Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Patent
1998-03-02
2000-07-11
Bell, Mark L.
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
502150, 502152, 502155, 502202, 526128, 526130, 526134, 526160, 526943, B01J 3100, C08F 444, C08F 406
Patent
active
060872934
DESCRIPTION:
BRIEF SUMMARY
This invention relates to supports and supported catalysts formed therefrom that are useful for polymerization of olefins. More particularly, the invention relates to such supports comprising an activator compound that is chemically bound or tethered to the support. The invention also relates to the preparation of such support materials and supported catalysts and to their use in an olefin polymerization process.
Several supported cation forming catalysts for use in olefin polymerization processes have been previously disclosed in the art. WO-91/09882 described a supported catalyst prepared by combining i) a bis(cyclopentadienyl) metal compound containing at least one ligand capable of reacting with a proton, ii) an activator component comprising a cation capable of donating a proton and a bulky, labile anion capable of stabilizing the metal cation formed as a result of reaction between the metal compound and the activator component, and iii) a catalyst support material. The support material could be subjected to a thermal or chemical dehydration treatment. In some of the examples triethylaluminum was added for this purpose. The maximum bulk density of polymers formed by use of the foregoing supported catalyst reported in WO91/09882 was 0.17 g/cm.sup.3. Catalyst efficiencies that were reported were less than satisfactory for commercial application.
WO-94/03506 described a supported ionic catalyst prepared by combining i) a monocyclopentadienyl metal compound, ii) an activator component comprising a cation which will irreversibly react with at least one ligand contained in said metal compound and an anion, said anion being a chemically stable, non-nucleophilic, anionic complex, and iii) a catalyst support material. Optionally, the supported ionic catalyst could be prepolymerized with an olefinic monomer. The support material could also be treated with a hydrolyzable organoadditive, preferably a Group 13 alkyl compound such as triethylaluminum. The reference also taught the use of such supported ionic catalysts in a gas phase polymerization process. Disadvantageously, the catalyst efficiencies obtained in WO-94/03506, were likewise insufficient for commercial use.
In U.S. Pat. No. 5,399,636, supported metallocene catalysts wherein the metallocene was chemically attached to support materials, including silica, alumina, clay, phosphated alumina, and mixtures thereof, were disclosed. In U.S. Pat. No. 5,427,991, certain catalyst supports comprising polyanionic moieties constituted of noncoordinating anionic groups chemically bonded to crosslinked polymeric core components were disclosed. At column 19, lines 4-12 the reference taught the desirability of masking or protecting hydroxyl groups on the substrate by using standard chemical treatments. However, masking or protecting the hydroxyl groups prior to the reaction with the noncoordinating anionic reactant renders them inert to further reaction, thereby defeating the purpose of the invention. Performing the masking or protecting after reaction of the noncoordinating anionic reactant detrimentally interferes with the desired chemically bonded anionic moieties. In FIG. 8, an alternative scheme comprising functionalizing surface hydroxyl groups by reaction with p-bromophenyl(trimethoxy)silane was postulated. No teaching of the desirability of limiting the quantity of surface hydroxyl functionality of the silica to amounts less than 1.0 mmol/g was provided. In addition no disclosure of forming reactive silane functionality instead of p-bromophenylsiloxane functionality is provided by the reference. For the foregoing reasons, the disclosure of this publication with respect to silica or alumina based starting materials is believed to be inoperable or deficient.
Cationic homogeneous catalysts prepared by the use of cation forming activator compounds are disclosed in numerous prior art references. In EP-A-277,004 and U.S. Pat. No. 5,064,802 the use of Bronsted acid salts able to form cations via hydrogen transfer is disclosed. In EP-A-277,003, a similar process using b
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Carnahan Edmund M.
Carney Michael J.
Neithamer David R.
Nickias Peter N.
Shih Keng-Yu
Bell Mark L.
Pasterczyk J.
The Dow Chemical Company
W.R. Grace & Co.-Conn.
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