公开(公告)号：JPH1045823A

公开(公告)日：1998-02-17

申请号：JP11230497

申请日：1997-04-30

Applicant: BASF AG

Inventor： KRISTEN MARC OLIVER DR ,  JUTZI PETER PROF DR ,  REDEKER THOMAS

IPC: C07F17/00 ,  C08F2/06 ,  C08F4/62 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/68 ,  C08F6/00 ,  C08F6/02 ,  C08F6/08 ,  C08F10/00

Abstract: PROBLEM TO BE SOLVED: To recover a metallocene complex salt extremely simply from the technical viewpoint without carrying out expensive after treatment by terminating polymerization by addition of an acid and extracting the complex salt from the reaction mixture. SOLUTION: When a metallocene complex salt of formula I M is titanium, zirconium, hafnium, vanadium, etc.; R to R are each H, a 1-10C alkyl, a (substituted) 5 to 7-membered cycloalkyl, a 6-15C aryl, etc.; R is a group of formula II [R to R are each a 1-10C alkyl, a 6-15C aryl, etc.; (n ) is 0-10], etc.; X to X are each fluorine, chlorine, bromine, iodine, hydrogen, a 1-10C alkyl, etc.; (o), (p), (q) and (r) are each 0-4 and the total [o+p+q+r+1] thereof is a number corresponding to a valence of (μ)} is used as an active catalyst composition component for producing a polymer of a 2-10C alkene, polymerization is terminated by addition of an acid (e.g. HCl) and the metallocene complex salt of formula I is recovered by extraction from the reaction mixture.

公开(公告)号：ES2136452T3

公开(公告)日：1999-11-16

申请号：ES97107021

申请日：1997-04-28

Applicant: BASF AG

Inventor： KRISTEN MARC OLIVER DR ,  JUTZI PETER PROF DR ,  REDEKER THOMAS

IPC: C07F17/00 ,  C08F2/06 ,  C08F4/62 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/68 ,  C08F6/00 ,  C08F6/02 ,  C08F6/08 ,  C08F10/00

Abstract: A process for the recovery of metallocene complexes of formula (I) used as active catalyst components in the production of polymers of 2-10C alkenes. M = Ti, Zr, Hf, V, Nb or Ta; R -R = H, 1-10C alkyl, 5- to 7-membered cycloalkyl (optionally substituted with 1-10C alkyl), or 6-15C aryl or aralkyl, 4-15C cyclic group (formed by two adjacent groups), Si(R )3, -(CR R )n-YHR R or -(CR R )n-ZHR ; R , R , R = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; R , R = H, 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; Y = N, P, As, Sb or Bi; Z = O, S, Se or Te; n = 0-10; R = -(CR R )n1-YHR R or -(CR R )n1-ZHR ; R , R = as for R and R ; R , R = as for R and R ; n1 = 0-10; X -X = F, Cl, Br, I, H, 1-10C alkyl, 6-15C aryl, (1-10C alkyl)-(6-20C aryl), -OR , -NR R or a cyclopentadienyl group substituted with 5 groups R -R ( = Cp); R , R = 1-10C alkyl, 6-15C aryl, alkaryl, aralkyl, fluoroalkyl or fluoroaryl with 1-10C alkyl and 6-20 C aryl groups; R -R = as for R -R , but with R -R = as for R -R respectively and n2 = 0-10 instead of n= 0-10; o, p, q, r = 0-4; o + p + q + r + 1 = the valency of M. The process comprises stopping the polymerisation by addition of acid and recovering (I) from the reaction mixture by extraction. Also claimed is a process for the production of polymers of 2-10C alkenes, especially ethylene, in presence of catalyst systems containing (A) a recovered metallocene complex (I) and (B) a metallocenium ion-forming compound.

公开(公告)号：DE4218201A1

公开(公告)日：1993-12-09

申请号：DE4218201

申请日：1992-06-03

Applicant: BASF AG

Inventor： EVERTZ KASPAR DR ,  SCHLUND RUEGER DR ,  JUTZI PETER PROF DR ,  MIELING INGRID

IPC: C08F4/58 ,  C08F4/60 ,  C08F4/646 ,  C08F4/659 ,  C08F4/6592 ,  C08F4/68 ,  C08F10/00 ,  C07F5/06 ,  C07F17/00

Abstract: Catalyst systems for polymerising C2 to C10-alk-1-enes contain as active components (a) a metallocene complex having the general formula (I), in which the substituents and indexes have the following meaning: M stands for a metal of the secondary group III, IV or V of the periodic table or for a metal from the group of the lanthanides; X stand for halogen, hydrogen, C1- to C10-alkyl, C3- to C10-cycloalkyl, C6- to C15-aryl, alkylaryl with 7 to 15 C atoms or -OR , in which R stands for C1 to C1 to C10-alkyl, C6- to C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroalkyl or fluoroaryl having each 1 to 10 C atoms in the alkyl residue and 6 to 20 C atoms in the aryl residue; n stands for the valency of M, less the number two; R to R stand for hydrogen, C1 to C10-alkyl, C3- to C10-cycloalkyl, which in turn can carry a C1- to C10-alkyl as substituent, C6- to C15-aryl or arylalkyl, whereas if required two adjacent residues may also stand together for cyclic groups having 4 to 15 C atoms, or Si(R )3, in which R stands for C1- to C10-alkyl, C6- to C15-aryl or C3- to C10-cycloalkyl; y , y stand for CH2, C(R )2, Si(R )2, Ge(R )2 or Sn(R )2, in which R stands for C1- to C10-alkyl, C6- to C15-aryl, C3- to C10-cycloalkyl, alkylaryl or Si(R )3, in which R stands for C1- to C10-alkyl, C6- to C15-aryl, C3- to C10-cycloalkyl or alkylaryl; as well as (b) an open-chain or cyclic alumoxane compound having the general formula (II) or (III), in which R stands for a C1- to C4-alkyl group and m is an integer between 5 and 30.

公开(公告)号：DE19618007A1

公开(公告)日：1997-11-06

申请号：DE19618007

申请日：1996-05-04

Applicant: BASF AG

Inventor： KRISTEN MARC OLIVER DR ,  JUTZI PETER PROF DR ,  REDEKER THOMAS

IPC: C07F17/00 ,  C08F2/06 ,  C08F4/62 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/68 ,  C08F6/00 ,  C08F6/02 ,  C08F6/08 ,  C08F10/00

Abstract: A process for the recovery of metallocene complexes of formula (I) used as active catalyst components in the production of polymers of 2-10C alkenes. M = Ti, Zr, Hf, V, Nb or Ta; R -R = H, 1-10C alkyl, 5- to 7-membered cycloalkyl (optionally substituted with 1-10C alkyl), or 6-15C aryl or aralkyl, 4-15C cyclic group (formed by two adjacent groups), Si(R )3, -(CR R )n-YHR R or -(CR R )n-ZHR ; R , R , R = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; R , R = H, 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; Y = N, P, As, Sb or Bi; Z = O, S, Se or Te; n = 0-10; R = -(CR R )n1-YHR R or -(CR R )n1-ZHR ; R , R = as for R and R ; R , R = as for R and R ; n1 = 0-10; X -X = F, Cl, Br, I, H, 1-10C alkyl, 6-15C aryl, (1-10C alkyl)-(6-20C aryl), -OR , -NR R or a cyclopentadienyl group substituted with 5 groups R -R ( = Cp); R , R = 1-10C alkyl, 6-15C aryl, alkaryl, aralkyl, fluoroalkyl or fluoroaryl with 1-10C alkyl and 6-20 C aryl groups; R -R = as for R -R , but with R -R = as for R -R respectively and n2 = 0-10 instead of n= 0-10; o, p, q, r = 0-4; o + p + q + r + 1 = the valency of M. The process comprises stopping the polymerisation by addition of acid and recovering (I) from the reaction mixture by extraction. Also claimed is a process for the production of polymers of 2-10C alkenes, especially ethylene, in presence of catalyst systems containing (A) a recovered metallocene complex (I) and (B) a metallocenium ion-forming compound.

公开(公告)号：DE4211086A1

公开(公告)日：1993-10-07

申请号：DE4211086

申请日：1992-04-03

Applicant: BASF AG

Inventor： EVERTZ KASPAR DR ,  SCHLUND RUEGER DR ,  SCHWEIER GUENTHER DR ,  BRINTZINGER HANS PROF DR ,  ROELL WERNER DR ,  JUTZI PETER PROF DR ,  MIELING INGRID ,  MENGELE WINFRIED

IPC: C07F17/00 ,  C08F4/42 ,  C08F4/60 ,  C08F4/602 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/642 ,  C08F4/6592 ,  C08F4/68 ,  C08F10/00 ,  C08F4/52

Abstract: Catalyst systems for polymerising C2 to C10 alk-1-enes containing as active components: a) a metallic complex of general formula (I) in which M is a metal of the III, IV or V sub-group of the periodic system or a metal from the lanthanide group; X is fluorine, chlorine, bromine, iodine, hydrogen, C1 to C10 alkyl, C6 to C15 aryl or -OR , where R is C1 to C10 alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, fluoralkyl or fluoraryl with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical; n is the valency of M minus 2; R to R are hydrogen, C1 to C10 alkyl, 5 to 7 membered cycloalkyl which in turn may have a C1 to C10 alkyl as a substituent, C6 to C15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 C atoms, or Si(R )3 where R is C1 to C10 alkyl, C6 to C15 aryl or C3 to C10 cycloalkyl; E , E are, independently, Si(R )2, Ge(R )2, Sn(R )2 or C(R )2-C(R )2 where R is C1 to C10 alkyl, C3 to C10 cycloalkyl or C6 to C15 aryl; and b) is an open-chained or cyclic alumoxane compound of general formula (II) or (III) in which R is a C1 to C4 alkyl group and m is an integer from 5 to 30.

公开(公告)号：DE4303647A1

公开(公告)日：1994-08-11

申请号：DE4303647

申请日：1993-02-09

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  SCHLUND RUEGER DR ,  LUX MARTIN DR ,  JUTZI PETER PROF DR ,  DAHLHAUS JUERGEN

IPC: C07C17/263 ,  C07C22/02 ,  C07C43/162 ,  C07C211/25 ,  C07C321/10 ,  C07C321/20

Abstract: Cyclopentadienes of the general formulae Ia to Ie in which the substituents and indices have the following meaning: R , R , R and R are C1- to C5-alkyl groups or C6- to C 15-aryl groups, X is NR R , OR , SR , Cl, Br or I, where R and R are hydrogen, C1- to C5-alkyl groups or C6- to C15-aryl groups and n is an integer from 2 to 5, and process for the preparation of cyclopentadienes of the general formulae IIa to IIe in which the substituents and indices have the following meaning: R , R , R and R are C1- to C5-alkyl groups or C6- to C 15-aryl groups, X is NR R , OR , SR , Cl, Br or I, where R and R are hydrogen, C1- to C5-alkyl groups or C6- to C15-aryl groups and m is an integer from 1 to 5, where in a first step lithium compounds of the general formula IIIa or IIIb or mixtures thereof and IIIc or IIId or mixtures thereof are converted with carboxylic acid esters of the general formula IV X(CH2)mCOOR in which R is a C1- to C4-alkyl group to dienols of the general formulae Va to Vd and the dienols of the general formulae Va to Vd are then converted by acid-catalysed ring closure to the cyclopentadienes of the general formulae IIa to IIe.