Supported polymerization catalyst

Claim 2

A process for making an olefinic polymer comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of (I) a cavity component comprising the product produced by the steps of (a) treating an inert inorganic compound to remove surface hydroxyl groups; (b) contacting the treated inert inorganic compound with a hydrocarbon soluble magnesium compound; (c) contacting the product of said step (b) with a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides, hexaalkyl disilazanes and mixtures thereof; and (d) contacting the product of said step (c) with a vanadium compound having the structural formula V(O) 2 X 1 4-s , is halogen and s is 0 or 1; a first titanium-containing compound having the structural formula Ti(OR 2 ) n X 2 m , where R 2 is hydrocarbyl, X 2 is halogen, n is an integer of 1 to 4, and m is 0 or an integer of 1 to 3 with the priviso that the sum of n and m is 4; and a second titanium-containing compound having the structural formula TiX 3 p (OR 3 ) q , where 3 is halogen, R 3 is hydrocarbyl, p is an integer of 1 to 4, and q is 0 or an integer of 1 to 3, with the provisos that the sum of p and q are 4 and that said first and said second titanium-containing compounds are not identical; (II) an aluminum compound; and (III) a silane compound.

Claim 3

A process in accordance with claim 1 wherein said inert inorganic support is selected from the group consisting of silica, alumina, titania and zirconia.

Claim 4

A process in accordance with claim 1 wherein said treatment of step (a) comprises heating said inert inorganic support to a temperature in the range of between about 100° C. and about 150° C. for a period of between about 30 minutes to about 3 hours.

Claim 5

A process in accordance with claim 3 wherein said inert inorganic support is silica pretreated with hexamethyl disilazane prior to said heating step.

Claim 6

A process in accordance with claim 1 wherein said hydrocarbon soluble magnesium compound has the structural formula Mg(OR) r X t , where R is hydrocarbyl; X is halogen; r is 1 or 2; and t is 0 or 1.

Claim 7

A process in accordance with claim 5 wherein R is C 1 -C 12 alkyl; and X is chloride or bromine.

Claim 8

A process in accordance with claim 6 wherein R is C 4 -C 10 alkyl; X is chlorine; and r and t are 1.

Claim 9

A process in accordance with claim 1 wherein said step (b) occurs at a temperature in the range of between about 40° C. and about 130° C. for a period in the range of between about 20 minutes and about 5 hours.

Claim 10

A process in accordance with claim 1 wherein said modifying compound is selected from the group consisting of silicon halides, boron halides and aluminum halides.

Claim 11

A process in accordance with claim 9 wherein said modifying compound is selected from the group consisting of silicon tetrachloride and silicon tetrabromide.

Claim 12

A process in accordance with claim 1 wherein said step (c) occurs at a temperature in the range of between about 15° C. and about 100° C. over a period in the range of between about 15 minutes and about 3 hours.

Claim 13

A process in accordance with claim 1 wherein said product of said step (c) is washed with an organic solvent.

Claim 14

A process in accordance with claim 1 wherein said vanadium compound is selected from the group consisting of vanadium oxychloride and vanadium tetrachloride.

Claim 15

A process in accordance with claim 1 wherein said first titanium-containing compound is characterized by R 2 being alkaryl or alkyl; n being 4; and m being 0.

Claim 16

A process in accordance with claim 1 wherein said second titanium-containing compound is characterized by X 3 being chlorine or bromine; p being 4; and q being 0.

Claim 17

A process in accordance with claim 1 wherein said step (d) occurs at a temperature in the range of between about 40° C. and about 140° C. over a period in the range of between about 15 minutes and about 3 hours.

Claim 18

A process in accordance with claim 1 wherein the product of step (c) is contacted with said vanadium compound and said first and said second titanium-containing compounds simultaneously or as a mixture.

Claim 19

A process in accordance with claim 1 wherein said vanadium compound and said first and said second titanium-containing compounds contact said product of said step (c) consecutively in any order.

Claim 20

A process in accordance with claim 18 wherein said product of said step (c) is contacted with said vanadium compound, the product of which is contacted with said first titanium-containing compound which product is contacted with said second titanium-containing compound.

Claim 21

A process in accordance with claim 1 comprising washing said product of said step (d) with an organic solvent.

Claim 22

A process for making an olefinic polymer comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of (I) a catalyst component comprising the product produced by the steps of: (a) heating silica to remove surface hydroxyl groups; (b) contacting the silica product of step (a) with a hydrocarbon soluble magnesium compound having the structural formula Mg(OR) r X t , where R is hydrocarbyl, X is halogen, r is 1 or 2, and t is 0 or 1; (c) treating the product of step (b) with a modifying compound selected from the group consisting of silicon halides boron halides and aluminum halides; and (d) contacting the product of step (c) with a halogen-containing vanadium compound having the structural formula V(O) s X 1 4-s , X 1 is bromine or chlorine, and s is 0 or 1; a titanium ester having the structural formula Ti(OR 2 ) 4 , where R 2 is alkyl or alkaryl, and a titanium halide having the structural formula TiX 3 4 , where X 3 is bromine or chlorine; (II) an aluminum compound selected from the group consisting of an aluminum alkyl and an alkylaluminum halide; and (III) a silane compound having the structural formula R 4 u (OR 5 ) 4-u Si, where R 4 and R 5 are the same or different and are hydrocarbyl, and u is an integer of 1 to 3.

Claim 23

A process for making an olefinic polymer comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of (I) a catalyst component comprising the product produced by the steps of: (a) heating silica to remove surface hydroxyl groups; (b) contacting the silica product of step (a) with a hydrocarbon soluble magnesium compound having the structural formula Mg(OR) r X t , where R is hydrocarbyl, X is halogen, r is 1 or 2, and t is 0 or 1; (c) treating the product of step (b) with a modifying compound selected from the group consisting of silicon halides boron halides and aluminum halides; and (d) contacting the product of step (c) with a halogen-containing vanadium compound having the structural formula V(O) s X 1 4-s , X 1 is bromine or chlorine, and s is 0 or 1; a titanium ester having the structural formula Ti(OR 2 ) 4 , where R 2 is alkyl or alkaryl, and a titanium halide having the structural formula TiX 3 4 , where X 3 is bromine or chlorine; (II) an aluminum compound selected from the group consisting of an aluminum alkyl and an alkylaluminum halide; and (III) a silane compound having the structural formula R 4 u (OR 5 ) 4-u Si, where R 4 and R 5 are the same or different and are hydrocarbyl, and u is an integer of 1 to 3.

Claim 24

A process in accordance with claim 21 wherein said silica is heated to a temperature in the range of between about 100° C. and about 135° C. for a period of between about 40 minutes and about 2 hours.

Claim 25

A process in accordance with claim 22 wherein said silica is pretreated with hexamethyl disilazane prior to said heating step.

Claim 26

A process in accordance with claim 21 wherein R is C 4 -C 10 alkyl; and X is chlorine.

Claim 27

A process in accordance with claim 24 wherein said hydrocarbon soluble magnesium compound is 2 methylpentyloxymagnesium chloride.

Claim 28

A process in accordance with claim 21 wherein said halogen-containing vanadium compound is selected from the group consisting of vanadium oxychloride and vanadium tetrachloride; said titanium ester is tetracresyl titanate; and said titanium halide is titanium tetrachloride.

Claim 29

A process in accordance with claim 21 wherein said product of said step (d) is washed with an alkane containing between about 5 and about 9 carbon atoms.

Claim 30

A process for making an olefinic polymer comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of (I) a catalyst component comprising the product produced by the steps of (a) heating silica at a temperature in the range of between about 100° C. and about 120° C. for a period in the range of between about 45 minutes and about 1.5 hours; (b) contacting the heated silica with 2-methylpentyloxymagnesium chloride initially at a temperature in the range of between about 40° C. and about 80° C. for a period in the range of between about 20 minutes and about 1 hour, followed by heating at a temperature in the range of between about 60° C. and about 100° C. for a period in the range of between about 10 minutes and about 1 hour, followed by heating at a temperature in the range of between about 80° C. and about 120° C. for a period in the range of between about 1 hour and about 2 hours. (c) contacting the product of step (b) with silicon tetrachloride for a period of between about 10 minutes and about 1.5 hours at a temperature in the range of between about 15° C. and about 50° C., followed by a heating at a temperature in the range of between 30° C. and about 100° C. for a period in the range of between about 10 minutes and about 1.5 hours; and (d) contacting the product of step (c) with vanadium oxychloride at about ambient temperature for a period in the range of between about 30 seconds to about 5 minutes, the product of which is contacted with tetracresyl titanate for a period in the range of between about 2 minutes and about 10 minutes at about ambient temperature, the product which is contacted with titanium tetrachloride at a temperature in the range of between about 80° C. and about 100° C. for a period in the range of between about 45 minutes and about 1.5 hours; (II) triethylaluminum; and (III) isobutylisopropyldimethoxysilane.

Claim 31

A process for making an olefinic polymer comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of (I) a catalyst component comprising the product produced by the steps of (a) heating silica at a temperature in the range of between about 100° C. and about 120° C. for a period in the range of between about 45 minutes and about 1.5 hours; (b) contacting the heated silica with 2-methylpentyloxymagnesium chloride initially at a temperature in the range of between about 40° C. and about 80° C. for a period in the range of between about 20 minutes and about 1 hour, followed by heating at a temperature in the range of between about 60° C. and about 100° C. for a period in the range of between about 10 minutes and about 1 hour, followed by heating at a temperature in the range of between about 80° C. and about 120° C. for a period in the range of between about 1 hour and about 2 hours. (c) contacting the product of step (b) with silicon tetrachloride for a period of between about 10 minutes and about 1.5 hours at a temperature in the range of between about 15° C. and about 50° C., followed by a heating at a temperature in the range of between 30° C. and about 100° C. for a period in the range of between about 10 minutes and about 1.5 hours; and (d) contacting the product of step (c) with vanadium oxychloride at about ambient temperature for a period in the range of between about 30 seconds to about 5 minutes, the product of which is contacted with tetracresyl titanate for a period in the range of between about 2 minutes and about 10 minutes at about ambient temperature, the product which is contacted with titanium tetrachloride at a temperature in the range of between about 80° C. and about 100° C. for a period in the range of between about 45 minutes and about 1.5 hours; (II) triethylaluminum; and (III) isobutylisopropyldimethoxysilane.

Claim 32

A process in accordance with claim 28 wherein said silica is pretreated with hexamethyldisilazane prior to said step (a).