Catalyst, method of producing the catalyst, and polymerization process employing the catalyst

Claim 2

A process for producing a polyolefin comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated diolefins, vinyl aromatic compounds and mixtures of any two or more thereof under polymerization conditions with a cocatalyst comprising at least one organometallic compound selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table and a catalyst prepared by (A) mixing a first catalyst component solution and a second catalyst component, wherein the first catalyst component is formed by the chemical combination of: (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group IIB metals, and (2) a transition metal compound in which the transition metals are selected from Groups IVB and VB and the transition metal is bonded to at least one radical selected from the group consisting of hydrocarbyloxides, amides, imides, and mercaptides; and wherein the second catalyst component comprises a precipitating agent selected from the group consisting of (a) organometallic compounds of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and organoaluminum compounds, (b) metal halides and oxyhalides of metals of Groups IIIA, IVA, IVB, VA, and VB, hydrogen halides, and organic acid halides selected from the group consisting of compounds having the formula ##STR2## wherein R"' is an alkyl, aryl, or cycloalkyl group or combinations thereof and X is a halide, and (B) depositing prepolymer on said catalyst in an aount sufficient to reduce the amount of polymer fines resulting from said polymerization by contacting said catalyst with monomer in the presence of an adequate amount of a cocatalyst selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table.

Claim 3

A process according to claim 1 wherein the cocatalysts for the polymerization and the prepolymerization can be the same or different and are selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, hydrocarbyl aluminum halides, and trihydrocarbyl aluminum compounds.

Claim 4

A process according to claim 2 wherein the solid product resulting from the reaction of said first and second components has been further reacted with a halide ion exchanging source.

Claim 5

A process according to claim 3 wherein said halide ion exchanging source is selected from the group consisting of titanium tetrahalides, vanadium oxychloride, and zirconium tetrachloride.

Claim 6

A process according to claim 4 wherein said prepolymer is deposited on the solid resulting from the reaction of said first and second components prior to treatment with the halide ion exchanging source.

Claim 7

A process according to claim 5 wherein said second catalyst component is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and hydrocarbyl aluminum halides.

Claim 8

A method according to claim 6 wherein the amount of prepolymer deposited on said catalyst is in the range of about 1 to about 50 weight percent of the prepolymerized catalyst.

Claim 9

A method according to claim 7 wherein said transition metal compound is of the formula Ti(OR) 4 wherein each R is individually selected from alkyl radicals containing 1 to 10 carbon atoms per radical.

Claim 10

A method according to claim 8 wherein said metal halide compound is magnesium dichloride.

Claim 11

A method according to claim 9 wherein said transition metal compound is titanium tetraethoxide.

Claim 12

A method according to claim 10 wherein the molar ratio of titanium to magnesium in the reactants used to make said first catalyst component are in the range of about 2:1 to about 1:2.

Claim 13

A method according to claim 11 wherein said halide ion exchanging source is titanium tetrachloride.

Claim 14

A method according to claim 12 wherein said titanium tetrachloride treatment is conducted at a temperature in the range of about 15° C. to about 50° C.

Claim 15

A method according to claim 13 wherein the prepolymer is deposited in such an amount that about 3 to about 40 weight percent of the prepolymerized catalyst is prepolymer.

Claim 16

A method according to claim 14 wherein said prepolymer is polyethylene.

Claim 17

A method according to claim 15 wherein the second catalyst component is selected from the group consisting of methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum, dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, methyl-n-propylaluminum bromide, di-n-octylaluminum bromide, diphenylaluminum chloride, dicyclohexylaluminum bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride, ethylaluminum sesquiiodide.

Claim 18

A method according to claim 15 wherein said second catalyst component is ethylaluminum sesquichloride.

Claim 19

A method according to claim 11 wherein said second catalyst component is ethylaluminum sesquichloride.

Claim 20

A method according to claim 11 wherein: the metal halide compound is selected from the group consisting of magnesium dihalides; the transition metal compound is selected from the group consisting of titanium tetraalkoxides; the second catalyst component is selected from the group consisting of ethylaluminum sesquichloride, ethylaluminum dichloride, and diethylaluminum chloride; and the halide ion exchanging source is titanium tetrachloride.

Claim 21

A method according to claim 11 wherein: the prepolymer comprises polymer polymerized from at least one monomer selected from the group consisting of aliphatic mono-1-olefins having from 2 to about 20 carbon atoms per molecule and conjugated dienes having from 4 to about 8 carbon atoms per molecule.

Claim 22

A process according to any of the preceding claims wherein the polymerizable compound comprises at least 90 weight percent aliphatic mono-1-olefin having from 2 to about 18 carbon atoms per molecule with the remainder of the polymerizable compound selected from the group consisting of acyclic conjugated dienes and vinylaromatic hydrocarbons.

Claim 23

A process according to claim 21 wherein the polymerizable compound comprises at least 90 percent ethylene.

Claim 24

A process according to claim 22 wherein the polymerizable compound consists essentially of ethylene.

Claim 25

A process according to claim 23 wherein during said polymerization said catalyst is employed in conjunction with a cocatalyst consisting essentially of triethylaluminum.

Claim 26

A process for producing a polyolefin comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated diolefins, vinyl aromatic compounds and mixtures of any two or more thereof under polymerization conditions with a cocatalyst comprising at least one organometallic compound selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table and a catalyst prepared by (A) mixing a first catalyst component solution and a second catalyst component, wherein the first catalyst component is formed by the chemical combination of: (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting Group IIA metals and Group IIB metals, and (2) a transition metal compound in which the transition metals are selected from Groups IVB and VB and the transition metal is bonded to at least one radical selected from the group consisting of hydrocarbyloxides, amides, imides, and mercaptides; and wherein the second catalyst comprises a precipitating agent selected from the group consisting of (a) organometallic compounds of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and organoaluminum compounds, (b) metal halides and oxyhalides of metals of Groups IIIA, IVA, IVB, VA, and VB, hydrogen halides, and organic acid halides selected from the group consisting of compounds having the formula ##STR3## wherein R"' is an alkyl, aryl, or cycloalkyl group or combinations thereof and X is a halide, and (B) depositing prepolymer on said catalyst in an amount such that the level of prepolymer in said prepolymerized catalyst is in the range of about 1 to about 50 weight percent by contacting said catalyst with monomer in the presence of an adequate amount of a cocatalyst selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table.

Claim 27

A process for producing a polyolefin comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated diolefins, vinyl aromatic compounds and mixtures of any two or more thereof under polymerization conditions with a cocatalyst comprising at least one organometallic compound selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table and a catalyst prepared by (A) mixing a first catalyst component solution and a second catalyst component, wherein the first catalyst component is formed by the chemical combination of: (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting Group IIA metals and Group IIB metals, and (2) a transition metal compound in which the transition metals are selected from Groups IVB and VB and the transition metal is bonded to at least one radical selected from the group consisting of hydrocarbyloxides, amides, imides, and mercaptides; and wherein the second catalyst comprises a precipitating agent selected from the group consisting of (a) organometallic compounds of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and organoaluminum compounds, (b) metal halides and oxyhalides of metals of Groups IIIA, IVA, IVB, VA, and VB, hydrogen halides, and organic acid halides selected from the group consisting of compounds having the formula ##STR3## wherein R"' is an alkyl, aryl, or cycloalkyl group or combinations thereof and X is a halide, and (B) depositing prepolymer on said catalyst in an amount such that the level of prepolymer in said prepolymerized catalyst is in the range of about 1 to about 50 weight percent by contacting said catalyst with monomer in the presence of an adequate amount of a cocatalyst selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table.

Claim 28

A process according to claim 25 wherein the cocatalysts for the polymerization and the prepolymerization can be the same or different and are selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, hydrocarbyl aluminum halides, and trihydrocarbyl aluminum compounds.

Claim 29

A process according to claim 26 wherein said transition metal compound is of the formula Ti(OR) 4 wherein each R is individually selected from alkyl radicals containing 1 to 10 carbon atoms per radical.

Claim 30

A process according to claim 25 wherein said metal halide comprises magnesium dichloride, said transition metal compound comprises titanium tetraethoxide, said second component comprises ethyl aluminum sesquichloride, and the solid product resulting from the reaction of said first and second components is reacted with titanium tetrachloride after the prepolymer has been deposited on said solid product.

Claim 31

A method according to claim 28 wherein the molar ratio of titanium to magnesium in the reactants used to make said first catalyst component are in the range of about 2:1 to about 1:2.

Claim 32

A method according to claim 29 wherein the prepolymer is deposited in such an amount that about 3 to about 40 weight percent of the prepolymerized catalyst is prepolymer.

Claim 33

A method according to claim 30 wherein said prepolymer is polyethylene.

Claim 34

A process according to claim 31 wherein the polymerizable compound comprises at least 90 percent ethylene.

Claim 35

A process according to claim 31 wherein the polymerizable compound is essentially ethylene.

Claim 36

A process according to claim 27 wherein said precipitating agent comprises a dialkyl magnesium compound.