Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-08-14
2004-01-27
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S118000, C502S119000, C502S120000, C502S121000, C502S122000, C502S123000, C502S124000, C502S125000, C502S126000, C502S127000, C502S128000, C502S129000, C502S130000, C502S131000, C502S132000, C502S133000, C502S134000
Reexamination Certificate
active
06683018
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATION
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
NOT APPLICABLE
INCORPORATION-BY-PREFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC (See 37 CFR 152(e)(5) and MPEP 608.05. Computer program listings (37 CFR 1.96(c)), “Sequence Listings” (37 CFR 1.821(c)), and tables having more than 50 pages of text are permitted to be submitted on compact discs.) or REFERENCE TO A “MICROFICHE APPENDIX” (See MPEP §608.05(a).
NOT APPLICABLE
The present invention relates to a process for the preparation of a supported catalyst system, an organic or inorganic carrier material being reacted in a first step with a metal compound of the formula I
M
1
(R
1
)
r
(R
2
)
s
(R
3
)
t
(R
4
)
u
I
where
M
1
is an alkali metal, an alkaline earth metal or a metal of main group III or IV of the Periodic Table,
R
1
is hydrogen, C
1
- to C
10
-alkyl, C
6
- to C
15
-aryl, alkylaryl or arylalkyl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
R
2
to R
4
are each hydrogen, halogen, C
1
- to C
10
-alkyl, C
6
- to C
15
-aryl, alkylaryl, arylalkyl, alkoxy, aryloxy or dialkylamino, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
r is an integer from 1 to 4
and
s, t and u are each an integer from 0 to 3, the sum r+s+t+u corresponding to the valency of M
1
,
in the presence of an inert solvent and, in a subsequent step, the suspension thus obtained being reacted with a metallocene complex and a compound forming metallocenium ions.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
(2) Description of Related Art Including Information Disclosed under 37 CFR and 1.98
Metallocene catalyst systems are becoming more and more important for the polymerization of olefins. Supported catalyst systems are used for this purpose, particularly for polymerization processes in the gas phase. The preparation of various supported catalyst systems has therefore long been known.
If the carrier material used is an inorganic one, such as silica gel, it is generally necessary to modify reactive groups, such as hydroxyl groups, on the surface of the carrier, which are capable of reacting with the central atom of the catalyst complex. Particularly when metallocene catalyst complexes are applied to the carrier, such surface modification is necessary.
Processes for supporting metallocenes on inorganic carrier materials, in which the carrier material is reacted with an organometallic compound before the reaction with the metallocene and, if required, further cocatalysts, are known. Such processes are described, for example, in WO 91/09882, WO 94/03506, WO 95/15815, WO 95/14044 and DE-A1-19606167. In all these processes, however, the silica gel modified with the organometallic compound is freed from the reaction solution—generally by filtration—before the reaction with the further catalyst components is carried out. However, this procedure is inconvenient, requires additional apparatus and therefore adversely affects the cost-efficiency of the process.
It is an object of the present invention to provide a process for the preparation of supported catalyst systems which does not have these disadvantages and leads in a simpler manner to a supported catalyst system of comparable productivity and quality.
BRIEF SUMMARY OF THE INVENTION
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
NOT APPLICABLE
DETAILED DESCRIPTION OF THE INVENTION
NOT APPLICABLE
CLAIM OR CLAIMS (commencing on a separate sheet)
ABSTRACT OF THE DISCLOSURE (commencing on a separate sheet)
SEQUENCE LISTING (See MPEP §2424 and 37 CFR 1.821-1.8725. A nucleotide or amino acid sequence as defined in 37 CFR 1.821(a) and if the required “Sequence Listing” is not submitted as an electronic document on compact disc).
NOT APPLICABLE
NOT APPLICABLE
DETAILED DESCRIPTION OF THE INVENTION
We have found that this object is achieved by a process for the preparation of a supported catalyst system, an inorganic carrier material being reacted with a metal compound described above and of the formula I in the presence of an inert solvent in a first step and, in a subsequent step, the suspension thus obtained being reacted with a metallocene complex and a compound forming metallocenium, in which process the solvent is not removed after the first step and the subsequent step is carried out without isolation of the pretreated carrier material thus obtained.
Preferably used carrier materials are inorganic solids whose particle diameters are from 1 to 200 &mgr;m, in particular from 30 to 70 &mgr;m.
Suitable carrier materials are preferably silica gels, particularly preferably those of the formula SiO
2
.aAl
2
O
3
, where a is from 0 to 2, preferably from 0 to 0.5; these are therefore aluminosilicates or silica. Such products are commercially available, e.g. Silica Gel 332 from Grace or ES70X from Cosfield.
To remove the adsorbed water, these carrier materials may be subjected to thermal treatment or may also be calcined, a treatment at 80-200° C., preferably 100-150° C., preferably being carried out.
Other inorganic compounds, such as Al
2
O
3
or MgCl
2
, or mixtures containing these compounds may also be used as carrier materials.
Preferred metal compounds of the formula I are those in which M
1
is a metal of main group III of the Periodic Table, in particular aluminum, R
1
is C
1
- to C
10
-alkyl and R
2
to R
4
are each C
1
- to C
10
-alkyl. For the particularly preferred case where M
1
is aluminum, u is zero. R
1
to R
3
advantageously have the same meaning and are each preferably methyl, ethyl, isobutyl or hexyl, especially isobutyl.
The metal compound of the formula I is preferably added in the form of a solution to a suspension of the carrier. Particularly suitable solvents or suspending agents are hydrocarbons, such as toluene or heptane. Solvents in which the metallocene complex is readily soluble are particularly preferred. The amount of metal compound I may vary within wide limits and the minimum amount depends on the number of hydroxyl groups of the carrier. Even without isolation of the pretreated carrier material after this first process step, small variations in the ratio of carrier to compound I lead only to slight differences in the performance of the catalyst system. Depending on the type of the carrier material, however, this ratio should be optimized by preliminary experiments. The temperatures, reaction times and pressures are not critical per se, temperatures of −20 to 100° C. and reaction times of from 0.1 to 48 hours being preferred.
The suspension thus obtained is then reacted in a subsequent step with a metallocene complex and a compound forming metallocenium ions, without isolation and removal of the solvent.
Examples of suitable metallocene complexes are the following compounds of the formula III:
where:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
X is fluorine, chlorine, bromine, iodine, hydrogen or C
1
- to C
10
-alkyl,
R
8
to R
12
are each hydrogen, C
1
- to C
10
-alkyl, 5- to 7-membered cycloalkyl, which in turn may carry C
1
- to C
10
-alkyl as a substituent, C
6
- to C
15
-aryl or arylalkyl, it also being possible for two neighboring radicals together to be a cyclic group of 4 to 15 carbon atoms, or Si(R
13
)
3
,
R
13
is C
1
- to C
10
-alkyl, C
3
- to C
10
-cycloalkyl or C
6
- to C
15
-aryl,
R
14
to R
18
are each hydrogen, C
1
- to C
10
-alkyl, 5- to 7-membered cycloalkyl, which in turn may carry C
1
- to C
10
-alkyl as a substituent, C
6
- to C
15
-aryl or arylalkyl, it also being possible for two neighboring radicals together to be a cyclic group of 4 to 15 carbon atoms, or Si(R
19
)
3
,
R
19
is C
1
- to C
10
-alkyl, C
6
- to C
15
-aryl or C
3
- to C
10
-cycloalkyl,
or R
11
and Z together form a group —R
20
—A—,
R
21
, R
22
and R
23
are identical or different and are each hydrogen, halogen, C
1
-C
10
alkyl, C
1
-C
10
fluoroalkyl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryl, C
1
-C
10
alkoxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
8
-C
4
Deloux Laurent
Kölle Peter
Kristen Marc Oliver
Moll Ulrich
Rief Ursula
BASF - Aktiengesellschaft
Bell Mark L.
Brown Jennine
Keil & Weinkauf
LandOfFree
Method for producing a supported catalyst system does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method for producing a supported catalyst system, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for producing a supported catalyst system will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3256358