Homogeneous, highly-filled, polyolefin composites

Claim 1

A solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (a) 10-75% by weight of polyolefin having an inherent viscosity of at least 2 selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbon atoms, and (b) 25-90% by weight of finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average average equivalent spherical particle diameter of 0.1 to less than 50μ, and having interacted at its surface sufficient catalytically-active transition metal compound which contains substantially no halogen bonded to the transition metal to provide 0.000001-1.7 milligram-atom of transition metal per gram of filler, said polyolefin being polymerized onto the surface of said filler, and said composite being substantially free of polymer-free filler and filler-free polymer, being a free-flowing powder, having particle sizes in the range of 0.1μ to 5 mm, and having a 10-second micronization homogeneity of at least 50% and a micronization homogeneity index of at least 20.

Claim 17

The method of preparing a solid, homogeneous, particulate, highly-filled polyolefin composite which comprises (A) dehydrating finely-divided aluminum silicate clay selected from the group consisting of kaolinite, attapulgite and fuller's earth, and containing at least 0.05% by weight of titania, said clay having a weight-average equivalent spherical particle diameter of less than 50μ, and being free of promotion with added transition metal coordination catalyst component, by heating at a temperature of 400°-1400° C. to reduce the water content to less than one mole of water per mole of aluminum silicate clay; (B) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound, said filler being (a) 70-100% by weight of said dehydrated aluminum silicate clay, and (b) 0-30% by weight of pigmentary oxide selected from the group consisting of titania, zinc oxide, antimony trioxide and mixtures thereof, said pigmentary oxide having a weight-average equivalent spherical particle diameter less than that of the clay, and (2) 0.001-1.0 millimole, per gram of filler, of organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each, in an inert, liquid hydrocarbon diluent; (C) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene with one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-250° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-70% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbons having an inherent viscosity of at least 4 is formed; and (D) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 18

The method of preparing a solid, homogeneous, particulate, highly-filled polyolefin composite which comprises (A) dehydrating finely-divided aluminum silicate clay selected from the group consisting of kaolinite, attapulgite and fuller's earth, and containing at least 0.05% by weight of titania, said clay having a weight-average equivalent spherical particle diameter of less than 50μ, and being free of promotion with added transition metal coordination catalyst component, by heating at a temperature of 400°-1400° C. to reduce the water content to less than one mole of water per mole of aluminum silicate clay; (B) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound, said filler being (a) 70-100% by weight of said dehydrated aluminum silicate clay, and (b) 0-30% by weight of pigmentary oxide selected from the group consisting of titania, zinc oxide, antimony trioxide and mixtures thereof, said pigmentary oxide having a weight-average equivalent spherical particle diameter less than that of the clay, and (2) 0.001-1.0 millimole, per gram of filler, of organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each, in an inert, liquid hydrocarbon diluent; (C) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene with one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-250° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-70% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbons having an inherent viscosity of at least 4 is formed; and (D) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 23

The method of preparing a solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (A) contacting a finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average equivalent spherical particle diameter of less than 50μ with sufficient hydrolyzable titanium compound to provide 0.000001-1.7 milligram-atom, per gram of filler, of titanium interacted at the surface of the filler; (B) removing unadsorbed titanium compound from the filler; (C) hydrolyzing the adsorbed titanium compound; (D) activating the titanium-treated filler by heating at a temperature of at least 100° C. to form a titania-modified filler; (E) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound, said filler being (a) 70-100% by weight of said titania-modified filler, and (b) 0-30% by weight of pigmentary oxide which is not titania-modified, said pigmentary oxide being selected from the group consisting of titania, zinc oxide, antimony trioxide and mixtures thereof and having a weight-average equivalent spherical particle diameter less than that of said titania-modified filler; and (2) 0.0001-1.0 millimole, per gram of filler, of organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each, in an inert, liquid hydrocarbon diluent; (F) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene with one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-250° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-70% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbons having an inherent viscosity of at least 4 is formed; and (G) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 24

The method of preparing a solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (A) contacting a finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average equivalent spherical particle diameter of less than 50μ with sufficient hydrolyzable titanium compound to provide 0.000001-1.7 milligram-atom, per gram of filler, of titanium interacted at the surface of the filler; (B) removing unadsorbed titanium compound from the filler; (C) hydrolyzing the adsorbed titanium compound; (D) activating the titanium-treated filler by heating at a temperature of at least 100° C. to form a titania-modified filler; (E) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound, said filler being (a) 70-100% by weight of said titania-modified filler, and (b) 0-30% by weight of pigmentary oxide which is not titania-modified, said pigmentary oxide being selected from the group consisting of titania, zinc oxide, antimony trioxide and mixtures thereof and having a weight-average equivalent spherical particle diameter less than that of said titania-modified filler; and (2) 0.0001-1.0 millimole, per gram of filler, of organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each, in an inert, liquid hydrocarbon diluent; (F) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene with one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-250° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-70% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbons having an inherent viscosity of at least 4 is formed; and (G) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 31

The method of preparing a solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (A) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average equivalent spherical particle diameter of less than 50 μ, and (2) 0.001-1.0 millimole, per gram of filler, of organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each, in an inert, liquid hydrocarbon diluent; (B) adding to the resulting dispersion catalytically-active, hydrocarbon-soluble, organic, transition metal compound which contains substantially no halogen bonded to the transition metal and which is at least 50 times more active when adsorbed onto the surface of the filler than in solution in an amount equivalent to 0.00001-0.1 milligram-atom of transition metal per gram of filler; (C) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene with one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-100° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-75% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbon atoms having an inherent viscosity of at least 2 is formed; and (D) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 32

The method of preparing a solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (A) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average equivalent spherical particle diameter of less than 50 μ, and (2) 0.001-1.0 millimole, per gram of filler, of organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each, in an inert, liquid hydrocarbon diluent; (B) adding to the resulting dispersion catalytically-active, hydrocarbon-soluble, organic, transition metal compound which contains substantially no halogen bonded to the transition metal and which is at least 50 times more active when adsorbed onto the surface of the filler than in solution in an amount equivalent to 0.00001-0.1 milligram-atom of transition metal per gram of filler; (C) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene with one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-100° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-75% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbon atoms having an inherent viscosity of at least 2 is formed; and (D) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 44

The method of preparing a solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (A) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average equivalent spherical particle diameter of 0.1 to less than 50μ, and (2) the organoaluminum compound-transition metal compound complex formed by reacting (a) organoaluminum compound selected from the group consisting of trialkylaluminum, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each with (b) catalytically-active, hydrocarbon-soluble, organic, transition metal compound which contains substantially no halogen bonded to the transition metal and which is at least 50 times more active when adsorbed onto the surface of the filler than in solution, in an amount sufficient to provide a mole ratio of organoaluminum compound to transition metal compound of 1000:1 to 4:1, in an amount equivalent to 0.001-1.0 millimole, per gram of filler, of organoaluminum compound and 0.00001-0.05 milligram-atom, per gram of filler, of transition metal in an inert, liquid hydrocarbon diluent; (B) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene and one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-100° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-75% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbons having an inherent viscosity of at least 2 is formed; and (C) isolating the resulting polyolefin/filler composite as a free-flowing powder.

Claim 45

The method of preparing a solid, homogeneous, particulate, highly-filled, polyolefin composite which comprises (A) dispersing (1) at least 1 weight/volume percent of finely-divided, inorganic filler compound having a neutral-to-acidic surface and a weight-average equivalent spherical particle diameter of 0.1 to less than 50μ, and (2) the organoaluminum compound-transition metal compound complex formed by reacting (a) organoaluminum compound selected from the group consisting of trialkylaluminum, dialkylaluminum hydrides, dialkylaluminum alkoxides, alkylaluminum halides and polymeric hydrocarbylaluminums in which the alkyl groups, alike or different, have 1-10 carbons each with (b) catalytically-active, hydrocarbon-soluble, organic, transition metal compound which contains substantially no halogen bonded to the transition metal and which is at least 50 times more active when adsorbed onto the surface of the filler than in solution, in an amount sufficient to provide a mole ratio of organoaluminum compound to transition metal compound of 1000:1 to 4:1, in an amount equivalent to 0.001-1.0 millimole, per gram of filler, of organoaluminum compound and 0.00001-0.05 milligram-atom, per gram of filler, of transition metal in an inert, liquid hydrocarbon diluent; (B) contacting the resulting dispersion with olefin selected from the group consisting of ethylene and mixtures of ethylene and one or more 1-alkenes of 3 to 10 carbons with agitation at a temperature of 0°-100° C. and a pressure from atmospheric to 500 atmospheres until a composite containing 10-75% by weight, based on the polyolefin and filler, of polyolefin selected from the group consisting of polyethylene and copolymers of ethylene containing up to 15% by weight of units derived from one or more 1-alkenes of 3 to 10 carbons having an inherent viscosity of at least 2 is formed; and (C) isolating the resulting polyolefin/filler composite as a free-flowing powder.