Polymer Science , 2009, 111(4): 1869–1877 doi: 10.1002/app.29207
