Catalyst preparation method
First Claim
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1. A method of preparing a supported catalyst system comprising combining 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound;
- and thereafter spray-drying the combination of
1) and
2); and
wherein the particle size of the first supported catalyst system is different from the particle size of the second supported catalyst system.
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Abstract
The present invention relates to a method of preparing a supported catalyst system, the method including combining 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound and thereafter spray-drying the combination.
55 Citations
24 Claims
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1. A method of preparing a supported catalyst system comprising combining 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound;
- and thereafter spray-drying the combination of
1) and
2); and
wherein the particle size of the first supported catalyst system is different from the particle size of the second supported catalyst system. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 21, 23)
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2. The method of claim 1 wherein the first catalyst compound is different from the second catalyst compound.
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3. The method of claim 1 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.
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4. The method of claim 1 wherein the combination to be spray dried is prepared by combining a two different supported activators with a catalyst compound.
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5. The method of claim 1 wherein the combination to be spray dried is prepared by combining a two or more different supported catalyst compounds with an activator.
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6. The method of claim 1 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.
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7. The method of claim 1 wherein at least one of the activators is selected from the group consisting of:
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trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;
di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate;
triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyl alumoxane, and modified methyl alumoxane.
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8. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.
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9. The method of claim 1 wherein one or more of the catalyst compounds is selected from the group consisting of:
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bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diphenyl, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)hafnium methyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl, bis(cyclopentadienyl)zirconium di-neopentyl, bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium dimethyl, bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium ethyl chloride, bis(cyclopentadienyl)zirconium phenyl chloride, bis(cyclopentadienyl)titanium methyl bromide, cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium trineopentyl, cyclopentadienyl hafnium trimethyl, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride;
bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl or dihalide, bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride, bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;
dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride, methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl titanium diphenyl or dichloride, isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)-hafnium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride, racemic-ethylene bis(1-indenyl)zirconium(W)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride, racemic-ethylene bis(1-indenyl)hafnium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)hafnium(IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride, racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride, indenyl zirconium tris(diethylcarbamate), indenyl zirconium tris(pivalate), indenyl zirconium tris(p-toluate), indenyl zirconium tris(benzoate), (1-methylindenyl) zirconium tris(pivalate), (2-methylindenyl)zirconium tris(diethylcarbamate), (methylcyclopentadienyl)zirconium tris(pivalate), cyclopentadienyl tris(pivalate), (pentamethylcyclopentadienyl)zirconium tris(benzoate), bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, (indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and (indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.
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10. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:
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bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;
bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));
bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;
bis(N-iso-butyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-iso-butyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;
bis(N-hexyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-phenyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-(2′
,6′
-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-(2′
,6′
-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV) di(bis(dimethylamide));
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimenthylbenzyl)phenoxide)titanium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimenthylbenzyl)phenoxide)titanium(IV)dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimenthylbenzyl)phenoxide)hafnium(IV)dibenzyl;
(N-phenyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;
(N-(2′
,6′
-di-iso-propylphenyl)-3,5-di-(1′
,1′
-dimenthylbenzyl)salicylimino)zirconium(IV)tribenzyl;
(N-(2′
,6′
-di-iso-propylphenyl)-3,5-di-(1′
,1′
-dimenthylbenzyl)salicylimino)titanium(IV)tribenzyl; and
(N-(2′
,6′
-di-iso-propylphenyl)-3,5-di-(1′
,1′
-dimenthylbenzyl)salicylimino)zirconium(IV) trichloride.
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11. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:
[(2,4,6-(CH3)3C6H2)NCH2CH2]2NH}MBz2(where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).
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21. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a Group 15 containing catalyst compound represented by the formulae:
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wherein M is a Group 4, 5, or 6 metal;
each X is independently an anionic leaving group;
y is 0 or 1; and
when y is 0 group L′
is absent;
n is the oxidation state of M;
m is the formal charge of the ligand represented by YZL or the YZL′
;
L is a Group 15 or 16 element;
L′
is a Group 15 or 16 element or Group 14 containing group;
Y is a Group 15 element;
Z is a Group 15 element;
divalent groups R1 and R2 are independently a C1 to C20 hydrocarbon group or a heteroatom containing group having up to twenty carbon atoms, the heteroatom selected from silicon, germanium, tin, lead, halogen and phosphorus;
R1 and R2 may also be interconnected to each other;
R3 is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group;
R4 and R5 are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;
R4 and R5 may be interconnected to each other;
R6 and R7 are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group; and
R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.
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23. The method of claim 8 wherein the bulky ligand metallocene compound is selected from compounds represented by the following formulae:
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2. The method of claim 1 wherein the first catalyst compound is different from the second catalyst compound.
- and thereafter spray-drying the combination of
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12. A composition of matter comprising a particle comprising a first supported catalyst system comprising a support, an activator and a metal catalyst compound and second supported catalyst system comprising a support, an activator and a metal catalyst compound;
- wherein the particle size of the first supported catalyst system is different from the particle size of the second supported catalyst system.
- View Dependent Claims (13, 14, 15, 16, 17, 18, 19, 20, 22, 24)
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13. The composition of claim 12 wherein the first catalyst compound is different from the second catalyst compound.
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14. The composition of claim 12 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.
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15. The composition of claim 12 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.
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16. The composition of claim 12 wherein at least one of the activators is selected from the group consisting of:
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trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;
di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate;
triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyl alumoxane, and modified methyl alumoxane.
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17. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.
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18. The composition of claim 12 wherein one or more of the catalyst compounds is selected from the group consisting of:
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bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diphenyl, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)hafnium methyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl, bis(cyclopentadienyl)zirconium di-neopentyl, bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium dimethyl, bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium ethyl chloride, bis(cyclopentadienyl)zirconium phenyl chloride, bis(cyclopentadienyl)titanium methyl bromide, cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium trineopentyl, cyclopentadienyl hafnium trimethyl, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride;
bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl or dihalide, bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride, bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;
dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride, methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl titanium diphenyl or dichloride, isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)zircomum dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)-hafnium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride, racemic-ethylene bis(1-indenyl)zirconium(W)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride. racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride, racemic-ethylene bis(1-indenyl)hafnium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)hafnium(IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride, ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride, racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride, indenyl zirconium tris(diethylcarbamate), indenyl zirconium tris(pivalate), indenyl zirconium tris(p-toluate), indenyl zirconium tris(benzoate),(1-methylindenyl)zirconium tris(pivalate), (2-methylindenyl)zirconium tris(diethylcarbamate), (methylcyclopentadienyl)zirconium tris(pivalate), cyclopentadienyl tris(pivalate), (pentamethylcyclopentadienyl)zirconium tris(benzoate), bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, (indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and (indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.
-
-
19. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:
-
bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;
bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));
bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;
bis(N-iso-butyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-iso-butyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;
bis(N-hexyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-phenyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-(1′
-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;
bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-(2′
,6′
-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl-3-(2′
,6′
-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;
bis(N-benzyl3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)di(bis(dimethylamide));
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimethylbenzyl)phenoxide)titanium(IV)dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′
,1′
-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;
(N-phenyl-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;
(N-(2′
,6′
-di-iso-propylphenyl)-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;
(N-(2′
,6′
-di-iso-propylphenyl)-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and
(N-(2′
,6′
-di-iso-propylphenyl)-3,5-di-(1′
,1′
-dimethylbenzyl)salicylimino)zirconium(IV)trichloride.
-
-
20. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:
[(2,4,6-(CH3)3C6H2)NCH2CH2]2NH}MBz2(where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).
-
22. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a Group 15 containing catalyst compound represented by the formulae:
-
wherein M is a Group 4, 5, or 6 metal;
each X is independently an anionic leaving group;
y is 0 or 1; and
when y is 0 group L′
is absent;
n is the oxidation state of M;
m is the formal charge of the ligand represented by YZL or the YZL′
;
L is a Group 15 or 16 element;
L′
is a Group 15 or 16 element or Group 14 containing group;
Y is a Group 15 element;
Z is a Group 15 element;
divalent groups R1 and R2 are independently a C1 to C20 hydrocarbon group or a heteroatom containing group having up to twenty carbon atoms, the heteroatom selected from silicon, germanium, tin, lead, halogen and phosphorus;
R1 and R2 may also be interconnected to each other;
R3 is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group;
R4 and R5 are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;
R4 and R5 may be interconnected to each other;
R6 and R7 are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group; and
R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.
-
-
24. The composition of claim 17 wherein the bulky ligand metallocene compound is selected from compounds represented by the following formulae:
-
13. The composition of claim 12 wherein the first catalyst compound is different from the second catalyst compound.
Specification
- Resources
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Current AssigneeUnivation Technologies LLC (Dow, Inc.)
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Original AssigneeUnivation Technologies LLC (Dow, Inc.)
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InventorsWenzel, Timothy T., Schreck, David James
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Primary Examiner(s)Bell, Mark L.
-
Assistant Examiner(s)BROWN, JENNINE M
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Application NumberUS09/729,842Publication NumberTime in Patent Office1,093 DaysField of Search502/117US Class Current502/117CPC Class CodesB01J 2531/0252 Salen ligands or analogues,...B01J 2531/0258 Flexible ligands, e.g. main...B01J 2531/46 TitaniumB01J 2531/48 ZirconiumB01J 2531/49 HafniumB01J 2531/56 VanadiumB01J 31/14 of aluminium or boronB01J 31/143 of aluminiumB01J 31/146 of boronB01J 31/1616 Coordination complexes, e.g...B01J 31/1805 the ligands containing nitr...B01J 31/2243 At least one oxygen and one...B01J 31/2295 Cyclic compounds, e.g. cycl...B01J 35/0006 Catalysts containing parts ...B01J 35/19 Catalysts containing parts ...B01J 37/0045 Drying a slurry, e.g. spray...C08F 10/00 Homopolymers and copolymers...C08F 10/02 EtheneC08F 110/02 EtheneC08F 210/08 ButenesC08F 210/14 : Monomers containing five or...C08F 210/16 : Copolymers of ethene with a...C08F 2410/06 : Catalyst characterized by i...C08F 4/65904 : in combination with another...C08F 4/65912 : in combination with an orga...C08F 4/65916 : supported on a carrier, e.g...C08F 4/65925 : two cyclopentadienyl rings ...C08F 4/65927 : two cyclopentadienyl rings ...