Process for polymerisation of alpha-mono olefins, supported catalyst therefor and method of preparing said catalyst

Claim 2

A catalyst for the polymerization or copolymerization of alpha-monoolefins, in the presence of an organoaluminum activator, consisting essentially of the product from the steps of reducing a transition metal compound with an excess of organomagnesium compound in the presence of a support material selected from the group consisting of silica, alumina and mixtures thereof, and then deactivating the excess organomagnesium compound with a deactivation agent therefor; said transition metal compoung being selected from the group consisting of the halides, oxyhalides, alcoholates of aliphatic alcohols having 1 to 6 carbon atoms in the alkyl groups, acetates, benzoates, acetylacetonates, and the dicyclopentadienyl salts of the metals of Groups IV-B, V-B, VI-B and VIII of the Periodic System; said organomagnesium compound being selected from the group ; consisting of compounds of formula RHgX where R is alkyl having 1 to 20 carbon atoms, or aryl having 6 to 10 carbon atoms and X is R, halide, or -OR, and complexes of RMgX with solubilizing agents; and said deactivating agent being selected from the group consisting of hydrogen chloride, hydrogen bromide, water, acetic acid, alcohols, carbonic acid, phosphorus pentachloride, silicon tetrachloride, acetylene and mixtures thereof.

Claim 3

The catalyst of Claim 1 wherein said transition metal compound is a compound of titanium, zirconium or vanadium.

Claim 4

The catalyst of Claim 2 wherein said titanium compound is selected from the group consisting of titanium tetrachloride, tetrapropyltitanate, tetrabutyltitanate and mixtures thereof.

Claim 5

The catalyst of any one of claims 1 to 3 wherein said support material is alumina.

Claim 6

The catalyst of any one of claims 1 to 3 wherein said support material is silica.

Claim 9

A process for the polymerization of alpha-monoolefins comprising contacting at least one monoolefin at a temperature of from 0 to 150°C at pressures of from 1 to 50 atmospheres in an inert hydrocarbon solvent with a mixture of an alkylaluminum compound as activator-scavenger and 0.001 to 10 millimoles per liter of solvent of a supported catalyst which is the reaction product from the steps of reducing a transition metal compound selected from the group consisting of the halides, oxyhalides, alcoholates of aliphatic alcohols having 1 to 6 carbon atoms in the alkyl groups, acetates, benzoates, acetylacetonates and the dicyclopentadienyl salts with an excess of an organomagnesium compound in the presence of a support material selected from the group consisting of silica, alumina and mixtures thereof, and then destroying excess reducing organomagnesium compound with a deactivation agent therefore; said deactivation agent being selected from the group consisting of hydrogen chloride, hydrogen bromide, water, acetic acid, alcohols, carbonic acid, phosphorus pentachloride, silicon tetrachloride, acetylene, and mixtures thereof; said transition metal being selected from the metals of Croups IV-B, V-B, VI-B, and VIII of the Periodic System, and said organomagnesium compound being selected from the group consisting of a compound of formula RMgX where R is an alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms and X is R, halide, or -OR, and complexes of RMgX with solubilizing agents.

Claim 10

A process for the polymerization of alpha-monoolefins comprising contacting at least one monoolefin at a temperature of from 0 to 150°C at pressures of from 1 to 50 atmospheres in an inert hydrocarbon solvent with a mixture of an alkylaluminum compound as activator-scavenger and 0.001 to 10 millimoles per liter of solvent of a supported catalyst which is the reaction product from the steps of reducing a transition metal compound selected from the group consisting of the halides, oxyhalides, alcoholates of aliphatic alcohols having 1 to 6 carbon atoms in the alkyl groups, acetates, benzoates, acetylacetonates and the dicyclopentadienyl salts with an excess of an organomagnesium compound in the presence of a support material selected from the group consisting of silica, alumina and mixtures thereof, and then destroying excess reducing organomagnesium compound with a deactivation agent therefore; said deactivation agent being selected from the group consisting of hydrogen chloride, hydrogen bromide, water, acetic acid, alcohols, carbonic acid, phosphorus pentachloride, silicon tetrachloride, acetylene, and mixtures thereof; said transition metal being selected from the metals of Croups IV-B, V-B, VI-B, and VIII of the Periodic System, and said organomagnesium compound being selected from the group consisting of a compound of formula RMgX where R is an alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms and X is R, halide, or -OR, and complexes of RMgX with solubilizing agents.

Claim 11

The process of Claim 7 wherein said monoolefin is ethylene, said solvent is hexane, said alkylaluminum activator is triisobutyl aluminum, said transition metal compound is a salt of titanium, and said deactivation agent is hydrogen chloride.

Claim 12

A process for the polymerization of monoolefins comprising contacting at least one monolefin at a temperature of from 0 to 150°C at pressures of from 1 to 50 atmospheres in gas phase with a mixture of an alkylaluminum compound as activator-scavenger and a supported catalyst which is the reaction product from the steps of reducing a transition metal compound selected from the group consisting of the halides, oxyhalides, alcoholates of aliphatic alcohols having 1 to 6 carbon atoms in the alkyl groups, acetates, benzoates, acetylacetonates and the dicyclopentadienyl salts with an excess of an organomagnesium compound in the presence of a support material selected from the group consisting of silica, alumina, and mixtures thereof, and then destroying excess reducing organomagnesium compound with a deactivation agent therefore; said deactivation agent being selected from the group consisting of hydrogen chloride, hydrogen bromide, water, acetic acid, alcohols, carbonic acid, phosphorus pentachloride, silicon tetrachloride, acetylene, and mixtures thereof; said transition metal being selected from the metals of Groups IV-B, V-B, VI-B, and VIII of the Periodic System, and said organomagnesium compound being selected from the group consisting of a compound of formula RMgX where R is an alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms and X is R, halide, or -OR, and complexes of RMgX with solubilizing agents.

Claim 13

A process for the polymerization of monoolefins comprising contacting at least one monolefin at a temperature of from 0 to 150°C at pressures of from 1 to 50 atmospheres in gas phase with a mixture of an alkylaluminum compound as activator-scavenger and a supported catalyst which is the reaction product from the steps of reducing a transition metal compound selected from the group consisting of the halides, oxyhalides, alcoholates of aliphatic alcohols having 1 to 6 carbon atoms in the alkyl groups, acetates, benzoates, acetylacetonates and the dicyclopentadienyl salts with an excess of an organomagnesium compound in the presence of a support material selected from the group consisting of silica, alumina, and mixtures thereof, and then destroying excess reducing organomagnesium compound with a deactivation agent therefore; said deactivation agent being selected from the group consisting of hydrogen chloride, hydrogen bromide, water, acetic acid, alcohols, carbonic acid, phosphorus pentachloride, silicon tetrachloride, acetylene, and mixtures thereof; said transition metal being selected from the metals of Groups IV-B, V-B, VI-B, and VIII of the Periodic System, and said organomagnesium compound being selected from the group consisting of a compound of formula RMgX where R is an alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms and X is R, halide, or -OR, and complexes of RMgX with solubilizing agents.

Claim 14

The process of Claim 7 or Claim 9 wherein said monoolofin is ethylene.

Claim 15

The process of Claim 7 or Claim 9 wherein said monoolefin is a mixture of ethylene and up to 20% by weight of an alphamonoolefin having 3 to 8 carbon atoms.