Organometallic compound, preparation method thereof and...

Details Organometallic compound, preparation method thereof and... Organometallic compound, preparation method thereof and...

1999-12-16

2002-04-02

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S348000, C526S153000, C526S159000, C526S141000, C526S147000, C526S164000, C526S160000, C526S943000, C502S123000, C502S152000

Reexamination Certificate

active

06365688

ABSTRACT:

The patent application relates to an organometallic compound comprising a central transition metal atom and a ligand coordinated thereto having a heteroatomic ring structure, a process for its preparation and a process for polymerization of olefins by means of catalyst compositions including said organometallic compounds.
For single active site olefin polymerizations is traditionally used organometallic compounds wherein a central transition metal atom is coordinated by one or more aromatic rings and optionally other groups which may be organic or halide groups, preferably alkyl or chloride groups. The aromatic rings have &pgr;-electrons by which the coordination to the metal is completed. Five members for the ring are most often used, and then the compounds are many times named as metallocenes. These cyclopentadienyl groups can be substituted in many ways: carbon atoms of the ring are connected by one or more separate groups which may contain heteroatoms and/or they can form one or more other rings. Fused rings connected to the cyclopentadienyl ring may constitute even very complicated compound structures. The cyclopentadienyl ring or its replacement rings with their fused rings may contain in their ring structure one or more heteroatoms, too.
This application relates in particular to the heteroatomic ring structure. Characterizing for the structure is that a ligand of the central transition metal atom includes at least three nitrogen atoms and essentially three nitrogens of them are bonded to the same central carbon atom forming a structure wherein the carbon atom is surrounded in three directions by the three nitrogens.
The structure of the organometallic compound may preferably be presented by the formula (1)
L
n
MX
m−n
  (1)
wherein at least one L denotes said ligand coordinated by a &pgr;-electron bond to M and includes a heterocyclic ring structure having at least two fused rings and at least three nitrogen atoms, three of them being connected to said same carbon atom, one of them being common for two rings and two of them being in separate rings, M is the central transition metal atom and belongs to Groups IV, V or VI of the Periodic Table of the Elements, X is an organic group or a halide coordinated to said central transition metal atom M, m signifies the coordination (ligand) number of said transition metal atom M, and n signifies an integer from 1 to m.
The ligand L, except one ligand according to the invention, may be also a cyclopentadienyl ring or its substituted derivative, or the ligand may be also a different kind of group, aromatic or not by its nature. Between the ligands can be a bridge group.
The inventional structure for the ligand (L) is preferably presented in the equation (2):
where groups R
1
, R
2
, R
3
and R
4
are the same or different selected from the group of H, C
1
-C
12
alkyl, alkenyl, aryl (phenyl preferable), alkylaryl, or the groups R
1
, R
2
, R
3
and R
4
may contain silicon atoms instead of one or more carbon atoms, preferably they are SiH
3
, SiH
2
R
5
, SiHR
6
R
7
, SiR
8
R
9
R
10
groups where groups R
5
to R
10
are also the groups recited above. The substituent groups may be also a combination of several groups recited above. The R
1
to R
4
can be interconnected to another one to form bridged structures. In the presence of a base a balance exists in the formula (2) between two ionic isomeric structures which are presented in the right of the formula (2). L is preferably a triaza bicyclo alkenyl, more preferably a 1,5,7-triazabicyclodec-5-enyl, most preferably a 1,5,7-triaza{4.4.0}bicyclodec-5-enyl.
Several compounds according to the invention are recited in a list below and they can be prepared in a similar method using proper reagents instead of those used in the TAB preparation and in the preparation of the inventional metallocene compounds including the ligand.
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium trichloride (3)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium chloride (4)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride (5)
Tetracis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium trichloride (2)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium chloride
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium dichloride
Tetracis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium trichloride
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium chloride
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium dichloride
Tetracis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium dichloride
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium chloride
(Dimethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride
(Diethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride
(Methyl-tertButyl-amine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride
(Dimethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium dichloride
(Diethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium dichloride
(Methyl-tertButyl-amine)-(1,5,7-triaza[4.4.0]bicyclo-deatomc-5-enyl)titanium dichloride
(Dimethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium dichloride
(Diethylatamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium dichloride
(Methyl-tertButyl-amine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium dichloride
(Dimethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium chloride
(Diethylamine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium
(Methyl-tertButyl-amine)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium chloride
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium di(N,N-dimethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium (N,N-dimethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium tri(N,N-dimethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium di(N,N-diethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium (N,N-diethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium tri(,N-diethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium di(N,N-dimethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium (N,N-dimethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium tri(N,N-diethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium di(N,N-diethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium (N,N-diethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)titanium tri(N,N-diethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium di(N,N-diethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium (N,N-dimethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium tri(N,N-dimethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium di(N,N-diethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium (N,N-diethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)hafnium tri(N,N-diethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium (N,N-dimethylamide)
(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium di(N,N-dimethylamide)
Bis(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium (N,N-diethylamide)
Tris(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)chromium
(1,5,7-triaza[4.4.]bicyclo-dec-5-enyl)chromium di(N,N-diethylamide)
(Cyclopentadienyl)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride
(n-Butyl-Cyclopentadienyl)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride
(Indenyl)-(1,5,7-triaza[4.4.0]bicyclo-dec-5-enyl)zirconium dichloride
(Fluoren

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