Source: http://www.google.com/patents/US6376627?dq=5927278
Timestamp: 2014-11-25 22:13:02
Document Index: 12057052

Matched Legal Cases: ['application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09', 'application No. 09']

Patent US6376627 - Coordination catalysts - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThis invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. The metallocene compositions may be represented by the formula: wherein M1 is selected from the group consisting of titanium, zirconium,...http://www.google.com/patents/US6376627?utm_source=gb-gplus-sharePatent US6376627 - Coordination catalystsAdvanced Patent SearchPublication numberUS6376627 B1Publication typeGrantApplication numberUS 09/619,748Publication dateApr 23, 2002Filing dateJul 19, 2000Priority dateJun 30, 2000Fee statusPaidAlso published asUS20020161143Publication number09619748, 619748, US 6376627 B1, US 6376627B1, US-B1-6376627, US6376627 B1, US6376627B1InventorsTerry J. Burkhardt, Udo M. Stehling, James R. Hart, William T. Haygood, Jr., Robert T. Li, James C. Vizzini, Matthew C. KuchtaOriginal AssigneeExxonmobil Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (28), Non-Patent Citations (20), Referenced by (10), Classifications (29), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetCoordination catalystsUS 6376627 B1Abstract This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. The metallocene compositions may be represented by the formula: wherein
We claim: 1. A polymerization process comprising contacting under suitable polymerization conditions one or more olefins and the reaction product of one or more activators and one or more compounds represented by the formula: wherein:
M1 is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten; R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C40 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, an OH group or a halogen atom, or a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen; R3 are identical or different and are each a halogen atom, a C3-C10 alkyl group which may be halogenated, a C6-C10 aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a �NR′2, �SR′, �OR′, �OSiR′3 or �PR′2 radical, wherein R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group; R4 to R7 are identical or different and are hydrogen, as defined for R3 or two or more adjacent radicals R5 to R7 together with the atoms connecting them form one or more rings; R13 is �B(R14)�, �Al(R14)�, �Ge�, �Sn�, �O�, �S�, �SO�, �SO2�, �N(R14)�, �CO�, �P(R14)�, or �P(O)(R14)�, or an amidoborane radical; wherein: R14, R15 and R16 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl or silaalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R14 and R15, together with the atoms binding them, form a cyclic ring; or, R13 is represented by the formula: wherein: R17 to R24 are as defined for R1 and R2, or two or more adjacent radicals R17 to R24, including R20 and R21, together with the atoms connecting them form one or more rings; M2 is one or more carbons, silicon, germanium or tin, provided that if M2 is more than one atom, then each M2 atom must be bound such that no one M2 atom is bound to both indenyl moieties; R8, R10 and R12 are identical or different and have the meanings stated for R4 to R7; and R9 and R11 are identical or different and are each a primary, secondary or tertiary butyl group, an aryl group, an isopropyl group, trialkyl silyl group, a fluoroalkyl group, or any other Group 14 radical having from 2 to 20 carbon atoms. 2. The process of claim 1 wherein R3 are identical C3-C10 alkyl groups.
3. The process of claim 1 wherein R4 to R7 are hydrogen atoms.
4. The process of claim 1 wherein the olefins are selected from C2-C14 olefins.
6. The process of claim 1 wherein R4 to R7 and R8, R10 and R12 are hydrogen.
7. The process of claim 1 wherein the olefins consist essentially of propylene.
8. The process of claim 1 wherein M1 is titanium, zirconium or hafnium.
9. The process of claim 1 wherein M1 is zirconium.
10. The process of claim 1 wherein R3 are identical C3 alkyl groups.
This application is based on U.S. Provisional Patent Application Ser. No. 60/215,459 filed Jun. 30, 2000.
or, R13 is represented by the formula: wherein: R17 to R24 are as defined for R1 and R2, or two or more adjacent radicals R17 to R24, including R20 and R21, together with the atoms connecting them form one or more rings; preferably, R17 to R24 are hydrogen;
rac-dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)2hafnium;
rac-dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl )2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-bis- trifluoromethylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)η4-1,4-diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-iso-propyl, 4-[3′,5′-bis- trifluoromethylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)η4-1,4-diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-iso-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2η4-1,4-diphenyl-1,3 -butadiene;
rac-9-silafluorendiyl(2-iso-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)2η4-1,4-diphenyl-1,3 -butadiene;
rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenly]indenyl)2η4-1,4diphenyl-1,3-butadiene;
rac-dimethylamidoborane(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylamidoborane(2n-butyl,4-[3′,5′-di-iso-proplyphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylamidoborane (2-iso -butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylamidoborane(2-ethyl) 4-[3′,5′-di-phenylpheny1]indenyl)2zirconium dimethyl;
rac-diisopropylamidoborane(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)2zirconium dichloride;,
rac-diisopropylamidoborane(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)η4-1,4-diphenyl-1,3-butadiene;
rac-bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)2zirconium dichioride;
rac-bis(trimethysilyl)amidoborane(2-iso-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-bis(trimethylsiiyl)amidoborane(2-iso-butyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl;
rac-bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
rac-bis(trimethylsilyl)aimiidoborane(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)2zirconium dimethyl;
Example 3 racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)2-methylindenyl)zirconium dichloride 1-bromo-3,5-di-tertbutylbenzene A 1000 mL three-neck, round-bottom flask was equipped with a mechanical stirrer, a pressure-compensating dropping funnel, and a reflux condenser. A nitrogen gas flow adapter with overpressure valve was attached on top of the reflux condenser. A slight nitrogen flow guaranteed an inert gas atmosphere in the apparatus. The flask was charged with 181 g triphenylphosphine (690 mmol) and 160 mL acetonitrile (HPLC grade). The white suspension was cooled in an ice bath for 15 minutes. While stirring, dropwise addition of 101.5 g bromine (635 mmol) took place within 40 minutes. After bromine addition, the ice bath was removed. 124 g of 3,5-di-tertbutylphenol (601 mmol) and 140 mL acetonitrile were added in one portion. The orange/white suspension converted into an orange solution upon heating. The mechanical stirrer was replaced by an egg-shape stir bar. The solution was stirred at gentle reflux temperature for three hours.
racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methyl-indenyl)zirconium dichloride 4 g of the above silane (5.77 mmol) were dissolved in 6 ml pentane and 43 mL THF. At −85� C. 4.6 mL n-BuLi (2.5M in hexanes, 11.5 mmol) were added within 11 minutes. The color of the solution turned from yellow to red-brown. The solution was warmed to −60� C. within 30 minutes and stirred at room temperature for one hour. The solvent was completely evaporated, 10 mL toluene were added, followed again by complete evaporation of the solvent. The red-brown residue was dissolved in 45 ml toluene and cooled to −85� C. Addition of 1.32 g ZrCl4 (5.66 mmol) gave a brown suspension. Within two hours the suspension was warmed to room temperature, and then refluxed for 6.5 hours. This gave a bright orange suspension. Toluene was completely evaporated, 60 mL pentane were added to stir the suspension overnight. Filtration over celite and washing of the orange residue with 45 mL pentane gave a clear orange filtrate. By slow evaporation of the pentate solution to the dry box atmosphere, the racemic zirconocene crystallized out of solution. The solution was decanted from the solid; the solid washed with a few mL cold pentane and dried. By washing the orange residue on celite above with toluene, a clear orange toluene solution can be obtained. Evaporation of half of the toluene and adding at least half the volume of pentane gives crystalline meso zirconocene. Yield of racemic zirconocene was 1.5 g (1.76 mmol, 30.5%). 0.51 g (0.60 mmol, 10.4%) meso zirconocene could be isolated. 1H-NMR (CHCl3=7.24 ppm): δ7.64 (d, 2�1H), 7.51 (s, 4H), 7.40 (d, 2�1H), 7.39 (s, 2H), 7.10 (t, 2�1H), 6.95 (s, 2�1H), 2.24 (s, 2�3H), 1.33 (s, 2�3H), 1.30 (s, 12�3H) for the racemic zirconocene, and δ7.62 (d, 2�1H), 7.45 (s, 4H), 7.37 (t, 2�1H), 7.11 (d, 2�1H), 6.86 (m, 2�1H), 6.78 (s, 2�1H), 2.44 (s, 2�3H), 1.46 (s, 3H), 1.31 (s, 12�3H), 1.23 (s, 3H) for the meso zirconocene.
Supported Metallocene Catalyst System 3A racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)2-methylindenyl)zirconium dichloride/MAO In a 100 mL round bottom flask racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl) zirconium dichloride (0.075 g) was added to a MAO solution (6.74 g, 7.4 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600� C. dehydration). This slurry was stirred for twenty minutes, then dried at 40� C. for one minutes under vacuum on a rotary evaporator until the liquid evaporated, and then the solid was further dried a total of about two hours and twenty minutes. The supported catalyst was recovered as a reddish pink, free flowing solid (5.4 g).
dimethylsiladiylbis[4-(3′,5′-di-tert-butylphenyl)-2-methylindenyl]zirconium dimethyl Dimethylsiladiylbis[4-(3′,5′-di-tert-butylphenyl)-2-methylindenyl]ZrCl2 (488 mgs, 0.57 mmol) was dissolved in 30 mL of toluene to give a clear orange solution. 3.0M MeMgBr solution in Et2O (0.76 mL, 2.28 mmol) was added at room temperature via syringe and the reaction was stirred at reflux overnight. After this time, the reaction was cooled and 0.5 mL of 1,4-dioxane and 0.5mL of Me3SiCl was added to the solution. This solution was filtered through a celite-packed frit and the toluene was removed in vacuo. The remaining yellow solid was washed with pentane and dried in vacuo to yield 257 mgs (55.3%) of the desired metallocene.
Supported Metallocene Catalyst System 3B racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dimethyl/NCA In a 50-ml beaker, 1.07 g (0.232 mmol) of an 11.05 wt % solution of tris (perfluorophenyl) borane in toluene was massed. 0.035 g (0.232 mmol) of N,N-diethylaniline (Aldrich, 98+%) was added followed by 4.5 g of toluene. A pink solution resulted. This solution was pipetted into a 50 ml round bottom flask containing 2.0 g of silica (Grace Davison, calcined at 500� C. with 3-wt % (NH4)2SiF6) and a magnetic stir bar. 4.5 g of toluene was used to rinse the beaker, pipette, and the sides of the flask. The flask was heated to 50� C. in an oil bath. The mixture was stirred for 30 minutes. 0.023 g (0.028 mmol) of the dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl) zirconium dimethyl was added as a solid to produce a red slurry. Stirring was continued for 1 hour at 50� C. After this time, the stirring and heating were discontinued. The solvent was stripped overnight in vacuo to give 2.13 g of a flesh colored powder. Composition by mass balance: Zirconium: 0.013 mmol/g catalyst, Boron: 0.11 mmol/g catalyst.
Supported Metallocene Catalyst System 3C racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dimethyl/NCA This catalyst preparation used the same raw materials as above. In a 50 mL beaker, 2.68 g (0.58 mmol) of an 11.05-wt % solution of tris (perfluorophenyl) borane in toluene was massed. 0.088 g (0.59 mmol) of N,N-diethylaniline was added followed by 15 g of toluene. A pink solution resulted. This solution was pipetted into a 100 mL round bottom flask containing 5.0 g of silica and a magnetic stir bar. 1.0 g of toluene was used to rinse the beaker, pipette, and the sides of the flask. The flask was heated to 50� C. in an oil bath. The mixture was stirred for 30 minutes. 0.0061 g (0.075 mmol) of the dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl) zirconium dimethyl was added as a solid to produce a red slurry. Stirring was continued for 30 minutes at 50� C. After this time, the stirring and heating were discontinued. The solvent was stripped overnight in vacuo to give 5.36 g of a flesh colored powder. Composition by mass balance: Zr: 0.013 mmol/g catalyst, B: 0.11 mmol/g catalyst.
Supported Metallocene Catalyst System 4 racemic [9-silafluorenebis(4(3′,5′-di-t-butylphenyl)-2-methylindene]zirconium dichloride In a 100 mL round bottom flask racemic [9-Silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]zirconium dichloride (0.085 g) was added to a MAO solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600� C. dehydration). This slurry was stirred for twenty minutes, then dried at 40� C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated, and then the solid was further dried a total of about two hours and twenty minutes. The supported catalyst was recovered as a pink reddish, free flowing solid (5.24 g).
Example 5 racemic [9-silafluorenebis(4(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconium dichloride 4-[3′,5′-di-t-butylphenyl]-2-isopropylindene 4-Chloro-2-isopropylindene (7.2 g, 37 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-Di-di-t-butylphenylmagnesium bromide (10 g, 37 mmol) as a Et2O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield is 5.8 g (45%).
dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-methylindene]ZrCl2 Dimethylsilylbis[4-(3′,5′-dimethylphenyl)2-methylindene] (4.23 g, 8.0 mmol) was dissolved in 60 mL of Et2O. While stirring, 6.4 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for two hours. After this time, the solution was cooled to −35� C. and ZrCl4 (1.58 g, 8.0 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to −35� C. to induce crystallization. 0.23 g (5.0%) of pure racemic compound was obtained.
Example 7 dimethylsiladiyl-bis-(4(3′,5′-bistrinfluoromethylphenyl)2-methyl-indenyl)zirconium dichloride 4-[3′,5′-bis(trifluoromethyl)phenyl]-2-methylindene 4-Bromo-2-methylindene (10.7 g, 51 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-bis(trifluoromethyl)phenylmagnesium bromide (51 mmol) as a Et2O solution was added under vigorous stirring and the reaction stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield was 2.2 g (13%).
dimethylsiladiylbis[4-(3′,5′-bis[trifluoromethyl]phenyl)-2-methylindene SiMe2Cl2 (0.48 g, 3.7 mmol) was dissolved in 80 mL of THF. While stirring, lithium 4-[3′,5′-bis(trifluoromethylphenyl]-2-methylindenide (2.6 g, 7.5 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo, and the crude product is loaded onto a silica gel column and eluted with hexane. Yield was 2.2 g (80%).
Supported Metallocene Catalyst System 7 dimethylsiladiyl-bis-(4(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconium dichloride/MAO In a 100 mL round bottom flask dimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconium dichloride (0.075 g) was added to a MAO solution (6.32 g, 6.75 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (13 mL). To the combined filtrates was added dehydrated silica (3.75 g, Davison 948 Regular, 600� C. dehydration). This slurry was stirred for thirty minutes then dried at 40� C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty minutes. The supported catalyst was recovered as a dull red pink, free flowing solid (5.03 g).
Dimethylsiladiylbis(4-(3′,5′-bis-trimethylsilyl-phenyl)-2-methylindenyl) zirconium dichloride 4.1 g Silane from above (5.4 mmol) were dissolved in 50 mL THF. At a cooling bath temperature of −83� C., 4.3 mL n-BuLi (2.5M in hexanes, 10.8 mmol) were added within one minute. The color of the solution turned from yellow to red-brown. The solution was warmed to −30� C. within 100 minutes and then stirred at room temperature for 100 minutes. The solvent was completely evaporated, 13 mL toluene were added following again complete evaporation of the solvent. The residue was dissolved in 50 ml toluene and cooled to −82� C. Addition of 1.26 g ZrCl2 (5.41 mmol) resulted in a light brown suspension. The suspension was stirred overnight at room temperature, refluxed for 5.5 hours, and again stirred overnight at room temperature. This resulted in an orange suspension. Filtration over celite and complete evaporation of toluene gave an orange solid. 40 mL Pentane was added to the solid, and the suspension stirred. Filtration, using a frit washing with 3 mL cold pentane, and drying under vacuo gave fraction 1 (1.56 g). Rac/meso ratio of fraction 1 is 8:92. All solvent was evaporated from the filtrate, and exactly 8 mL pentane were added to dissolve the residue. The solution was placed in a freezer at −35� C. which initiated the crystallization of a solid compound. Filtration, using a frit, washing with a few mL cold pentane, and drying under vacuo gave fraction 2 (0.63 g). Rac/meso ratio of fraction 2 is 85:15. All solvent was evaporated from the filtrate, and the solid kept as fraction 3 (1.77 g). Rac/meso ratio of fraction 3 is 73:27. 1H-NMR (CHCl3=7.24 ppm): δ7.78 (s, 2�2H), 7.70 (d, 2�1H), 7.64 (s, 2�1H), 7.41 (d, 2�1H), 7.12 (m, 2�1H), 6.91 (s, 2�1H), 2.25 (s, 2�3H), 1.32 (s, 2�3H), 0.24 (s, 12�3H) for the racemic zirconocene, and δ7.72 (s, 2�2H), 7.66 (s, 2�1H), 7.62 (s, 2�1H), 7.12 (d, 2�1H), 6.88 (m, 2�1H), 6.75 (s, 2�1H), 2.43 (s, 2�3H), 1.46 (s, 3H), 1.23 (s, 3H), 0.25 (s, 12�3H) for the meso zirconocene.
Example 9 dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconium dichloride 4-(3′,5′-dimethylphenyl)-2-isopropylindene 4-chloro-2-isopropylindene (10.0 g, 54 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-dimethylphenylmagnesium bromide (54 mmol) as a Et2O solution was added under vigorous stirring and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield was 5.5 g (39%).
9,9-Dichloro-9-silafluorene Lithium wire (3.33 g, 0.08 mol) was washed with pentane, carefully cut into small pieces, and suspended in 150 mL of Et2O. While stirring, 2,2-dibromobiphenyl (25 g, 0.08 mol) 100 mL of diethyl ether was added dropwise over 1 hour and the contents were allowed to stir for 10 hours. The mixture was filtered through a frit to remove any unreacted Li and LiBr. The filtrated was loaded into an addition funnel and slowly dropped into a solution containing SiCl4 (50 g, 0.08 mol) in 200 mL of Et2O. After addition, the contents were stirred at room temperature for 5 hours. The solvent was removed in vacuo and 300 mL of pentane was added. The solution was filtered to remove LiCl and the solvents were again removed in vacuo. The solids were then loaded into a sublimator and allowed to sublime at 150� C. under fill vacuum. Yield was 10.0 g (51%).
4-(3′,5′-dimethylphenyl)-2-isopropylindene 4-chloro-2-isopropylindene (10 g, 54 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-Dimethylphenylmagnesium bromide (54 mmol) as a Et2O solution was added under vigorous stirring and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq) neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield was 5.5 g (39%).
[9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]ZrCl2 The crude solid from the previous step (2.1 g, 3.2 mmol) was taken up in 50 mL of diethyl ether. To this solution was slowly added n-BuLi (2.56 mL, 2.5M in hexane) and then stirred for 3 hours at room temperature. The solution was cooled to −30� C. and ZrCl4 (0.74 g, 3.2 mmol) was added as a dry powder and stirred at room temperature for two hours. The solvent was removed in vacuo and toluene was added to the crude residue. The solution was filtered to remove LiCl. The filtrate was concentrated and pentane was added under heating. The solution was cooled to induce crystallization. Yield of pure rac/meso metallocene was 120 mgs (3.8%).
Supported Metallocene Catalyst System 10 Rac/meso [9-silafluorenebis(4-(3′,5′-dimethylphenyl)2-isopropylindene]zirconium dichloride/MAO In a 100 mL round bottom flask rac/meso [9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconium dichloride (0.076 g) was added to the MAO solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600� C. dehydration). This slurry was stirred for twenty minutes, then dried at 40� C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated, and then the solid was further dried a total of about two hours and thirty minutes. The supported catalyst was recovered as a dull purple, free flowing solid (5.06 g).
Impact Copolymers (ICP) The polymerization procedure for producing ICP with the supported catalyst systems prepared as described above was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The quantity of hydrogen is 1.55 millimoles for each psi added as shown in the Tables. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70� C, the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was vented to about 170 psig pressure and then an ethylene/propylene gas mixture was passed through the reactor at the rates indicated while maintaining 200 psig. At the end of the gas phase stage, typically 90 to 150 minutes, the reactor was vented and cooled under N2. The granular ICP polymer was removed and dried.
racemic dimethylsiladiyl-bis-(4-(3′-5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dichloride/MAO
racemic dimethylsiladiyl-bis-(4-(3′-5′-di-tertbutylphenyl)-2-methylindenyl)zirconium
dichloride/NCA
racemic dimethylsiladiyl-bis-(4-(3′-5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dichloride/NCA
(delti psi)
334.68, 127.37
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS5658997 *Jun 7, 1995Aug 19, 1997Mitsui Petrochemical Industries, Ltd.Process for polymerizing propylene by using a novel metallocene catalystUS5753769Apr 11, 1995May 19, 1998Mitsui Petrochemical Industries, Ltd.Process for preparing propylene polymer composition and propylene polymer compositionUS5770753Jun 7, 1995Jun 23, 1998Targor GmbhAddition polymerization catalystUS5786432 *Jun 7, 1995Jul 28, 1998Targor GmbhPolymerizing or copolymerizing olefin in presence of transition metal metallocene catalyst and cocatalystUS5789634Feb 5, 1997Aug 4, 1998Boulder Scientific CompanyCoupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst intermediatesUS5840644Dec 28, 1995Nov 24, 1998Targor GmbhOlefin polymerization catalystsUS5936053Jun 6, 1997Aug 10, 1999Mitsui Chemicals, Inc.Propylene polymer, copolymers and elastomerUS6057408 *Apr 13, 1998May 2, 2000Targor GmbhHigh molecular weight copolymers of propylene and olefins having 2 or 4 to 32 carbon atomsUS6136742 *May 22, 1997Oct 24, 2000Exxon Chemical Patents, Inc.Metallocene catalyst systemsUS6242544 *Dec 30, 1997Jun 5, 2001Targor GmbhPolyolefins prepared using soluble metallocene compounds in combination with aluminoxanes; high molecular weight and isotacticityUS6255506 *Dec 21, 1998Jul 3, 2001Targor GmbhSupported system in polymerization or copolymerization of high molecular weight polyolefins of high isotacticity and narrow molecular-weight distribution; films, sheets or large hollow articles or moldingsCA2191661A1Nov 29, 1996Jun 2, 1997Andreas WinterHigh molecular weight copolymersEP0576970A1 *Jun 22, 1993Jan 5, 1994Hoechst AktiengesellschaftMetallocenes with arylsubstituted indenyl-derivatives as ligands, process for their preparation and their use as catalystsEP0629632A2Jun 6, 1994Dec 21, 1994Mitsui Petrochemical Industries, Ltd.Novel transition metal compound for use as a polymerization catalystEP0646624A1Jan 11, 1994Apr 5, 1995Mitsui Petrochemical Industries, Ltd.Propylene polymer compositionEP0704461A2Sep 29, 1995Apr 3, 1996Mitsui Petrochemical Industries, Ltd.Olefin polymerization catalyst and process for olefin polymerizationEP0704463A1Apr 11, 1995Apr 3, 1996Mitsui Petrochemical Industries, Ltd.Process for producing propylene polymer composition, and propylene polymer compositionEP0775148B1Jul 14, 1995Aug 25, 1999The Dow Chemical CompanyBiscyclopentadienyl diene complexesEP0776913A2Nov 26, 1996Jun 4, 1997Hoechst AktiengesellschaftHigh molecular weight copolymersEP0816395A2Apr 11, 1995Jan 7, 1998Mitsui Petrochemical Industries, Ltd.Process for preparing propylene polymer composition and propylene polymer compositionEP0846696A1Dec 9, 1997Jun 10, 1998Mitsubishi Chemical CorporationCatalyst for polymerization of alpha-olefinsWO1998040331A1Mar 5, 1998Sep 17, 1998Targor GmbhPreparation of preparing substituted indanonesWO1998040416A1Mar 5, 1998Sep 17, 1998Targor GmbhSupported catalyst system, method for the production and use thereof in olefin polymerizationWO1998040419A1Mar 5, 1998Sep 17, 1998Wolfgang BidellMethod for producing olefin polymers with a higher melting pointWO1999012943A1Sep 3, 1998Mar 18, 1999Targor GmbhMethod for producing metallocenesWO1999033881A1Dec 10, 1998Jul 8, 1999Targor GmbhSupported catalyst system for the polymerisation of olefinsWO1999042497A1Feb 13, 1999Aug 26, 1999Carsten BingelCatalyst system, method for the production thereof and its use for the polymerization of olefinsWO2000020462A2Sep 8, 1999Apr 13, 2000Dow Chemical CoBridged metal complexes for gas phase polymerizations* Cited by examinerNon-Patent CitationsReference1D.P. Krut'ko et al., "Synthesis and photoinduced isomerization of ansa-{eta5, eta5'-[1,1'-(1-silacyclopent-3-ene3-1m,1-diyl)bis(indenyl)]}-dichlorozirconium. The crystal structure of its meso form"-Russian Chemical Bulletin vol. 47 (11), Nov., 1998-pp. 2280-2285.2D.P. Krut'ko et al., "Synthesis and photoinduced isomerization of ansa-{η5, η5′-[1,1′-(1-silacyclopent-3-ene3-1m,1-diyl)bis(indenyl)]}-dichlorozirconium. The crystal structure of its meso form"�Russian Chemical Bulletin vol. 47 (11), Nov., 1998�pp. 2280-2285.3U.S. application No. 09/619,749, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040H).4U.S. application No. 09/619,750, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040G).5U.S. application No. 09/619,751, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039D).6U.S. application No. 09/619,752, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040F).7U.S. application No. 09/619,757, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039E).8U.S. application No. 09/619,759, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040B).9U.S. application No. 09/619,764, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040J).10U.S. application No. 09/620,046, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039A).11U.S. application No. 09/620,175, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040A).12U.S. application No. 09/620,198, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040L).13U.S. application No. 09/620,302, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040K).14U.S. application No. 09/620,303, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040I).15U.S. application No. 09/620,304, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040D).16U.S. application No. 09/620,341, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039C).17U.S. application No. 09/620,359, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039B).18U.S. application No. 09/620,522, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040E).19U.S. application No. 09/620,613, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039F).20Woei-Min Tsai et al., "Silolene-Bridged Zirconocenium Polymerization Catalysts" Journal of Polymer Science, Part A: Polymer Chemistry, vol. 32, pp. 149-158 (1994).Referenced byCiting PatentFiling datePublication dateApplicantTitleUS6916892Nov 15, 2002Jul 12, 2005Fina Technology, Inc.Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropyleneUS7169864Dec 1, 2004Jan 30, 2007Novolen Technology Holdings, C.V.Metallocene catalysts, their synthesis and their use for the polymerization of olefinsUS7232869May 17, 2005Jun 19, 2007Novolen Technology Holdings, C.V.Combining a Lewis base, organometallic component, then a metallocene compound, where the specific stoichiometric ratio of the catalyst components is controlled, which unexpectedly displays very high polymerization activities and gives a good polymer morphology; for olefin polymerizationUS7297747Oct 27, 2004Nov 20, 2007Exxonmobil Chemical Patents Inc.Polymerization process and polymer compositionUS7468416May 16, 2007Dec 23, 2008Lummus Technology Inc.Catalyst composition for olefin polymerizationUS20060293462 *Dec 7, 2005Dec 28, 2006Sunny JacobHeterogeneous polymer blend and process of making the sameEP2573091A1Sep 23, 2011Mar 27, 2013Lummus Novolen Technology GmbhProcess for recycling of free ligand from their corresponding metallocene complexesWO2008079483A1Oct 17, 2007Jul 3, 2008Exxonmobil Chem Patents IncProcess of making polymer blendsWO2008079509A1Oct 26, 2007Jul 3, 2008Exxonmobil Chem Patents IncProcess of making polymer blendsWO2013041619A1Sep 20, 2012Mar 28, 2013Lummus Novolen Technology GmbhProcess for recycling of free ligand from their corresponding metallocene complexes* Cited by examinerClassifications U.S. Classification526/127, 502/117, 502/152, 502/155, 526/160, 526/943, 502/103International ClassificationC08F110/02, C08F210/16, C08F210/06, C08F4/02, C08F110/06, C08F4/60, C07F17/00, C08F4/659, C08F10/00, C08F4/44Cooperative ClassificationY10S526/943, C08F210/06, C08F10/00, C07F17/00, C08F4/65908, C08F210/16, C08F110/02, C08F4/65912, C08F110/06, C08F4/65916European ClassificationC08F10/00, C07F17/00Legal EventsDateCodeEventDescriptionSep 25, 2013FPAYFee paymentYear of fee payment: 12Sep 22, 2009FPAYFee paymentYear of fee payment: 8Sep 27, 2005FPAYFee paymentYear of fee payment: 4Feb 25, 2002ASAssignmentOwner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXASFree format text: CHANGE OF NAME;ASSIGNOR:EXXON CHEMICAL PATENTS INC.;REEL/FRAME:012657/0374Effective date: 20010124Owner name: EXXONMOBIL CHEMICAL PATENTS INC. 13501 KATY FREEWAFree format text: CHANGE OF NAME;ASSIGNOR:EXXON CHEMICAL PATENTS INC. /AR;REEL/FRAME:012657/0374Oct 23, 2000ASAssignmentOwner name: EXXON CHEMICAL PATENTS INC., TEXASFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BURKHARDT, TERRY J.;STEHLING, UDO M.;HART, JAMES R.;AND OTHERS;REEL/FRAME:011255/0271;SIGNING DATES FROM 20000911 TO 20000920Owner name: EXXON CHEMICAL PATENTS INC. 13501 KATY FREEWAY HOURotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google