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US4950631A Expired / Lapsed US ⏱️ 0.0 years remaining

Modified silica based catalyst

Assignee: Equistar Chemicals LP
•
Filing: 1989-03-21
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Granted: 1990-08-21
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Expires: 2009-03-21
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Abstract

Abstract A catalyst comprising the product formed by (a) treating silica to remove surface hydroxyl groups; (b) contacting said treated silica with (1) a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof; and (2) at least one hydrocarbon soluble magnesium-containing compound selected from the group consisting of hydrocarbyloxy magnesium, hydrocarbyloxymagnesium halides and mixtures thereof; said contacting steps (1) and (2) occurring in random order; (c) contacting the product of step (b) with at least one titanium-containing compound having the structural formula Ti(OR) n X m , where R is aryl, alkyl or mixtures thereof; X is halogen; n is an integer of 1 to 4; m is 0 or an integer of 1 to 3; and the sum of m and n is 4; and (d) treating the product of step (c) with a titanium-containing compound having the structural formula TiX 1 p OR 1 ) q , where X 1 is halogen; R 1 is aryl or alkyl; p is an integer of 1 to 4; q is 0 or an integer of 1 to 3; and the sum of p and q is 4, with the proviso that the titanium-containing compound of this step is not the same as the titanium-containing compound of step (c). The catalyst is useful in polymerizing propylene. In this application propylene is polymerized under propylene polymerization conditions in the presence of a first co-catalyst, an aluminum-containing compound, and a second co-catalyst, a slane.

Inventors

  • 👤 Charles K. Buehler
  • 👤 Richard W. Fries
  • 👤 Thomas J. Pullukat

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-09 06:21
CPC Classifications
C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 24
Claim 1
Independent Claim 219 words
A catalyst comprising the product obtained by: (a) treating silica to remove surface hydroxyl groups ##STR3## (b) contacting said treated silica with (1) a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof; and (2) at least one hydrocarbon soluble magnesium-containing compound selected from the group consisting of hydrocarbyloxy magnesiums, hydrocarbyloxymagnesium halides and mixtures thereof; said contacting steps (1) and (2) occurring in random order; (c) contacting said product of step (b) with at least one titanium-containing compound having the structural formula Ti(OR) n X m , where R is aryl, alkyl or mixtures thereof; X is halogen; n is an integer of 1 to 4; m is 0 or an integer of 1 to 3; and the sum of m and n is 4; and (d) treating the product of step (c) with a titanium-containing compound having the structural formula TiX 1 p (OR 1 ) q , where X 1 is halogen; R 1 is aryl or alkyl; p is an integer of 1 to 4; q is 0 or an integer of 1 to 3; and the sum of p and q is 4, with the proviso that the titanium-containing compound of this step is not the same as the titanium-containing compound of step (c).
Claim 2
Dependent Claim 219 words
A catalyst comprising the product obtained by: (a) treating silica to remove surface hydroxyl groups ##STR3## (b) contacting said treated silica with (1) a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof; and (2) at least one hydrocarbon soluble magnesium-containing compound selected from the group consisting of hydrocarbyloxy magnesiums, hydrocarbyloxymagnesium halides and mixtures thereof; said contacting steps (1) and (2) occurring in random order; (c) contacting said product of step (b) with at least one titanium-containing compound having the structural formula Ti(OR) n X m , where R is aryl, alkyl or mixtures thereof; X is halogen; n is an integer of 1 to 4; m is 0 or an integer of 1 to 3; and the sum of m and n is 4; and (d) treating the product of step (c) with a titanium-containing compound having the structural formula TiX 1 p (OR 1 ) q , where X 1 is halogen; R 1 is aryl or alkyl; p is an integer of 1 to 4; q is 0 or an integer of 1 to 3; and the sum of p and q is 4, with the proviso that the titanium-containing compound of this step is not the same as the titanium-containing compound of step (c).
Claim 3
Dependent Claim 19 words
A catalyst in accordance with claim 1 wherein said step (a) comprises calcining said silica in an inert atmosphere.
Claim 4
Dependent Claim 19 words
A catalyst in accordance with claim 1 wherein said step (a) comprises treating said silica with a hexaalkyl disilazane.
Claim 5
Dependent Claim 50 words
A catalyst in accordance with claim 1 wherein said silica has a surface area in the range of between about 80 and about 300 m 2 /g, a median particle size of about 20 to about 200 microns and a pore volume of between about 0.6 to about 3.0 cc/g.
Claim 6
Dependent Claim 36 words
A catalyst in accordance with claim 4 wherein said silica support is selected from the group consisting of pure silica, silica containing minor amounts of one or more of alumina, titania, zirconia, magnesia and mixtures thereof.
Claim 7
Dependent Claim 33 words
A catalyst in accordance with claim 1 wherein said compound having the structural formula Ti(OR) n X m is selected from the group consisting of tetrahydrocarbyloxytitaniums, trihydrocarbyloxytitanium halides, dihydrocarbyloxytitanium dihalides and mixtures thereof.
Claim 8
Dependent Claim 15 words
A catalyst in accordance with claim 6 wherein n is 4 and m is 0.
Claim 9
Dependent Claim 23 words
A catalyst in accordance with claim 1 wherein p is an integer of 2 to 4 and q is 0, 1 or 2.
Claim 10
Dependent Claim 15 words
A catalyst in accordance with claim 8 wherein p is 4 and q is 0.
Claim 11
Dependent Claim 32 words
A catalyst in accordance with claim 1 wherein each of steps (a), (b) and (c) are conducted at a temperature in the range of between about 0° C. and about 100° C.
Claim 12
Dependent Claim 165 words
A catalyst comprising the product of the steps of: (a) treating silica having a surface area of about 80 to about 300 m 2 /g, a median particle size of about 20 to about 200 microns and a pore volume of about 0.6 to about 3.0 cc/g whereby hydroxyl groups on the surface of said silica are removed ##STR4## (b) contacting said treated silica with (1) a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides and mixtures thereof; and (2) a hydrocarbon soluble magnesium-containing compound selected from the group consisting of hydrocarbyloxy magnesiums, hydrocarbyloxymagnesium halides and mixtures thereof; said sequence of contacting steps (1) and (2) being random; (c) contacting said product of step (b) with a titanium ester having the structural formula Ti(OR) 4 , where R is aryl, alkyl or mixtures thereof; and (d) treating said product of step (c) with a titanium halide having the structural formula TiX 1 4 , where X 1 is halogen.
Claim 13
Dependent Claim 165 words
A catalyst comprising the product of the steps of: (a) treating silica having a surface area of about 80 to about 300 m 2 /g, a median particle size of about 20 to about 200 microns and a pore volume of about 0.6 to about 3.0 cc/g whereby hydroxyl groups on the surface of said silica are removed ##STR4## (b) contacting said treated silica with (1) a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides and mixtures thereof; and (2) a hydrocarbon soluble magnesium-containing compound selected from the group consisting of hydrocarbyloxy magnesiums, hydrocarbyloxymagnesium halides and mixtures thereof; said sequence of contacting steps (1) and (2) being random; (c) contacting said product of step (b) with a titanium ester having the structural formula Ti(OR) 4 , where R is aryl, alkyl or mixtures thereof; and (d) treating said product of step (c) with a titanium halide having the structural formula TiX 1 4 , where X 1 is halogen.
Claim 14
Dependent Claim 33 words
A catalyst in accordance with claim 11 wherein said step (a) comprises calcining silica at a temperature in the range of between about 550° C. and about 650° C. in a nitrogen atmosphere.
Claim 15
Dependent Claim 17 words
A catalyst in accordance with claim 11 wherein said step (a) comprises treating silica with hexamethyl disilazane.
Claim 16
Dependent Claim 25 words
A catalyst in accordance with claim 11 wherein said modifying compound is selected from the group consisting of silicon tetrachloride, boron trichloride and aluminum trichloride.
Claim 17
Dependent Claim 25 words
A catalyst in accordance with claim 11 wherein said magnesium compound is selected from the group consisting of magnesium alkoxides, alkoxymagnesium halides and mixtures thereof.
Claim 18
Dependent Claim 26 words
A catalyst in accordance with claim 15 wherein said magnesium compound is selected from the group consisting of 2-methylpenyloxymagnesium chloride, di-2-ethylhexyloxymagnesium, pentoxymagnesium chloride and mixtures thereof.
Claim 19
Dependent Claim 34 words
A catalyst in accordance with claim 11 wherein said titanium ester is selected from the group consisting of tetracresyl titanate, titanium tetrabutoxide, titanium tetranonolate and tetra-2-ethylhexyltitanate, tetraisobutyltitanate, tetra n-propyltitanate, tetraisopropyl titanate and mixtures thereof.
Claim 20
Dependent Claim 14 words
A catalyst in accordance with claim 17 wherein said titanium halide is titanium tetrachloride.
Claim 21
Dependent Claim 110 words
A catalyst comprising the product obtained by: (a) treating silica having a surface area of about 80 to about 300 m 2 /g, a median particle size of about 20 to about 200 microns and a pore volume of about 0.6 to about 3.0 cc/g to remove hydroxyl groups from the surface of said silica; (b) contacting said treated silica with (1) a compound selected from the group consisting of silicon tetrachloride, boron trichloride and aluminum trichloride; and (2) 2-methylpentyloxymagnesium chloride; said contacting steps (1) and (2) being random; (c) contacting said product of step (b) with tetracresyl titanate; and (d) treating the product of step (c) with titanium tetrachloride.
Claim 22
Dependent Claim 110 words
A catalyst comprising the product obtained by: (a) treating silica having a surface area of about 80 to about 300 m 2 /g, a median particle size of about 20 to about 200 microns and a pore volume of about 0.6 to about 3.0 cc/g to remove hydroxyl groups from the surface of said silica; (b) contacting said treated silica with (1) a compound selected from the group consisting of silicon tetrachloride, boron trichloride and aluminum trichloride; and (2) 2-methylpentyloxymagnesium chloride; said contacting steps (1) and (2) being random; (c) contacting said product of step (b) with tetracresyl titanate; and (d) treating the product of step (c) with titanium tetrachloride.
Claim 23
Dependent Claim 22 words
A catalyst in accordance with claim 19 wherein said step (a) comprises calcining said silica at a temperature of about 600° C.
Claim 24
Dependent Claim 18 words
A catalyst in accordance with claim 19 wherein said step (a) comprises treating said silica with hexamethyl disilazane.

References Cited (Backward Citations)

US3135809A Cited
US3591656A Cited
US4565795A Cited
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US4508843A Cited
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EP0292134A2 Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1993-08-20 1994-02-19 1994-08-21 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1997-08-20 1998-02-19 1998-08-21 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2001-08-20 2002-02-19 2002-08-21 $7700.00 Window Closed / Lapsed

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