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
1999-03-15
2001-09-18
Wood, Elizabeth D. (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...
C502S110000, C502S127000, C502S132000, C502S133000
Reexamination Certificate
active
06291385
ABSTRACT:
BACKGROUND OF INVENTION
The present invention, which is the improvement of U.S. Pat. No. 5,459,116, relating to a catalyst for polymerization and copolymerization of olefin, particularly relates to a catalyst for production of polymers, which has high activity and provides polymer with narrow molecular weight distribution, and narrow particle size distribution, yielding small amount of low polymers.
Prior arts in olefin polymerization or copolymerization are the two: either production of solid catalytic components by reacting, with a halogen-containing titanium compound, the compound produced by reaction of a magnesium compound with alcohol, organic carboxylic acid, aldehyde, and amine and their mixture, in an inert hydrocarbon solvent; or production of solid titanium catalytic components by first producing an active carrier by the use of a halogen-containing silicon compound, tin compound, or an aluminum compound as recrystallized compounds, and next by contacting it with a titanium halide compound.
Now, U.S. Pat. Nos. 4,336,360 and 4,330,649 describe a method for producing a polymerization catalyst with high activity containing titanium components, by liquefying a magnesium carrier by reacting it with an electron donor such as alcohol in a hydrocarbon solvent, reacting it with such a halogen compound as silicon tetrachloride, which is a recrystallization process of the magnesium carrier component, in order to produce a solid magnesium carrier, and after all these processes, by having it supported by such a titanium compound as titanium tetrachloride, or by having it precipitated by pouring in titanium tetrachloride. But when olefin is polymerized or copolymerized with the use of a catalyst produced in the way given above, the resultant polymer has too much of fine powder, the particle size distribution being broad, and the bulk density low. Other defects include a rather broad molecular weight distribution and the yield of so much of low polymer soluble in such a solvent as hexane at the time of slurry polymerization. Here, a low polymer means a polymer which usually has a melting index of over 5000 and a molecular weight of under 1000.
U.S. Pat. No. 5,419,116, on the other hand, describes a method for producing a solid polymerization catalyst containing a magnesium compound, titanium compound, and electron donor components, for the purpose of remedying such defects of conventional catalysts as indicated above and yielding a catalyst possessed of a high activity, greater bulk density, by first liquefying a magnesium compound by reacting it with an electron donor such as alcohol in a hydrocarbon solvent, then, after reacting it with an ester compound having at least one hydroxy group, getting it to precipitate by reacting with such a titanium compound as titanium tetrachloride.
However, if olefin polymerization or copolymerization is performed with the use of such a catalyst produced that way, the catalyst does show a high activity and the resultant polymer has a merit of relatively high bulk density, but it nevertheless has such demerits as a broad particle size distribution, a broad molecular weight distribution, and a large yield of low polymer soluble in the solvents such as hexane at slurry polymerization.
SUMMARY OF INVENTION
The target of the present invention is to remedy all such defects of conventional catalysts as listed above and produce a new highly active catalyst to result in a polymer of granular grains, a narrow molecular weight distribution, high bulk density, a narrow particle size distribution, and also a minimum yield of low polymer if impossible to avoid low-density polymer at all.
DETAILED DESCRIPTION OF INVENTION
The catalyst of the present invention is characterized in that it utilizes, as inorganic substance, the mixture obtained by addition of an aluminum compound to a magnesium compound, and, as electron donor, an ester compound having at least one hydroxy group and a silane compound having at least one alkoxy group. In case the solid titanium catalyst of the present invention is used in polymerization the resultant polymer is one of a narrow molecular distribution and granular form of a narrow particle size distribution, the yield of low polymer being remarkably decreased.
A more detailed description of the invention is as follows:
The catalyst of the present invention is produced by (1) producing a liquid magnesium solution by reacting a mixture of a magnesium compound and an aluminum compound with alcohol in a solvent of inert hydrocarbon, (2) getting the liquefied magnesium solution to react with an ester compound having at least one hydroxy group and a silane compound having at least one alkoxy group, as electron donors, and then by reacting it by addition of a titanium compound.
The magnesium compounds used in production of the catalyst of the present invention may include such magnesium halides as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide; such alkoxy magnesium halides as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride; and such magnesium alkoxides as magnesium ethoxide, magnesium isopropoxide, and magnesium butoxide, etc.
The aluminum compounds used in production of the catalyst of the present invention may include such aluminum halides as aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide; such aluminum alkoxides as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, and aluminum tributoxide; aluminum hydroxide; etc. As to the quantity of aluminum compounds for use, according to that of magnesium for basis, preferably 0.01~2 mole, more preferably 0.05~1 mole, to 1 mol of magnesium is suitable in order to successfully obtain the desired properties of the catalyst.
As the solvent for production of the liquid magnesium solution, a hydrocarbon solution is used, and such aliphatic hydrocarbons as hexane, heptane, octane, decane, and kerosine, such cycloaliphatic hydrocarbons as cyclohexane and cyclooctane, and such aromatic hydrocarbons as benzene, toluene, xylene, and ethylbenzene can all be used. The quantity will, by that of magnesium as basis, preferably be 1~30 mole, more preferably 3~10 mole to each mol of magnesium.
Alcohols used in production of the liquid magnesium solution will include such aliphatic alcohols as methanol, ethanol, butanol, isopropanol, hexanol, 2-ethylhexanol, and decanol; such cycloaliphatic alcohols as cyclohexanol; such aromatic alcohols as phenol; etc. The quantity will be 0.1~10 mols to each mol of magnesium. The quantity of alcohol used to produce even liquid form of a magnesium compound is most preferably about 3~6 mole. The contact temperature of the magnesium compound and alcohol is preferably about 60~140 C., more preferably about 80~120 C., to be kept for one to four hours.
The ester compound having at least one hydroxy group, among the electron donors to react with the liquid magnesium solution in production of the catalyst of the present invention, may include such unsaturated aliphatic esters having at least one hydroxy group as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate; such aliphatic monoesters or polyesters having at least one hydroxy group as 2-hydroxyethyl acetate, methyl-3-hydroxy butylate, ethyl-3-hydroxy butylate, methyl-2-hydroxy isobutylate, ethyl-2-hydroxy isobutylate, methyl-3-hydroxy-2-methyl propionate, 2,2-dimethyl-3-hydroxy propionate, ethyl-6-hydroxy hexanoate, t-butyl-2-hydroxy isobutylate, diethyl-3-hydroxy glutarate, ethyl lactate, isopropyl lactate, butyl lactate, butylisobutyl lactate, isobutyl lactate, ethyl mandelate, dimethyltartrate, diethyltartrate, dibutyltartrate, trimethyl citrate, triethyl citrate, ethyl-2-hydroxy caproate, and diethyl bis-(hydroxy methyl)malonate; such aromatic esters having at least one hydroxy group as 2-hydroxyethyl benzoate, 2-hydroxy ethyl salicylate, methyl 4-(hydroxy methyl) benzoate, methy
Kang Youn-Kyung
Lee Young-Sub
Conley Rose & Tayon PC
Meyertons Eric B.
Pasterczyk J.
Samsung General Chemicals Co. Ltd.
Wood Elizabeth D.
LandOfFree
Catalyst for polymerization or copolymerization of olefin does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Catalyst for polymerization or copolymerization of olefin, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Catalyst for polymerization or copolymerization of olefin will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2541444