Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2001-03-12
2003-07-01
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S117000, C502S104000, C502S155000
Reexamination Certificate
active
06586358
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a new class of nickel and palladium complexes useful in the (co)polymerization of olefins.
BACKGROUND OF THE INVENTION
It has been recently discovered that complexes of nickel or palladium with alpha-diimine ligand can be used as catalysts for polymerizing olefins; for instance WO 96/23010 discloses with several examples various types of these complexes, showing that they can be used for polymerizing a large number of olefins.
Immobilizing these complexes on solid supports to enable heterogeneous polymerization processes, such as those based on gas-phase, bulk or slurry processes, is important for their efficient industrial utilization. In particular, some non supported nickel catalysts give rise to polymers 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.
WO 96/23010 discloses supported diimine palladium or nickel catalysts. It exemplifies a process wherein a complex activated with a cocatalyst is adsorbed on silica.
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.
For avoiding the drawback of the migration of the active species into the homogeneous phase during the polymerization reaction, a chemical bond between the carrier and the diimino-complex could be desirable.
An object of the present invention is a bidentate diimino-complex of nickel or palladium containing a siloxy group, that can be easily supported on a carrier through a chemical bond between the carrier and the complex itself.
Another object of the present invention is an olefin polymerization catalyst comprising as catalyst component a diimino-complex of nickel or palladium containing a siloxy group.
A further object of the present invention is a solid polymerization catalyst comprising the diimino-complex of nickel or palladium object of the present invention, a carrier and a cocatalyst.
In this solid catalyst, the catalytic centres are attached to the support by means of the alkoxysilane functionality, thus providing a true heterogeneous catalyst. The preparation of said catalyst precursor results in little or no contaminating secondary reaction products, hence the catalyst is substantially or completely free from undesirable impurities. The catalysts can be used in solution, high pressure, slurry or gas-phase processes. The catalysts are especially useful for the production of branched polyethylene without requiring co-monomer.
SUMMARY OF THE INVENTION
The present invention relates to a bidentate diimino-complex of nickel or palladium containing at least one group OSi(R)
3
wherein each R, equal to or different from each other, 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, and C
8
-C
20
alkenylaryl, linear or branched, preferably each R is independently methyl, ethyl or propyl.
The present invention also relates to the process for the preparation of bidentate diimino complexes of nickel and palladium as well as the process for their use in olefin polymerization.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a bidentate diimino-complex of nickel or palladium containing at least one group OSi(R)
3
wherein each R, equal to or different from each other, 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, and C
8
-C
20
alkenylaryl, linear or branched, preferably R is methyl, ethyl or propyl. Preferably the bidenitate diimino-complex of nickel and palladium is defined by the following general formulas:
wherein
M is nickel or palladium, n is 0, 1, 2 or 3; m is 1, 2 or 3,
each X, equal to or different from each other, is independently selected from the group consisting of: halogen, hydrogen, OR, N(R)
2
, R, 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, and C
8
-C
20
alkenylaryl; linear or branched, preferably each R is independently methyl, ethyl or propyl; two X taken together can also form an aromatic or aliphatic divalent ligand, containing two equal or different donor atoms belonging to the group 14-16 of the periodic table of the elements, such as catecholate, 1,2-ethanediolate or 1,2-phenylenediamide, &agr;-deprotonated-&bgr;-diketone, &agr;-deprotonated-&bgr;-ketoester such as acetylacetonate or hexafluoracetylacetonate;
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 or boron; with the proviso that at least one R
1
group is represented by the formula: R
4
OSi(R)
3
;
wherein
each R
4
, 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 to 16 of the periodic table of the elements and/or boron;
preferably it is CR
5
2
(R
6
)
a
CR
5
2
,
wherein
each R
5
, equal to or different from each other, is selected from the group consisting of: hydrogen and R; two R
5
can also unite to form a ring;
R
6
is a divalent radical selected from the group comprising: O, NR, S, SiR
5
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
arylalkylidene, or C
8
-C
20
alkenylarylidene, linear or branched, 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 boron;
preferably each R
2
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, optionally substituted by BR
5
2
, OR
5
, SiR
5
3
, or NR
5
2
, most preferably R
2
is a alkylsubstituted phenyl, naphthyl or anthracyl, most preferably R
2
is a 2,6 dialkylphenyl group, optionally substituted in position 4 by a group R as defined above.
each R
3
, 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;
preferably R
3
is independently selected from the group consisting of: hydrogen, 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, and C
8
-C
20
alkenylaryl, linear or branched, optionally substituted by BR
5
2
, OR
5
, SiR
5
3
, or NR
5
2
where R
5
is defined above;
two or more R
1
, R
2
, R
3
and R
4
can also unite to form a from 4 to 15 membered aliphatic or aromatic ring; the ring optionally contains heteroatoms of group 14 to 16 of the periodic table of the elements and boron.
Preferably R
1
is selected from the group consisting of: hydrogen; C
1
-C
20
alkyl; C
3
-C
20
cycloalkyl; C
6
-C
20
aryl; C
2
-C
20
alk
Guzman Ernesto Carmona
Lafuente Antonio Muñoz-Escalona
Llatas Luis Mendez
Perez Juan Campora
Reyes Manuel Lopez
Bell Mark L.
Pasterczyk J.
Repsol Quimica S.A.
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