USRE37384EExpiredUtility
2-substituted disindenylmetallocenes, process for their preparation, and their use as catalysts in the polymerization of olefins
Est. expiryNov 12, 2010(expired)· nominal 20-yr term from priority
C07F 17/00C08F 10/00C07F 7/0805C08F 4/63927Y10S526/943C08F 110/06C08F 4/63912
92
PatentIndex Score
52
Cited by
15
References
27
Claims
Abstract
The novel metallocenes of the formula I in which, preferably, M 1 is Zr or Hf, R 1 and R 2 are alkyl or halogen, R 3 and R 4 are hydrogen, R 5 and R 6 are alkyl or haloalkyl, —(CR 8 R 9 ) m —R 7 —(CR 8 R 9 ) n — is a single- or multi-membered chain in which R 7 may also be a (substituted) hetero atom, and m+n is zero or 1, form, together with aluminoxanes as cocatalysts, a very effective catalyst system for the preparation of polyolefins of high molecular weight.
Claims
exact text as granted — not AI-modifiedWe claim:
1. A compound of the formula I
in which
M 1 is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group, a C 8 -C 40 -arylalkenyl group or a halogen atom,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, which is optionally halogenated, a C 6 -C 10 -aryl group, an —NR 2 10 , —SR 10 , —OSiR 2 10 . —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 -alkyl group or a C 6 -C 10 -aryl group,
R 5 and R 6 are identical or different and are as defined for R 3 and R 4 , with the proviso that R 5 and R 6 are not hydrogen,
═Br 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P(O)R 11 ,
where
R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group or a C 7 -C 40 -alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M 2 is silicon, germanium or tin,
R 8 and R 9 are identical or different and are as defined for R 11 , and
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2 .
2. A compound of the formula I as claimed in claim 1 , wherein, in the formula I, M 1 is Zr or Hf, R 1 and R 2 are identical or different and are methyl or chlorine, R 3 and R 4 are hydrogen, R 5 and R 6 are identical or different and are methyl, ethyl or trifluoromethyl, R 7 is a
radical, and n plus m is zero or 1 .
3. A compound of the formula I as claimed in claim 1 , wherein the compound is Rac selected from the group consisting of rac-dimethylsilyl(2-methyl -1-indenyl) 2 zirconium dichloride, rac-ethylene-(2-methyl-1-indenyl) 2 zirconium dichloride, rac-dimethylsilyl(2-methyl-1-indenyl) 2 dimethylzirconium, rac-ethylene(2-methyl-1-indenyl) 2 dimethylzirconium, rac-phenyl(methyl)silyl(2-methyl-1-indenyl) 2 zirconium dichloride, rac-diphenylsilyl(2-methyl-1-indenyl) 2 zirconium dichloride, rac-methylethylene(2-methyl-1-indenyl) 2 zirconium dichloride, rac-dimethylsilyl (2-ethyl-1-indenyl) 2 zirconium dichloride, rac-ethylene(2-ethyl-1-indenyl) 2 zirconiumdichloride, rac-isopropylidene(2-methyl-1-indenyl) 2 zirconium dichloride or rac-phenyl(methyl)silyl(2-methyl 1-indenyl) 2 dimethyl zirconium.
4. A process for the preparation of a compound of the formula I as claimed in claim 1 , which comprises reacting a compound of the formula II
where R 3 -R 9 , m and n are as described in the formula I, and M 3 is an alkali metal,
a) with a compound of the formula III
M 1 X 4 (III)
in which M 1 is as defined in the formula I, and X is a halogen atom, or
b) with a compound of the formula IIIa
M 1 X 4 L 2 (IIIa)
in which M 1 and X are as defined above, and L is a donor ligand,
and optionally derivatizing the resultant reaction product.
5. A process for the preparation of a compound of the formula I as claimed in claim 4 , wherein M 3 is lithium.
6. A process for the preparation of a compound of the formula I as claimed in claim 4 , wherein X is chlorine.
7. A catalyst composition which comprises: a compound of the formula I as claimed in claim 1 and an aluminoxane.
8. A compound as claimed in claim 1 , wherein M 1 is zirconium, hafnium or titanium.
9. a A compound as claimed in calim claim 1 , wherein R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 3 -alkyl group, a C 1 -C 3 -alkoxy group, a C 6 -C 8 -aryl group, a C 6 -C 8 -aryloxy group, a C 2 -C 4 -alkenyl group, a C 7 -C 10 -arylalkyl group, a C 7 -C 12 -alkylaryl group, a C 8 -C 12 -arylalkenyl group or chlorine.
10. A compound as claimed in claim 1 , wherien R 3 and R 4 are identical or different and are a hydrogen atom, a fluorine, chlorine or bromine atom, a C 1 -C 4 -alkyl group which may be halogenated, a C 6 -C 8 -aryl group, a —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a chlorine atom, or a C 1 -C 3 alkyl group or a C 6 -C 8 -aryl group.
11. A compound as claimed in claim 1 , wherein R 3 and R 4 are hydrogen.
12. A compound as claimed in claim 1 , wherein R 5 and R 6 are identical.
13. A compound as claimed in claim 1 , wherein R 5 and R 6 are (C 1 -C 4 )-alkyl, which may be halogenated with methyl.
14. A compound as claimed in claim 1 , wherein R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a CF 3 group, a C 6 -C 8 -aryl group, a pentafluorophenyl group, a C 1 -C 4 -alkoxy group a C 2 -C 4 -alkenyl group, a C 7 -C 10 -arylalkyl group, a C 8 -C 12 -arylalkenyl group and a C 7 -C 12 -alkylaryl group, or R 11 or R 12 or R 11 and R 13 , in each case together with the atoms connecting them, form a ring.
15. A compound as claimed in claim 1 , wherein M 2 is silicon or germanium.
16. A compound as claimed in claim 1 , wherein R 7 is ═CR 11 R 12 , ═SiR 11 R 12 , ═GeR 11 R 12 , —O—, —S—, ═SO, ═PR 11 or ═P(O)R 11 .
17. A compound as claimed in claim 1 , wherein m and n are identical or different and are zero or 1 .
18. A compound as claimed in claim 1 , wherein m plus n is zero or 1 .
19. A compound as claimed in claim 1 , wherein M 1 is Zr or Hf, R 1 and R 2 are identical or different and are methyl or chlorine, R 3 and R 4 are hydrogen, R 5 and R 6 are identical or different and are methyl, ethyl or trifluoromethyl, and n plus m is zero or 1 .
20. A compound of the formula I
in which
M
1
is zirconium or titanium,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen atom,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
R
7
is
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO,═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 , where R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different are zero, 1 or 2 , m plus n being zero, 1 or 2 .
21. The compound as claimed in claim 20 , wherein M 1 is zirconium.
22. A compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 is a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group or a C 8 -C 40 - arylalkenyl group,
R 2 is a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen group,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
R
7
is
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 ,
where
R 11 , and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group,
R 12 is a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different and are zero, 1 or 2 , m plus n being zero, 1 or 2 .
23. A compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen atom,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
R
7
is
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO,═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 ,
where
R 12 is a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group,
R 11 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different and are zero, 1 or 2 , m plus n being zero, 1 or 2 .
24. A compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen atom,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO,═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 ,
where
R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different and are zero, 1 or 2 , m plus n being zero, 1 or 2 .
25. A compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen atom,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group which is halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R 5 and R 6 are identical or different and are a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
7
is
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO,═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 ,
where
R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different and are zero, 1 or 2 , m plus n being zero, 1 or 2 .
26. A compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen atom,
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R 5 and R 6 are identical or different and are a halogen atom, a C 1 -C 10 - alkyl group which is halogenated, a C 6 -C 10 - aryl group, an —NR— 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
7
is
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO,═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 ,
where
R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 or R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different and are zero, 1 or 2 , m plus n being zero, 1 or 2 .
27. A compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - alkoxy group, a C 6 -C 10 - aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 - arylalkenyl group or a halogen atom,
R 3 and R 4 are different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, which is optionally halogenated, a C 6 -C 10 - aryl group, an —NR 2 10 , —SR 10 , —OSiR 3 10 , —SiR 3 10 or —PR 2 10 radical in which R 10 is a halogen atom, a C 1 -C 10 - alkyl group or a C 6 -C 10 - aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
R
7
is
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO,═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P ( O ) R 11 ,
where
R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 - alkyl group, a C 1 -C 10 - fluoroalkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 - fluoroaryl group, a C 1 -C 10 - alkoxy group, a C 2 -C 10 - alkenyl group, a C 7 -C 40 - arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 - alkylaryl group, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
and m and n are identical or different and are zero, 1 or 2 , m plus n being zero, 1 or 2 .Cited by (0)
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