Diimino compounds

Details Diimino compounds Diimino compounds

2001-03-12

2002-06-25

Shaver, Paul F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C556S423000, C556S403000, C556S404000, C549S004000, C549S214000, C546S014000, C548S110000, C526S090000, C526S126000, C526S128000, C526S340000, C526S352000, C502S185000, C502S155000

Reexamination Certificate

active

06410768

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a new class of diimino compounds useful as ligands for obtaining late transition metal complexes covalently bonded to an inorganic support.
BACKGROUND OF THE INVENTION
It has been recently discovered that alpha-diimino ligands can be used for synthesizing complexes of late transition metals that are useful as catalyst for polymerizing olefins. For instance WO 96/23010 discloses, with several examples, various types of nickel or palladium diiniine complexes, showing that they can be used for polymerizing a large number of olefins.
In WO 98/27124 and WO 98/30612 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines) complexes of iron and cobalt are disclosed for polymerizing ethylene and propylene. WO 99/12981 relates to substituted 2,6 diimino pyridines complexes of Fe[II], Fe[III], Co[I], Co[II], Co[III]), Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] and Ru[IV].
Immobilizing these complexes on solid supports to enable heterogeneous polymerization process such as those based on gas phase, bulky or slurry processes, is important for their efficient industrial utilization. In particular, some non-supported nickel catalysts give rise to polymer characterized by a high level of branching. The melting points of these polymers are anticipated to be as low as to present problems with reactor operation at typical industrial operating temperatures, especially when heat dissipation by solvents is unavailable, as in continuous gas phase polymerization.
Supported diimino nickel or palladium catalysts are disclosed in WO 96/23010, WO 97/48736, WO 98/56832.
WO 96/23010 discloses supported diimino palladium or nickel catalysts. A process wherein a complex activated with a cocatalyst is adsorbed on silica is exemplified.
WO 97/48736 relates to immobilized catalysts; they are substantially obtained by preparing a precursor solution mixing together the complex with an aluminoxane and adding this precursor solution to a porous support.
In some examples of WO 98/56832 the cocatalyst was supported on an inorganic support and then a diimino complex was added, then the obtained catalyst was prepolymerized.
In these applications the diimino ligand is not functionalized for optimizing the bond between the support and the complex. As a result, in the supported catalyst obtained, the migration of the active species into the homogeneous phase during the polymerization reaction may happen.
Therefore the development of a new ligand class that permits a chemical bond between the carTier and the diimino complex is desirable.
An object of the present invention is a new class of diimino ligands functionalized with a siloxy group.
A further object of the present invention is a solid catalyst component for polymerizing olefins comprising: an inorganic support, a diimino ligand chemically bonded to the support and a transition metal.
In this solid component, chemical bonding to the support provides a firm attach of the catalytic centres to the support, resulting in a heterogeneous catalyst component. The preparation of said catalyst precursor results in no contaminating secondary reaction products, hence the catalyst is fiee from undesired impurities. The catalysts can be used in slurry or gas-phase processes. The catalysts are especially useful for the production of branched polyolefins from a single type of monomer.
SUMMARY OF THE INVENTION
The present invention relates to diimino compounds defined by following formulae:
wherein
n is 0 or 1; m is 1, 2 or 3;
each R
1
, equal to or different from each other, is selected from the group consisting of hydrogen, a monovalent aliphatic or aromatic hydrocarbon group, optionally containing heteroatonis of group 14 to 16 of the periodic table of the elements and boron; with the proviso that al least one R
1
group is represented by the formula R
5
OSi(R)
3
;
wherein
each R is independently selected from the group consisting of: C
1
-C
20
allkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
2
-C
20
alkenyl, C
7
-C
20
arylalkyl, C
7
-C
20
alkylaryl, C
8
-C
20
arylalkenyl, C
8
-C
20
alkenylaryl liear or branched; preferably it is methyl, ethyl or propyl;
each R
5
, equal to or different from each other, is a divalent aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing from 1 to 5 heteroatoms of groups 14, 15 or 16 of the periodic table of the elements and/or boron;
each R
2
, equal to or different from each other, is a radical which contains from 1 to 20 carbon atoms; this group optionally contains heteroatoms of group 14 to 16 of the periodic table of the elements and/or boron;
R
3
is a divalent aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing from 1 to 5 heteroatoms of groups 14, 15 and 16 of the periodic table of the elements and/or boron;
R
4
, equal to or different from each other, is hydrogen or a radical which contains from 1 to 20 carbon atoms; this group optionally contains heteroatoms of group 14 to 16 of the periodic table of the elements and/or boron;
This invention also relates to a process to prepare compounds represented by formula I or II above. Likewise this invention relates to a catalyst component comprising the product of the combination of the dilmino ligand and a porous inorganic support.
Further this invention also relates to the use of the catalyst component in combination with a cocatalyst to polymerize olefins
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to diimino compounds defined by the following formulae:
wherein
n is 0 or 1; m is 1, 2 or 3;
each R
1
, equal to or different from each other, is selected from the group consisting of: hydrogen, a monovalent aliphatic or aromatic hydrocarbon group, optionally containing heteroatoms of group 14 to 16 of the periodic table of the elements and/or boron; with the proviso that al least one R
1
group is represented by the formula R
5
OSi(R)
3
;
wherein
each R is independently selected from the group consisting of: C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
2
-C
20
alkenyl, C
7
-C
20
arylalkyl, C
7
-C
20
alkylaryl, C
8
-C
20
arylalkenyl, C
8
-C
20
alkenylaryl linear or branched; preferably it is methyl, ethyl or propyl;
each R
5
, equal to or different from each other, is a divalent aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing from 1 to 5 heteroatoms of groups 14, 15 and 16 of the periodic table of the elements and/or boron; preferably it is CR
6
2
(R
7
)
a
CR
6
2
;
wherein
each R
6
, equal to or different from each other, is selected from the group consisting of: hydrogen or R; two R
6
can also unite to form a ring; R
7
is selected from the group consisting of: O, NR, S, SiR
6
2
, C
1
-C
20
alkylidene, C
3
-C
20
cycloalkylidene, C
2
-C
20
alkenylidene, C
6
-C
20
arylidene, C
7
-C
20
alkylarylidene, C
7
-C
20
arylalkylidene, C
8
-C
20
arylalkenylidene, C
8
-C
20
alkenylarylidene, optionally containing heteroatoms of group 14 to 16 of the periodic table of the elements, and/or boron; a is 0 or 1;
each R
2
, equal to or different from each other, is a radical which contains from 1 to 20 carbon atoms; this group optionally contains heteroatoms of group 14 to 16 of the periodic table of the elements and/or boron;
preferably R
2
is selected from the group consisting of: C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
2
-C
20
alkenyl, C
7
-C
20
arylalkyl, C
7
-C
20
alkylaryl, C
8
-C
20
arylalkenyl alkenylaryl, linear or branched, optionally substituted by BR
6
2
, OR
6
, SiR
6
3
, NR
6
2
; most preferably R
2
is an alkylsubstituted phenyl, naphthyl, or anthracyl; most preferably R
2
is a 2,6 dialkylphenyl group, optionally substituted in position 4 by a group R;
R
3
is a divalent aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing from 1 to

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