公开(公告)号：DE19741876A1

公开(公告)日：1999-03-25

申请号：DE19741876

申请日：1997-09-23

Applicant: BASF AG

Inventor： GREGORIUS HEIKE DR ,  SUELING CARSTEN DR ,  BIDELL WOLFGANG DR ,  BRINTZINGER HANS-HERBERT PROF ,  DAMRAU HANS-ROBERT-HELLMUTH ,  WEBER ARMIN

IPC: C07B53/00 ,  C07F17/00 ,  C08F4/60 ,  C08F4/6192 ,  C08F4/64 ,  C08F4/76 ,  C08F10/00

Abstract: Racemic metallocene complexes (I) are prepared from bridged transition metal phenolate complexes (II) and alkali metal or alkaline earth metal cyclopentadienyl derivatives. Some (I) are new. Preparation of racemic metallocene complexes (I) involves reaction of bridged transition metal phenolate complexes of formula (II) with alkali metal or alkaline earth metal (preferably magnesium) cyclopentadienyl derivatives and optionally subsequently substituting the bridged phenolate ligands. M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Group III transition metal or lanthanoid; X = halo, H, alkyl, Ar, alkylaryl, OR10 or NR10R11; n = 1-4, i.e. the valency of M minus 2; R1,R8 = halo, 1-20C alkyl, 3-8C cycloalkyl (optionally substituted by alkyl), alkylaryl, arylalkyl or Si(R9)3; R9 = 1-20C alkyl, cycloalkyl or Ar; R2-R8 = H; or as R1 with the exception of halo; R2-R7 = adjacent groups optionally forming 4-15 C saturated, partially saturated or unsaturated cyclic group; residues in R1-R9 = optionally, partially or completely substituted by heteroatoms; R10,R11 = alkyl, Ar, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl; Y,Y1 = Q, Q-Q, Q-Q', Q', O-Q, Q'-Q', BR12, AlR12, Ge, Sn, O, S, SO, SO2, NR12, CO, PR12 or P(O)R12; Q = M1(R12)2; Q' = C(R12)2; R12 = H, halo, alkyl, fluoroalkyl, 6-10 C fluoroaryl, 6-10 C aryl, alkoxy, 2-10 C alkenyl, 7-40 C arylalkyl, 8-40 C arylalkenyl or 7-40 C alkylaryl; or two R12 groups together complete a ring; M1 = Si, Ge or Sn; m = 0-3; Ar = 6-15 C aryl. Unless specified otherwise alkyl moieties have 1-10 C, aryl 6-20 C and cycloalkyl 3-10 C. An Independent claim relates to novel racemic metallocene complex products of formula (I'): X1 = group of formula (i); Z = group of formula (ii); E = A or group of formula (iii); R13-R17, R19-R23 = H, 1-20 C alkyl, 5-7 membered cycloalkyl (optionally substituted by alkyl), Ar or arylalkyl (C-number not specified) (where adjacent groups can form a 4-15 C cyclic group); or Si(R)3; or R16 + Z = -(T(R25)(R26))q-E-; R25,R26 = H, 1-20 C alkyl, cycloalkyl or Ar; q = 1-4; A = O, S, NR27 or PR27; R27 = alkyl, Ar, cycloalkyl, alkylaryl (C-number not specified) or Si(R28)3; R28 = alkyl, Ar, cycloalkyl or alkylaryl (C-number not specified).

公开(公告)号：ES2100752T3

公开(公告)日：1997-06-16

申请号：ES95102479

申请日：1995-02-22

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  FISCHER DAVID DR ,  KERTH JURGEN DR ,  SCHWEIER GUNTHER DR ,  BARSTIES ELKE ,  BRINTZINGER HANS-HERBERT PROF

IPC: C08F4/622 ,  C08F4/02 ,  C08F4/60 ,  C08F4/602 ,  C08F4/616 ,  C08F4/628 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/656 ,  C08F4/6592 ,  C08F4/68 ,  C08F10/00

Abstract: 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 -OR ; R = 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; R -R and R -R = 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(R )3; R = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; R = : Q = N,P, As, Sb or Bi; R , R = 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 R and R may form a 2-15C heterocyclic gp. contg. 1-8 heteroatoms from main gps. III-VI of the periodic table; R = 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(R )3 or a gp. of formula R = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; Q = N, P, As, Sb, or Bi; R , R = 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; R -R = 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; X = F, Cl, Br, I, SO3 , SO4 or NO3 ; a = 1-2; R = 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.

公开(公告)号：ES2096396T3

公开(公告)日：1997-03-01

申请号：ES94116512

申请日：1994-10-20

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  KERTH JURGEN DR ,  SCHWEIER GUNTHER DR ,  BRINTZINGER HANS-HERBERT PROF ,  MANSEL STEFAN ,  ROELL WERNER DR

IPC: C08F4/622 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/646 ,  C08F4/68 ,  C08F10/00 ,  C08F110/06

Abstract: A process for the preparation of polymers of C2- to C10-alk-1-enes at pressures of from 0.5 to 3000 bar and temperatures of from -50 to 300 DEG C using a catalyst system, characterised in that the catalyst systems used are those containing, as active constituents, a) metallocene complexes of the formula I b) an open-chain or cyclic aluminoxane compound. lk

公开(公告)号：DE19519884A1

公开(公告)日：1996-12-05

申请号：DE19519884

申请日：1995-05-31

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  FISCHER DAVID DR ,  SCHWEIER GUENTHER DR ,  BRINTZINGER HANS-HERBERT PROF ,  DAMRAU HANS-ROBERT-HELLMUTH

IPC: C07F3/00 ,  C07F7/08 ,  C07F17/00

公开(公告)号：DE59407909D1

公开(公告)日：1999-04-15

申请号：DE59407909

申请日：1994-10-20

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  KERTH JUERGEN DR ,  SCHWEIER GUENTHER DR ,  BRINTZINGER HANS-HERBERT PROF ,  MANSEL STEFAN

IPC: C07C22/02 ,  C07F7/08 ,  C07F17/00 ,  C08F4/6192 ,  C08F4/622 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/646 ,  C08F4/68 ,  C08F10/00

Abstract: Metallocene complexes of the general formula I in which the substituents have the following meaning: M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, 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, fluoroalkyl or fluoroaryl in each case having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, R to R are hydrogen, C1- to C10-alkyl, 5- to 7-membered cycloalkyl which for its part can carry C1- to C10-alkyls as substituents, C6- to C15-aryl or arylalkyl, where, if appropriate, two adjacent radicals together can also 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, Z is silicon, germanium, tin or carbon, Y and Y are where R to R are hydrogen, C1- to C10-alkyl, 5- to 7-membered cycloalkyl which for its part can carry C1- to C10-alkyls as substituents, C6- to C15-aryl or arylalkyl, where, if appropriate, two adjacent radicals together can also 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, and u, v and w are integers from 0 to 7, with the proviso that the sum u + v + w >/= 2, and cyclopentadienyl compounds of the general formula II and cyclopentadienyl compounds of the general formula III as intermediates.t

公开(公告)号：DE19730880A1

公开(公告)日：1999-01-21

申请号：DE19730880

申请日：1997-07-18

Applicant: BASF AG

Inventor： SUELING CARSTEN DR ,  HUETTENHOFER MARIO ,  BRINTZINGER HANS-HERBERT PROF ,  SCHAPER FRANK

IPC: C07F7/22 ,  C07F17/00 ,  C08F4/642 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/00 ,  C07F7/00

Abstract: A tin compound (I) of formula (1) is prepared by reaction of a bridged cyclopentadiene derivative of formula (2) with a tin tetra-amide of formula (3). Also claimed is a process for the production of a racemic ansa metallocene complex of formula (4) by reaction of the tin compound (I) with a transition metal compound of formula MXn (5). where R -R = H, 1-10C alkyl, 5-7 membered cycloalkyl optionally substituted with 1-10C alkyl, 6-15C aryl or arylalkyl or two neighbouring groups can form a 4-15C cyclic group or Si(R")3. R" = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; R = -M R R - , -M R R -M R R -, -M R R -CR2 -, -CR R -, -O-M R R -, -CR R -CR R -, =BR , =AlR , Ge, O, S, =SO, =SO2, =NR , =CO, =PR or =P(O)R ; M = Si or Ge, R , R = 1-10C alkyl, 3-10C cycloalkyl, 1-10C fluoroalkyl, 6-10C aryl, 1-10C alkoxy, 2-10C alkenyl, 7-40C arylalkyl, 8-40C arylalkenyl or 7-40C alkylaryl or R ad R or R and R together form a ring. M = Ti, Zr, Hf, V, Nb or Ta X = F, Cl, Br, I or -OR R = 1-10C alkyl, 6-15C aryl, alkylaryl, arylalkyl, fluoralkyl or fluoroaryl with 1-10C in alkyl group and 6-20C in aryl group n = 3-5.

公开(公告)号：DE59500200D1

公开(公告)日：1997-06-05

申请号：DE59500200

申请日：1995-02-22

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  FISCHER DAVID DR ,  KERTH JUERGEN DR ,  SCHWEIER GUENTHER DR ,  BARSTIES ELKE ,  BRINTZINGER HANS-HERBERT PROF ,  SCHAIBLE STEFAN ,  ROELL WERNER DR

IPC: C08F4/622 ,  C08F4/02 ,  C08F4/60 ,  C08F4/602 ,  C08F4/616 ,  C08F4/628 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/656 ,  C08F4/6592 ,  C08F4/68 ,  C08F10/00

Abstract: 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 -OR ; R = 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; R -R and R -R = 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(R )3; R = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; R = : Q = N,P, As, Sb or Bi; R , R = 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 R and R may form a 2-15C heterocyclic gp. contg. 1-8 heteroatoms from main gps. III-VI of the periodic table; R = 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(R )3 or a gp. of formula R = 1-10C alkyl, 6-15C aryl or 3-10C cycloalkyl; Q = N, P, As, Sb, or Bi; R , R = 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; R -R = 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; X = F, Cl, Br, I, SO3 , SO4 or NO3 ; a = 1-2; R = 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.

公开(公告)号：DE4406963A1

公开(公告)日：1995-09-07

申请号：DE4406963

申请日：1994-03-03

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  FISCHER DAVID DR ,  KERTH JUERGEN DR ,  SCHWEIER GUENTHER DR ,  BRINTZINGER HANS-HERBERT PROF ,  BARSTIES ELKE ,  ROELL WERNER DR

IPC: C07F7/00 ,  C07F7/08 ,  C07F7/10 ,  C07F7/22 ,  C07F7/30 ,  C07F9/72 ,  C07F9/90 ,  C07F17/00 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/642 ,  C08F4/659 ,  C08F4/68 ,  C08F10/00 ,  C07C13/28 ,  C07C23/18 ,  C08F4/76 ,  C08L23/02

公开(公告)号：ES2128486T3

公开(公告)日：1999-05-16

申请号：ES94116511

申请日：1994-10-20

Applicant: BASF AG

Inventor： LANGHAUSER FRANZ DR ,  KERTH JURGEN DR ,  SCHWEIER GUNTHER DR ,  BRINTZINGER HANS-HERBERT PROF ,  MANSEL STEFAN

IPC: C07C22/02 ,  C07F7/08 ,  C07F17/00 ,  C08F4/6192 ,  C08F4/622 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/646 ,  C08F4/68 ,  C08F10/00

Abstract: Metallocene complexes of the general formula I in which the substituents have the following meaning: M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, 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, fluoroalkyl or fluoroaryl in each case having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, R to R are hydrogen, C1- to C10-alkyl, 5- to 7-membered cycloalkyl which for its part can carry C1- to C10-alkyls as substituents, C6- to C15-aryl or arylalkyl, where, if appropriate, two adjacent radicals together can also 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, Z is silicon, germanium, tin or carbon, Y and Y are where R to R are hydrogen, C1- to C10-alkyl, 5- to 7-membered cycloalkyl which for its part can carry C1- to C10-alkyls as substituents, C6- to C15-aryl or arylalkyl, where, if appropriate, two adjacent radicals together can also 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, and u, v and w are integers from 0 to 7, with the proviso that the sum u + v + w >/= 2, and cyclopentadienyl compounds of the general formula II and cyclopentadienyl compounds of the general formula III as intermediates.t

公开(公告)号：DE59209329D1

公开(公告)日：1998-06-18

申请号：DE59209329

申请日：1992-05-27

Applicant: BASF AG

Inventor： KARL EBERHARD ,  ROELL WERNER DR ,  BRINTZINGER HANS-HERBERT PROF ,  RIEGER BERNHARD DR ,  STEHLING UDO

IPC: C07F17/00 ,  C08F4/60 ,  C08F4/642 ,  C08F4/622 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/646 ,  C08F4/649 ,  C08F4/6592 ,  C08F4/68 ,  C08F10/00 ,  C08F10/06 ,  C08F110/06

Abstract: Polymers of 2-10C alk-1-ene are obtd. by polymerisation at 0.1-3000 bar and -20 to 300 degrees C in the presence of a catalyst system contg.: (a) a bis-cyclopentadienyl complex of formula (I), and (b) an open-chain or cyclic aluminoxane of formulae (II) or (III). (R )2Al-Ä-O-Al(R )-Üm-R (II) M = Ti, Zr, Hf, V, Nb or Ta; X = halo or 1-8C alkyl; Y = C, P, S, Si or Ge; Z = 1-8C alkyl, 3-10C cycloalkyl or 6-10C aryl; R , R = 1-4C alkyl; R -R = H or 1-4C alkyl; or R +R or R +R may form a 4-15C hydrocarbon ring system; n = 0, 1 or 2; R = 1-4C alkyl; and m = 5-30. The following cpds. are excluded: dimethylsilyl- bis-(2-methyl indenyl)-, phenyl(methyl)silyl- bis-(2-methyl indenyl)-, diphenylsilyl- bis-(2-methyl indenyl)-, dimethylsilyl- bis-(2-ethyl indenyl)- and isopropylidene- bis-(2-methyl indenyl)- zirconium dichloride, and dimethylsilyl- and phenyl(methyl)silyl- bis-(2-methyl indenyl)- zirconium-dimethyl.