PROPENE POLYMERIZATION USING HOMOGENEOUS MAO-ACTIVATED METALLOCENE CATALYSTS - ME(2)SI(BENZ[E]INDENYL)(2)ZRCL2/MAO VS ME(2)SI(2-ME-BENZ[E]INDENYL)(2)ZRCL2/MAO

被引:105
作者
JUNGLING, S
MULHAUPT, R
STEHLING, U
BRINTZINGER, HH
FISCHER, D
LANGHAUSER, F
机构
[1] UNIV FREIBURG, FREIBURGER MAT FORSCHUNGSZENTRUM, D-79104 FREIBURG, GERMANY
[2] UNIV KONSTANZ, FAK CHEM, D-78434 CONSTANCE, GERMANY
[3] BASF AG, ZKP ABT, D-67056 LUDWIGSHAFEN, GERMANY
关键词
PROPENE; POLYMERIZATION; ZIRCONOCENE; METHYLALUMOXANE; CHAIN TRANSFER; END GROUPS; HYDROGEN; 2,1-INSERTION;
D O I
10.1002/pola.1995.080330813
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Propene was polymerized at 40 degrees C and 2-bar propene in toluene using methylalumoxane (MAO) activated rac-Me(2)Si(Benz[e]Indenyl)(2)Zr Cl-2 (BI) and rac-Me(2)Si(2-Me-Benz[e]Indenyl)(2)ZrCl2 (MBI). Catalyst BI/MAO polymerizes propene with high activity to afford low molecular weight polypropylene, whereas MBI/MAO is less active and produces high molecular weight polypropylene. Variation of reaction conditions such as propene concentration, temperature, concentration of catalyst components, and addition of hydrogen reveals that the lower molecular weight polypropylene produced with BI/MAO results from chain transfer to propene monomer following a 2,1-insertion. A large fraction of both metallocene catalyst systems is deactivated upon 2,1-insertion. Such dormant sites can be reactivated by H-2-addition, which affords active metallocene hydrides. This effect of H, addition is reflected by a decreasing content of head-to-head enchainment and the formation of polypropylene with n-butyl end groups. Both catalysts show a strong dependence of activity on propene concentration that indicates a formal reaction order of 1.7 with respect to propene. MBI/MAO shows a much higher dependence of the activity on temperature than BI/MAO. At elevated temperatures, MBI/MAO polymerizes propene faster than BI/ MAO. (C) 1995 John Wiley and Sons, Inc.
引用
收藏
页码:1305 / 1317
页数:13
相关论文
共 36 条
  • [1] HALOGEN-FREE SOLUBLE ZIEGLER CATALYSTS FOR POLYMERIZATION OF ETHYLENE - CONTROL OF MOLECULAR-WEIGHT BY CHOICE OF TEMPERATURE
    ANDRESEN, A
    CORDES, HG
    HERWIG, J
    KAMINSKY, W
    MERCK, A
    MOTTWEILER, R
    PEIN, J
    SINN, H
    VOLLMER, HJ
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1976, 15 (10): : 630 - 632
  • [2] ANDRESEN A, 1985, ANGEW CHEM INT EDIT, V24, P507
  • [3] Andresen A, 1976, ANGEW CHEM, V88, P689
  • [4] STRUCTURE-ACTIVITY AND STRUCTURE-SELECTIVITY CORRELATIONS IN METALLOCENE-BASED CATALYSTS FOR ALPHA-OLEFIN POLYMERIZATION
    BURGER, P
    HORTMANN, K
    BRINTZINGER, HH
    [J]. MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA, 1993, 66 : 127 - 139
  • [5] BUSICO V, 1993, MAKROMOL CHEM, V194, P1079
  • [6] BUSICO V, 1993, MAKROMOL CHEM-RAPID, V14, P97
  • [7] HYDROGEN ACTIVATION IN PROPENE POLYMERIZATION WITH MGCL2-SUPPORTED ZIEGLER-NATTA CATALYSTS - THE EFFECT OF THE EXTERNAL DONOR
    CHADWICK, JC
    MIEDEMA, A
    SUDMEIJER, O
    [J]. MACROMOLECULAR CHEMISTRY AND PHYSICS, 1994, 195 (01) : 167 - 172
  • [8] CHENG HN, 1989, MAKROMOL CHEM, V190, P1931
  • [9] A KINETIC MATHEMATICAL-MODEL FOR HETEROGENEOUS ZIEGLER-NATTA COPOLYMERIZATION
    DECARVALHO, AB
    GLOOR, PE
    HAMIELEC, AE
    [J]. POLYMER, 1989, 30 (02) : 280 - 296
  • [10] METALLOCENE POLYPROPYLENE STRUCTURAL RELATIONSHIPS - IMPLICATIONS ON POLYMERIZATION AND STEREOCHEMICAL CONTROL MECHANISMS
    EWEN, JA
    ELDER, MJ
    JONES, RL
    HASPESLAGH, L
    ATWOOD, JL
    BOTT, SG
    ROBINSON, K
    [J]. MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA, 1991, 48-9 : 253 - 295