Supported metallocene complexes having heterofunctional groups in the cyclopentadienyl system as catalyst system

摘要

New supported catalyst systems prepd. by the following method: (a) reaction of a fine particled carrier with an alpha -tris-alkoxysilyl- OMEGA -haloalkyl cpd.; (b) addn. of a metallocene complex of formula (I); (c) reaction with a quaternising agent of formula (V); and (d) opt. addn. of an open chain or cyclic alumoxane cpd. of formula (VI) or (VII). M = Ti, Zr, Hf,V, Nb or Ta; X = F, Cl, Br, I, H 1-10C alkyl, 6-15C aryl or -OR5; R5 = 1-10C alkyl, 6-15C aryl, 1-10C alkyl, 6-20C aryl, 6-20C aryl - 1-10C alkyl, 1-10C fluoroalkyl or 6-20C fluoroaryl; R1-R3 and R6-R8 = H, 1-10C alkyl, opt.1-10C alkyl substd. 5-7 membered cycloalkyl or 6-15C aryl(alkyl),with which two neighbouring gps. may opt. form 4-15C cyclic gps., or Si(R10)3; R10 = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; R4 = : Q1 = N,P, As, Sb or Bi; R11, R12 = 1-10C alkyl, 3-15C cycloalkyl, 6-15C aryl, 1-10C alkyl- 6-20C aryl, 6-20C aryl -1-10C alkyl, 1-10C fluoroalkyl or 5-20C fluoroaryl, or R11 and R12 may form a 2-15C heterocyclic gp. contg. 1-8 heteroatoms from main gps. III-VI of the periodic table; R9 = H, 1-10C alkyl, opt.1-10C alkyl substd. 5-7 membered cycloalkyl, 6-15C aryl(alkyl) in which two neighbouring gps. may opt. form 4-15C cyclic gps. Si(R13)3 or a gp. of formula R13 = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; Q2 = N, P, As, Sb, or Bi; R14, R15 = 1-10C alkyl, 3-15C cycloalkyl, 6-15C aryl, 1-10C alkyl 6-20C aryl, 6-20C aryl -1-10C alkyl, 1-10C fluoroalkyl, 6-20C fluoroaryl or R14 and R15 may form a 2-15C heterocyclic gp.contg. 1-8 heteroatoms from main gps. III-VI of the periodic table; Y = a gp. of formula Z = Si,Ge, Sn or C; R16-R19 = H, 1-10C alkyl, 3-10C cycloalkyl or 6-15C aryl, with two neighbouring gps. opt. forming a 4-15C cyclic gp.; A = 1-10C alkyl, 3-15C cycloalkyl, 6-15C aryl, 1-10C alkyl-6-20C aryl, 6-20C aryl-1-10C alkyl, 1-10C fluoroalkyl or 6-20C fluoroaryl; X2 = F, Cl, Br, I, SO32-, SO42- or NO3-; a = 1-2; R20 = 1-4C alky; and m = 5-30. Also claimed are (i) the prepn. of the supported catalyst systems, and (ii) use of the catalyst systems for the prepn. of 2-10C alk-1-enes at -50 to 300 degrees C. 0.5-3000 bar.