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US5786291A
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Engineered catalyst systems and methods for their production and use
Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1997-02-18
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Granted: 1998-07-28
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Expires: 2017-02-18
Abstract
Abstract This invention relates to supported metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to supported catalyst systems having unique, predetermined properties resulting from the designed distribution of catalyst components within and upon porous support particles. The designed distribution of catalyst components is obtained through sequential deposition of catalyst components with intervening removal of solvent.
Inventors
- 👤 Anthony N. Speca
- 👤 Jeffrey L. Brinen
- 👤 James J. McAlpin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 14:04
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/619; C08F4/61916; D; D04; D04H; D04H3/00; D04H3/08; D04H3/16; B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/143; B01J31/16; B01J31/1616; B01J31/22; B01J31/2282; B01J31/2295; C08F10/00; C08F110/00; C08F4/02; C08F4/025; C08F4/61904; C08F4/61912; C08F4/6192; C08F4/61922; C08F4/61927; C08F4/62; C08F4/639; C08F4/63904; C08F4/63912; C08F4/63916; C08F4/6392; C08F4/63922; C08F4/63927; D01; D01F; D01F6/00; D01F6/02; D01F6/04; D01F6/06; B01J21/00; B01J21/06; B01J21/08; B01J2531/00; B01J2531/40; B01J2531/46; B01J2531/48; B01J2531/49; B01J2531/50; B01J2531/56; B01J2531/57; B01J2531/58; B01J31/165; C08F110/04; C08F110/06; C08F4/64; C08F4/659; C08F4/65912; C08F4/65916; C08F4/6592; C08F4/65922; C08F4/65927; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
82 words
A method for preparing a supported metallocene catalyst, said method comprising the steps of: (a) combining support material and a first solution comprising a first metallocene thereby forming a mixture; then (b) removing the solvent from the mixture thereby forming a supported first metallocene; then (c) combining the supported first metallocene with a second solution comprising a second metallocene wherein the second metallocene is different from the first thereby forming a resultant mixture; then (d) removing the solvent from said resulting mixture.
Claim 2
Independent Claim
82 words
A method for preparing a supported metallocene catalyst, said method comprising the steps of: (a) combining support material and a first solution comprising a first metallocene thereby forming a mixture; then (b) removing the solvent from the mixture thereby forming a supported first metallocene; then (c) combining the supported first metallocene with a second solution comprising a second metallocene wherein the second metallocene is different from the first thereby forming a resultant mixture; then (d) removing the solvent from said resulting mixture.
Claim 3
Dependent Claim
11 words
The method of claim 1 wherein the support material is porous.
Claim 4
Dependent Claim
26 words
The method of claim 2 wherein the volume of the first solution is less than about 3 times the total pore volume of the porous support.
Claim 5
Dependent Claim
26 words
The method of claim 2 wherein the volume of the first solution is less than about 2 times the total pore volume of the porous support.
Claim 6
Dependent Claim
26 words
The method of claim 2 wherein the volume of the first solution is less than about 1.5 times the total pore volume of the porous support.
Claim 7
Dependent Claim
26 words
The method of claim 3 wherein the volume of the second solution is less than about 3 times the total pore volume of the porous support.
Claim 8
Dependent Claim
26 words
The method of claim 3 wherein the volume of the second solution is less than about 2 times the total pore volume of the porous support.
Claim 9
Dependent Claim
26 words
The method of claim 3 wherein the volume of the second solution is less than about 1.5 times the total pore volume of the porous support.
Claim 10
Dependent Claim
15 words
The method of claim 1 wherein the first solution comprises a metallocene and an activator.
Claim 11
Dependent Claim
11 words
The method of claim 9 wherein the activator is an alumoxane.
Claim 12
Dependent Claim
15 words
The method of claim 1 wherein the second solution comprises a metallocene and an activator.
Claim 13
Dependent Claim
11 words
The method of claim 11 wherein the activator is an alumoxane.
Claim 14
Dependent Claim
77 words
The method of claim 1 wherein the first metallocene is represented by the formula: ##STR7## wherein M' is a Group 4, 5, or 6 transition metal; Q' and Q" are the same or different hydride, halogen, hydrocarbyl or alkyl radical having up to about 6 carbon atoms; A' and A" are the same or different asymmetrical substituted cyclopentadienyl or indenyl group; and D is a linear or cyclic hydrocarbon radical bridge of from one to six atoms.
Claim 15
Dependent Claim
456 words
The method of claim 1 wherein the second metallocene is represented by the formula: ##STR8## wherein M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten; R 1 and R 2 are identical or different, and are one of a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 2 -C 4 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, or a halogen atom; R 3 and R 4 are hydrogen atoms; R 5 and R 6 are identical or different, and are one of a halogen atom, a C 1 -C 10 alkyl group which may be halogenated, a C 6 -C 10 aryl group which may be halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, an --NR 2 15 , --SR 15 , --OR 15 , --OSiR 3 15 or --PR 2 15 radical, wherein R 15 is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group; R 7 is ##STR9## --B(R 11 )--, - Al(R 11 )--, --Ge--, --Sn--, --O--, --S--, --SO--, --SO 2 --, --N(R 11 )--, --CO--, --P(R 11 )--, or --P(O)(R 11 )--; wherein: R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 , or R 11 and R 13 , together with the atoms binding them, can form ring systems; M 2 is silicon, germanium or tin; R 8 and R 9 are identical or different and have the meanings stated for R 11 ; m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and the radicals R 10 are identical or different and have the meanings stated for R 11 , R 12 and R 13 and two adjacent R 10 radicals can be joined together to form a ring system.
Claim 16
Independent Claim
128 words
A method for preparing a supported metallocene catalyst, said method comprising the steps of: (a) combining porous support material and a first solution comprising solvent and a first metallocene wherein the volume of said first solution is less than about three times the total pore volume of the porous support thereby forming a mixture; then (b) removing the solvent from the mixture thereby forming a supported first metallocene; then (c) combining the supported first metallocene with a second solution comprising solvent and a second metallocene wherein the second metallocene is different from the first and wherein the volume of solution is less than about three times the total pore volume of the supported first metallocene forming a resulting mixture; then (d) removing the solvent from said resulting mixture.
Claim 17
Independent Claim
128 words
A method for preparing a supported metallocene catalyst, said method comprising the steps of: (a) combining porous support material and a first solution comprising solvent and a first metallocene wherein the volume of said first solution is less than about three times the total pore volume of the porous support thereby forming a mixture; then (b) removing the solvent from the mixture thereby forming a supported first metallocene; then (c) combining the supported first metallocene with a second solution comprising solvent and a second metallocene wherein the second metallocene is different from the first and wherein the volume of solution is less than about three times the total pore volume of the supported first metallocene forming a resulting mixture; then (d) removing the solvent from said resulting mixture.
Claim 18
Dependent Claim
25 words
The method of claim 15 wherein the volume of first solution is less than about two times the total pore volume of the porous support.
Claim 19
Dependent Claim
25 words
The method of claim 15 wherein the volume of second solution is less than about two times the total pore volume of the porous support.
Claim 20
Dependent Claim
17 words
The method of claim 15 wherein the first solution comprises a solvent, a metallocene and an activator.
Claim 21
Dependent Claim
11 words
The method of claim 18 wherein the activator is an alumoxane.
Claim 22
Dependent Claim
17 words
The method of claim 15 wherein the second solution comprises a solvent, a metallocene and an activator.
Claim 23
Dependent Claim
11 words
The method of claim 20 wherein the activator is an alumoxane.
Claim 24
Dependent Claim
528 words
The method of claim 15 wherein the first metallocene is represented by the formula: ##STR10## wherein M' is a Group 4, 5, or 6 transition metal; Q' and Q" are the same or different hydride, halogen, hydrocarbyl or alkyl radical having up to about 6 carbon atoms; A' and A" are the same or different asymmetrical substituted cyclopentadienyl or indenyl group; and D is a linear or cyclic hydrocarbon radical bridge of from one to six atoms; and wherein the second metallocene is represented by the formula: ##STR11## wherein M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten; R 1 and R 2 are identical or different, and are one of a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 2 -C 4 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, or a halogen atom; R 3 and R 4 are hydrogen atoms; R 5 and R 6 are identical or different, and are one of a halogen atom, a C 1 -C 10 alkyl group which may be halogenated, a C 6 -C 10 aryl group which may be halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, an --NR 2 15 , --SR 15 , --OR 15 , --OSiR 3 15 or --PR 2 15 radical, wherein R 15 is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group; R 7 is ##STR12## --B(R 11 )--, - Al(R 11 )--, --Ge--, --Sn--, --O--, --S--, --SO--, --SO 2 --, --N(R 11 )--,--CO--, --P(R 11 )--, or --P(O)(R 11 )--; wherein: R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 , or R 11 and R 13 , together with the atoms binding them, can form ring systems; M 2 is silicon, germanium or tin; R 8 and R 9 are identical or different and have the meanings stated for R 11 ; m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and the radicals R 10 are identical or different and have the meanings stated for R 11 , R 12 and R 13 and two adjacent R 10 radicals can be joined together to form a ring system.
Claim 25
Independent Claim
138 words
A method for preparing a supported metallocene catalyst, said method comprising the steps of; (a) combining porous support material having active surface hydroxyl groups and a first solution consisting essentially of solvent and a first metallocene wherein the volume of said first solution is less than about 2.5 times the total pore volume of the porous support thereby forming a mixture; then (b) removing the solvent from the mixture thereby forming a supported first metallocene; then (c) combining the supported first metallocene with a second solution comprising solvent, a second metallocene, and an alumoxane wherein the second metallocene is different from the first and wherein the volume of solution is less than about 2.5 times the total pore volume of the supported first metallocene thereby forming a resulting mixture; then (d) removing the solvent from said resulting mixture.
Claim 26
Independent Claim
138 words
A method for preparing a supported metallocene catalyst, said method comprising the steps of; (a) combining porous support material having active surface hydroxyl groups and a first solution consisting essentially of solvent and a first metallocene wherein the volume of said first solution is less than about 2.5 times the total pore volume of the porous support thereby forming a mixture; then (b) removing the solvent from the mixture thereby forming a supported first metallocene; then (c) combining the supported first metallocene with a second solution comprising solvent, a second metallocene, and an alumoxane wherein the second metallocene is different from the first and wherein the volume of solution is less than about 2.5 times the total pore volume of the supported first metallocene thereby forming a resulting mixture; then (d) removing the solvent from said resulting mixture.
Claim 27
Dependent Claim
456 words
The method of claim 23 wherein the second metallocene is represented by the formula: ##STR13## wherein M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten; R 1 and R 2 are identical or different, and are one of a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 2 -C 4 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, or a halogen atom; R 3 and R 4 are hydrogen atoms; R 5 and R 6 are identical or different, and are one of a halogen atom, a C 1 -C 10 alkyl group which may be halogenated, a C 6 -C 10 aryl group which may be halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, an --NR 2 15 , --SR 15 , --OR 15 , --OSiR 3 15 or --PR 2 15 radical, wherein R 15 is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group; R 7 is ##STR14## --B(R 11 )--, - Al(R 11 )--, --Ge--, --Sn--, --O--, --S--, --SO--, --SO 2 --, --N(R 11 )--, --CO--, --P(R 11 )--, or --P(O)(R 11 )--; wherein: R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 , or R 11 and R 13 , together with the atoms binding them, can form ring systems; M 2 is silicon, germanium or tin; R 8 and R 9 are identical or different and have the meanings stated for R 11 ; m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and the radicals R 10 are identical or different and have the meanings stated for R 11 , R 12 and R 13 and two adjacent R 10 radicals can be joined together to form a ring system.
Claim 28
Dependent Claim
77 words
The method of claim 24 wherein the first metallocene is represented by the formula: ##STR15## wherein M' is a Group 4, 5, or 6 transition metal; Q' and Q" are the same or different hydride, halogen, hydrocarbyl or alkyl radical having up to about 6 carbon atoms; A' and A" are the same or different asymmetrical substituted cyclopentadienyl or indenyl group; and D is a linear or cyclic hydrocarbon radical bridge of from one to six atoms.
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