C08F4/24

Polyethylene copolymer resins and films

An ethylene/alpha-olefin copolymer that can be synthesized in a fluidized-bed, gas phase polymerization reactor and made into a blown film. The ethylene/alpha-olefin copolymer is characterized by a bubble stability-effective combination of properties comprising density, melt flow ratio (“I.sub.21/I.sub.5”), and melt storage modulus G′ (G″=3,000 Pa). The synthesis in the FB-GPP reactor is characterized by a property-imparting-effective combination of operating conditions comprising reactor bed temperature and H2/C2 gas molar ratio. An embodiment of the blown film consisting of the ethylene/alpha-olefin copolymer is characterized by enhanced bubble stability. A method of making the ethylene/alpha-olefin copolymer. A film comprising the ethylene/alpha-olefin copolymer. A method of making the film. A manufactured article comprising the film.

Modified Supported Chromium Catalysts and Ethylene-Based Polymers Produced Therefrom

Supported chromium catalysts with an average valence less than +6 and having a hydrocarbon-containing or halogenated hydrocarbon-containing ligand attached to at least one bonding site on the chromium are disclosed, as well as ethylene-based polymers with terminal alkane, aromatic, or halogenated hydrocarbon chain ends. Another ethylene polymer characterized by at least 2 wt. % of the polymer having a molecular weight greater than 1,000,000 g/mol and at least 1.5 wt. % of the polymer having a molecular weight less than 1000 g/mol is provided, as well as an ethylene homopolymer with at least 3.5 methyl short chain branches and less than 0.6 butyl short chain branches per 1000 total carbon atoms.

Modified Supported Chromium Catalysts and Ethylene-Based Polymers Produced Therefrom

Supported chromium catalysts with an average valence less than +6 and having a hydrocarbon-containing or halogenated hydrocarbon-containing ligand attached to at least one bonding site on the chromium are disclosed, as well as ethylene-based polymers with terminal alkane, aromatic, or halogenated hydrocarbon chain ends. Another ethylene polymer characterized by at least 2 wt. % of the polymer having a molecular weight greater than 1,000,000 g/mol and at least 1.5 wt. % of the polymer having a molecular weight less than 1000 g/mol is provided, as well as an ethylene homopolymer with at least 3.5 methyl short chain branches and less than 0.6 butyl short chain branches per 1000 total carbon atoms.

Particle size control of supported chromium catalysts in loop slurry polymerization reactors

Supported chromium catalysts containing a solid oxide and 0.1 to 15 wt. % chromium, in which the solid oxide or the supported chromium catalyst has a particle size span from 0.5 to 1.4, less than 3 wt. % has a particle size greater than 100 μm, and less than 10 wt. % has a particle size less than 10 μm, can be contacted with an olefin monomer in a loop slurry reactor to produce an olefin polymer. Representative ethylene-based polymers produced using the chromium catalysts have a HLMI of 4 to 70 g/10 min, a density from 0.93 to 0.96 g/cm.sup.3, from 150 to 680 ppm solid oxide (such as silica), from 1.5 to 6.8 ppm chromium, and a film gel count of less than 15 catalyst particle gels per ft.sup.2 of 25 micron thick film and/or a gel count of less than or equal to 50 catalyst particles of greater than 100 μm per five grams of the ethylene polymer.

Particle size control of supported chromium catalysts in loop slurry polymerization reactors

Supported chromium catalysts containing a solid oxide and 0.1 to 15 wt. % chromium, in which the solid oxide or the supported chromium catalyst has a particle size span from 0.5 to 1.4, less than 3 wt. % has a particle size greater than 100 μm, and less than 10 wt. % has a particle size less than 10 μm, can be contacted with an olefin monomer in a loop slurry reactor to produce an olefin polymer. Representative ethylene-based polymers produced using the chromium catalysts have a HLMI of 4 to 70 g/10 min, a density from 0.93 to 0.96 g/cm.sup.3, from 150 to 680 ppm solid oxide (such as silica), from 1.5 to 6.8 ppm chromium, and a film gel count of less than 15 catalyst particle gels per ft.sup.2 of 25 micron thick film and/or a gel count of less than or equal to 50 catalyst particles of greater than 100 μm per five grams of the ethylene polymer.

Methods of preparing a catalyst

A method comprising a) drying a support material comprising silica at temperature in the range of from about 150° C. to about 220° C. to form a dried support; b) contacting the dried support with methanol to form a slurried support; c) subsequent to b), cooling the slurried support to a temperature of less than about 60° C. to form a cooled slurried support; d) subsequent to c), contacting the cooled slurried support with a titanium alkoxide to form a titanated support; and e) thermally treating the titanated support by heating to a temperature of equal to or greater than about 150° C. for a time period of from about 5 hours to about 30 hours to remove the methanol and yield a dried titanated support.

Methods of preparing a catalyst

A method comprising a) drying a support material comprising silica at temperature in the range of from about 150° C. to about 220° C. to form a dried support; b) contacting the dried support with methanol to form a slurried support; c) subsequent to b), cooling the slurried support to a temperature of less than about 60° C. to form a cooled slurried support; d) subsequent to c), contacting the cooled slurried support with a titanium alkoxide to form a titanated support; and e) thermally treating the titanated support by heating to a temperature of equal to or greater than about 150° C. for a time period of from about 5 hours to about 30 hours to remove the methanol and yield a dried titanated support.

Methods of preparing a catalyst utilizing hydrated reagents

A method comprising a) contacting a solvent, a carboxylic acid, and a peroxide-containing compound to form an acidic mixture wherein a weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) contacting a titanium-containing compound and the acidic mixture to form a solubilized titanium mixture wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4 and an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1 wt. % to about 20 wt. % water and the solubilized titanium mixture to form an addition product and drying the addition product by heating to a temperature in a range of from about 50° C. to about 150° C. and maintaining the temperature in the range of from about 50° C. to about 150° C. for a time period of from about 30 minutes to about 6 hours to form a pre-catalyst.

Methods of preparing a catalyst utilizing hydrated reagents

A method comprising a) contacting a solvent, a carboxylic acid, and a peroxide-containing compound to form an acidic mixture wherein a weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) contacting a titanium-containing compound and the acidic mixture to form a solubilized titanium mixture wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4 and an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1 wt. % to about 20 wt. % water and the solubilized titanium mixture to form an addition product and drying the addition product by heating to a temperature in a range of from about 50° C. to about 150° C. and maintaining the temperature in the range of from about 50° C. to about 150° C. for a time period of from about 30 minutes to about 6 hours to form a pre-catalyst.

Methods of preparing a catalyst

A method of preparing a catalyst comprising a) contacting a non-aqueous solvent, a carboxylic acid, and a chromium-containing compound to form an acidic mixture; b) contacting a titanium-containing compound with the acidic mixture to form a titanium treatment solution; c) contacting a pre-formed silica-support comprising from about 0.1 wt. % to about 20 wt. % water with the titanium treatment solution to form a pre-catalyst; and d) thermally treating the pre-catalyst to form the catalyst. A method of preparing a catalyst comprising a) contacting a non-aqueous solvent and a carboxylic acid to form an acidic mixture; b) contacting a titanium-containing compound with the acidic mixture to form a titanium treatment solution; c) contacting a pre-formed chrominated silica-support comprising from about 0.1 wt. % to about 20 wt. % water with the titanium treatment solution to form a pre-catalyst; and d) thermally treating the pre-catalyst to form the catalyst.