Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
2000-12-01
2004-07-13
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S127000, C502S125000, C502S121000, C502S129000, C502S132000, C502S134000, C502S104000, C502S110000
Reexamination Certificate
active
06762145
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a catalyst for polymerization and co-polymerization of ethylene, or more particularly to a solid titanium catalyst supported onto a carrier containing magnesium, which has a very high catalytic activity with excellent catalyst morphology.
2. Description of the Relevant Art
Catalysts containing magnesium for polymerization and co-polymerization of ethylene are known to have very high catalytic activities and to accord high bulk density, which are suitable for liquid or gas phase polymerization. By liquid phase polymerization of ethylene, it denotes a polymerization process performed in a medium such as bulk ethylene, isopentane, or hexane, and as for the important characteristics of the catalyst used in this process, they are as follows: high activity, bulk density of produced polymers, the amount of low molecular weight polymer dissolved in a medium, etc. Of these characteristics, it could be said that catalytic activity is the most important characteristics of a catalyst.
Many of the titanium-based catalysts containing magnesium for olefin polymerization, and the manufacturing methods thereof have been reported. Especially, many processes making use of magnesium solutions to obtain olefin polymerization catalysts of high bulk density have been known. There is a means of obtaining magnesium solution by reacting a magnesium compound with an electron donor such as alcohol, amine, cyclic ether, or organic carboxylic acid in the presence of a hydrocarbon solvent. As for the cases of using alcohol, they are disclosed in U.S. Pat. Nos. 4,330,649 and 5,106,807. Further, a method for producing a magnesium-supported catalyst by reacting a liquid-phase magnesium solution with a halogen compound such as titanium tetrachloride is well known. Although these types of catalysts provide high bulk density, there are disadvantages at the production stage, such as a need for improvement with respect to catalytic activity, a large quantity of expensive TiCl
4
in use, and a large amount of hydrogen chloride produced during the manufacturing process.
U.S. Pat. No. 5,459,116 discloses a method of producing a solid titanium catalyst by contact-reacting a magnesium solution having an ester of at least one hydroxy group as an electron donor with a titanium compound. By using this method, a catalyst with a high polymerization activity and superior bulk density of polymers may be obtained. Yet, there are disadvantages at the production stage, such as a large quantity of expensive TiCl
4
in use, and a large amount of hydrogen chloride produced during the manufacturing process.
U.S. Pat. No. 4,843,049 discloses a method of producing a catalyst having high titanium content by reacting a magnesium chloride-ethanol substrate, produced by spray-drying, with titanium alkoxide, followed by reacting diethyl aluminum chloride or ethyl aluminum sesquichloride. However, this method has disadvantages of having alcohol content outside the range of 18-25% and deteriorating bulk density of polymers produced when compounds other than diethyl aluminum chloride or ethyl aluminum sesquichloride are used. Further, there is a problem of setting the titanium content to at least 8 wt % or more in order to obtain high catalytic activity.
U.S. Pat. Nos. 5,726,261 and 5,585,317 disclose a method of producing a catalyst having a porosity of 0.35~0.7, supported with a titanium compound having at least one titanium-halogen and one hydroxy group, by treating the magnesium-ethanol substrate produced by means of a spray-drying method with triethyl aluminum, or heat-treating the same, and then treating it with a titanium alkoxide compound, titanium alkoxide or silicon tetraethoxide, etc. Yet, this method has a disadvantage of somewhat low catalytic activity.
SUMMARY OF THE INVENTION
As shown above, there is a need for the development of a new catalyst for polymerization or co-polymerization of ethylene with the following conditions: simple manufacturing process, high polymerization activity while not using a large amount of expensive titanium compounds, and high bulk density of polymers by means of controlling the catalyst particles. In an embodiment recited herein is disclosed a method for producing, from low-cost compounds via a simple process, a catalyst having excellent catalytic activity, capable of producing polymers of high bulk density by controlling the catalyst particle morphology.
Consequently, one embodiment described herein is directed to a new catalyst for polymerization or co-polymerization of ethylene, wherein said catalyst has enhanced catalytic activity and is capable of producing polymers of high bulk density.
An advantage of the disclosed method is to provide a simple process specifically for producing a catalyst for polymerization or co-polymerization of ethylene.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A solid titanium catalyst of high catalytic activity, capable of producing polymers having high bulk density as described herein, is produced by a simple yet efficient manufacturing process, which includes (i) preparing a magnesium solution by contact-reacting a halogenated magnesium compound with alcohol; (ii) reacting the same with an ester compound that includes at least one hydroxy group, or a silicon compound containing an alkoxyl group and a phosphorous compound; (iii) reacting the same with an aluminum compound, and then producing a solid titanium catalyst by adding a titanium compound, or a titanium compound and a vanadium compound.
Examples of halogenated magnesium compounds used in the present invention are as follows: di-halogenated magnesium such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; alkymagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, and amylmagnesium halide; alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagensium halide, isopropoxymagnesium halide, butoxymagnesium halide, octoxymagnesium halide; and aryloxymagnesium halides such as phenoxymagnesium halide and methyl-phenoxymagnesium halide. Of the above magnesium compounds, two or more compounds may be used in a mixture. Further, the above magnesium compounds may be effectively used in the form of a complex compound with other metals.
Of the compounds listed above, some may be represented by a simple chemical formula, but the others cannot be so represented depending on the production methods of magnesium compounds. In the latter cases, it may be generally regarded as a mixture of some of the above listed compounds as follows: compounds obtained by reacting a magnesium compound with a polysiloxane compound, a silane compound containing halogen, ester, alcohol, etc.; and compounds obtained by reacting a magnesium metal with alcohol, phenol, or ether in the presence of halosilane, phosphorus pentachloride, or thionyl chloride. However, the preferable magnesium compounds are magnesium halides, especially magnesium chlorides or alkylmagnesium chlorides, preferably those having an alkyl group of 1~10 carbons; alkoxymagnesium chlorides, preferably those having an alkoxy group of 1~10 carbons; and aryloxymagnesium chlorides, preferably those having an aryloxy group of 6~20 carbons. The magnesium solution used may be made by dissolving the aforementioned compounds in alcohol solvent in the presence or absence of a hydrocarbon solvent.
Examples of the types of hydrocarbon solvents used in the present invention are as follows: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride, and chlorobenzene.
When a magnesium compound is converted into a magnesium s
Kim Sang-Yull
Lee Weon
Yang Chun-Byung
Bell Mark L.
Brown Jennine
Meyertons Eric B.
Meyertons Hood Kivlin Kowert & Goetzel P.C.
Samsung General Chemicals Co. Ltd.
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