Ethylene polymerization using dealuminated ZSM-2 zeolite nanocrystals as an active metallocene catalyst support

被引:28
作者
Covarrubias, Cristian [1 ]
Quijada, Raul [1 ,2 ]
Rojas, Rene [1 ,3 ]
机构
[1] Univ Chile, Ctr Adv Interdisciplinary Res Mat, Santiago, Chile
[2] Univ Chile, Fac Ciencias Fis & Matemat, Dept Ingn Quim & Biotecnol, Santiago, Chile
[3] Pontificia Univ Catolica Chile, Fac Quim, Dept Quim Inorgan, Santiago, Chile
关键词
ethylene polymerization; metallocene supports; metallocene activation; nanosized zeolites;
D O I
10.1016/j.apcata.2008.06.023
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The preparation of dealuminated (DEAL) ZSM-2 zeolite nanocrystals for use as an active metallocene polymerization catalyst support is presented. The DEAL-ZSM-2 zeolite form was prepared by using steam treatment; metallocene catalyst was directly supported on the zeolite: and evaluated in the polymerization of ethylene using either methylaluminoxane (MAO) or an alkylaluminun as cocatalysts. in order to elucidate the activator effect of the acidic zeolite support. a detailed material characterization was performed. Metallocene catalyst supported on DEAL-ZSM-2 zeolite exhibited high activity values. The metallocene activation is attributed to the action of soluble cocatalyst (MAO or alkylaluminun) into the reactor and to the activator effect of extraframework aluminum species with strong Lewis acidity existing in the DEAL-ZSM-2 zeolite structure. High external surface area of the nanosized zeolite also contributes to reduce the diffusion effects commonly observed in microsized zeolite supports. The results of this work demonstrate that DEAL-ZSM-2 zeolite support does not necessitate to be treated with MAO previous fixation of the metallocene catalyst, and that polymerization activity can be also achieved using a trialkyaluminum as cocatalyst. Thus, the use of DEAL-ZSM-2 zeolite as metallocene support could contribute to reduce the amount of MAO required for ethylene polymerization. (C) 2008 Elsevier B.V. All rights reserved.
引用
收藏
页码:223 / 233
页数:11
相关论文
共 61 条
[1]   Supported organometallics. Highly electrophilic cationic metallocene hydrogenation and polymerization catalysts formed via protonolytic chemisorption on sulfated zirconia [J].
Ahn, H ;
Marks, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (51) :13533-13534
[2]   HYDROTHERMAL CHEMISTRY OF SILICATES .21. ZEOLITES FROM REACTION OF LITHIUM AND CESIUM IONS WITH TETRAMETHYLAMMONIUM ALUMINOSILICATE SOLUTIONS [J].
BARRER, RM ;
SIEBER, W .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1977, (10) :1020-&
[3]  
Benavente R, 2001, J POLYM SCI POL PHYS, V39, P277, DOI 10.1002/1099-0488(20010201)39:3<277::AID-POLB1000>3.0.CO
[4]  
2-3
[5]   Metallocene supported on a polyhedral oligomeric silsesquioxane-modified silica with high catalytic activity for ethylene polymerization [J].
Bianchini, D ;
Galland, GB ;
Dos Santos, JHZ ;
Williams, RJJ ;
Fasce, DP ;
Dell'Erba, IE ;
Quijada, R ;
Perez, M .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2005, 43 (22) :5465-5476
[6]   STEREOSPECIFIC OLEFIN POLYMERIZATION WITH CHIRAL METALLOCENE CATALYSTS [J].
BRINTZINGER, HH ;
FISCHER, D ;
MULHAUPT, R ;
RIEGER, B ;
WAYMOUTH, RM .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1995, 34 (11) :1143-1170
[7]  
Brockmeier N., 1998, METALLOCENE CATALYZE, P11
[8]   Borane-functionalized silica supports In situ activated heterogeneous zirconocene catalysts for MAO-free ethylene polymerization [J].
Charoenchaidet, S ;
Chavadej, S ;
Gulari, E .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2002, 185 (1-2) :167-177
[9]   Cocatalysts for metal-catalyzed olefin polymerization: Activators, activation processes, and structure-activity relationships [J].
Chen, EYX ;
Marks, TJ .
CHEMICAL REVIEWS, 2000, 100 (04) :1391-1434
[10]   POTENTIOMETRIC METHOD FOR DETERMINING THE NUMBER AND RELATIVE STRENGTH OF ACID SITES IN COLORED CATALYSTS [J].
CID, R ;
PECCHI, G .
APPLIED CATALYSIS, 1985, 14 (1-3) :15-21