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Patent US6376407 - Metallocene compositions - 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/US6376407?utm_source=gb-gplus-sharePatent US6376407 - Metallocene compositionsAdvanced Patent SearchPublication numberUS6376407 B1Publication typeGrantApplication numberUS 09/619,749Publication dateApr 23, 2002Filing dateJul 19, 2000Priority dateJun 30, 2000Fee statusPaidPublication number09619749, 619749, US 6376407 B1, US 6376407B1, US-B1-6376407, US6376407 B1, US6376407B1InventorsTerry John Burkhardt, William T. Haygood, Jr., Robert Tan Li, James Charles Vizzini, Matthew Cornyn Kuchta, Udo M. Stehling, James R. HartOriginal AssigneeExxonmobil Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (32), Non-Patent Citations (20), Referenced by (12), Classifications (27), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetMetallocene compositionsUS 6376407 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
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;
We claim: 1. A supported catalyst system comprising the product of one or more support materials, one or more activator, 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 hydrogen atom, a halogen atom, a C1-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 �NR2 15, �SR15, �OR15, �OSiR3 15 or �PR2 15 radical, wherein R15 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, or 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 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, fluoroalkyl group or any other Group 14 radical having from 1 to 20 carbon atoms. 2. The supported catalyst system of claim 1 wherein R3 are identical C1-C4 alkyl groups.
3. The supported catalyst system of claim 1 wherein R4 to R7 are hydrogen atoms.
4. The supported catalyst system of claim 1 wherein R3 are both C3 alkyl groups and R9 and R11 are both tertiary butyl groups.
5. The supported catalyst system of claim 1 wherein R17 to R24 are hydrogen an M2 is silicon.
6. The supported catalyst system of claim 1 wherein the activator comprises one or more non-coordinated anion activators.
7. The supported catalyst system of claim 1 wherein the activator comprises one or more alkylalumoxane activators.
8. The supported catalyst system of claim 1 wherein the activator comprises a non-coordinating anion activator and an alkylalumoxane activator.
9. The supported catalyst system of claim 1 wherein the support material comprises magnesium chloride, silica or a combination thereof.
10. The supported catalyst system of claim 1 wherein M1 is zirconium.
11. The supported catalyst system of claim 1 wherein R4 to R7 and R8, R10 and R11 are hydrogen.
R3 are identical or different and are each a hydrogen atom, a halogen atom, a C1-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; preferably R3 is not a hydrogen atom;
preferably, R14, R15and R16 are identical and are a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a CF3 group, a C6-C8 aryl group, a C6-C10 fluoroaryl group, more preferably a pentafluorophenyl group, a C1-C4 alkoxy group, in particular a methoxy group, a C2-C4 alkenyl group, a C7-C10 arylalkyl group, a C8-C12 arylalkenyl group, or a C7-C14 alkylaryl group;
R14, R15and 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;
rac-dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2hafnium
rac-dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2hafnium dichloride;
rac-dimethylsiladiyl(2-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2hafnium dichloride;
rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2zirconium dichloride;
rac-9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2hafnium dichloride;
rac-9-silafluorendiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2hafnium dichloride;
rac-dimethylsiladiyl(2-methyl, 4-[3′,5 ′-di-tbutylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylsiladiyl(2-tert-butyl, 4-[3′,5 ′-di-tbutylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylsiladiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2hafnium dimethyl;
rac-9-silafluorendiyl(2-n-butyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride,
rac-9-silafluorendiyl(2-tert-butyl, 4-[3′,5′-bistrifluoromethylphenyl]indenyl)2hafnium dichloride;
rac-dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)2hafnium dimethyl,
rac-dimethylsiladiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)2 η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2η41,4-diphenyl-1,3-butadiene;
rac-dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2η4-1,4diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2η4-1,4diphenyl-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-tert-butyl, 4-8 3′,5′-di-phenylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylamidoborane(2-iso-propyl, 4-[3′,5′-ditbutylphenyl]indenyl)2zirconium dichloride;
rac-dimethylamidoborane(2-n-propyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride,
rac-dimethylamidoborane(2-sec-butyl, 4-[3 ′,5′-bis-trifluoromethylphenyl]indenyl) 2zirconium dichloride;
rac-dimethylamidoborane(2-n-propyl, 4-[3′,5′-diphenylphenyl]indenyl)2zirconium dichloride;
rac-dimethylamidoborane(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylamidoborane(2-iso-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl) 2η4-1,4-diphenyl-1,3-butadiene;
rac-dimethylamidoborane(2-iso-propyl, 4-[3′,5′-ditbutylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylamidoborane(2-n-propyl, 4-[3′,5′-di-isopropylphenyl]indenyl)2zirconium dimethyl
rac-dimethylamidoborane(2-iso-propyl, 4-[3′,5′-di-isopropylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylamidoborane(2-n-butyl, 4-[3′,5′-di-isopropylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylamidoborane(2-iso-butyl, 4-[3′,5′-di-isopropylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylamidoborane(2-sec-butyl, 4-[3′,5′-di-isopropylphenyl]indenyl)2zirconium dimethyl;
rac-dimethylamidoborane(2-tert-butyl, 4-[3′,5′-di-isopropylphenyl]indenyl)2zirconium dimethyl;
rac-diisopropylamidoborane(2-tert-butyl, 4-[3′,5′-ditbutylphenyl]indenyl)2zirconium dichloride;
rac-diisopropylamidoborane(2-n-butyl, 4-[3′,5′-bistrifluoromethylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
rac-diisopropylamidoborane(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)2η4-1,4diphenyl-1,3-butadiene;
rac-diisopropylamidoborane(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)2η4-1,4diphenyl-1,3-butadiene;
rac -diisopropylamidoborane(2-n-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
rac-bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3 ′,5′-di-tbutylphenyl]indenyl)2η4-1,4-diphenyl-1,3-butadiene;
Rac/meso metallocene isomer separation is facilitated when metallocenes containing certain bridging groups are prepared. We have found this to be true when the bridging group, R13, is represented by the formula: wherein
M2 and R17 to R24 are as defined above.
R(AlRO )xAlR2 for linear species and
(AlRO )x for cyclic species where R is a C1-C8 alkyl including mixed alkyls. Compounds in which R is methyl are particularly preferred. Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180, each fully incorporated herein by reference.
EXAMPLES All air sensitive experiments are carried out in nitrogen purged dry boxes. All solvents were purchased from commercial sources. 4-Bromo-2-methyl indene, 4-chloro-2-methyl-indene and tris (perfluorophenyl) borane in toluene were purchased from commercial sources. Aluminum alkyls were purchased as hydrocarbon solutions from commercial sources. The commercial methylalumoxane (�MAO�) was purchased from Albemarle as a 30 wt % solution in toluene. The metallocenes racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride and racemic dimethylsiladiyl(4-[1-naphthy]-2-methylindenyl)2 zirconium dichloride were obtained from commercial sources.
Comparative Example 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2zirconium dichloride Supported Comparison Metallocene Catalyst System 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2zirconium dichloride/MAO In a 100 mL round bottom flask racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride (Comparison metallocene 1, 0.055 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 two minutes. The supported catalyst was recovered as a light orange, free flowing solid (5.63 g).
Comparative Example 2 racemic dimethylsiladiyl(2-methyl-4-[1-naphthy)indenyl)2zirconium dichloride Supported Comparison Metallocene Catalyst System 2 racemic dimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)2zirconium dichloride/MAO
In a 100 mL round bottom flask racemic dimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)2 zirconium dichloride (Comparison metallocene 2, 0.064 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. The supported catalyst was recovered as an orange, free flowing solid (4.72 g).
4-(3′,5′-Di-tertbutylphenyl)-2-methylindene Preparation of the Grignard salt: A 100 ml flask was charged with 1.88 g Mg (77.3 mmol) and 10 mL THF. 13.36 g 3,5-di-tertbutyl-bromobenzene (49.6 mmol) were dissolved in 45 mL THF and slowly added to the Mg-turnings. The flask was heated to 50� C. in an oil bath as soon as the reaction started, and this temperature was kept for one hour after addition of the bromobenzene was complete. The oil bath temperature was raised and a gentle reflux maintained for four hours.
Coupling reaction: A 100 mL flask was charged with 7.42 g 4-chloro-2-methylindene (45.1 mmol), 0.723 g 1,3-bis(diphenylphosphino)propane nickel(II)chloride, (1.334 mmol) and 30 mL Et2O. The red suspension was cooled to −20� C., and the Grignard-salt suspension from above added within 20 minutes. The suspension was heated in an oil bath to 50� C., and stirred for 40 hours at this temperature. The flask was cooled in an ice bath. While stirring, 4 ml water and 15 ml 10% aqueous HCl were added. The THF phase was separated, the water phase washed with Et2O, and the combined organic phases dried with MgSO4. A purification by column chromatography followed after evaporation of the solvent. Silica was used as the stationary phase and pentane as the solvent. Later the solvent was changed to a pentane/Et2O mixture (98:2). All fractions containing product were combined, the solvent completely evaporated. The product was recrystallized in the smallest possible amount of pentane, stored at 4� C., the solvent decanted, and the solid dried under vacuum. Yield was 3.14 g (9.96 mmol, 21.9%). The product is a mixture of two isomers
1H-NMR (CHCl3=7.24 ppm): δ7.40-7.12 (m, 2�6H), 6.64 (s, 1H), 6.53 (t, 1H), 3.36 (s, 2�2H), 2.13 (s, 2�3H), 1.36 (s, 2�18H).
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 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.
9-silafluorenebis-[4-(3′,5′-di-t-butylphenyl)-2-methylindene 9,9-Dichloro-9-silafluorene (1.2 g, 9.2 mmol) was dissolved in 80 mL of THF. To this solution was slowly added lithium 4-(3′,5′-di-t-butylphenyl)-2-methylindene (3.0 g, 9.2 mmol) as a dry powder and the solution was stirred overnight. After this time, the solvent was removed in vacuo and the residue was taken up in diethyl ether. The solution was filtered through a frit to remove LiCl and the solvent was removed in vacuo and used as a crude product (4.1 g) for the next step.
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%).
9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]ZrCl2 The crude solid from the previous step (3.9 g, 4.6 mmol) was taken up in 50 mL of diethyl ether. To this solution was slowly added n-BuLi (3.7 mL, 2.5 M in hexane) and stirred for 3 hours at room temperature. The solution was cooled to −30� C and ZrCl4 (1.1 g, 4.6 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 added under heating. The solution was cooled to induce crystallization. Yield of pure racemic isomer was 280 mgs (6.0%
dimethylsilbis[4-(3′,5′-dimethylphenyl)-2-methylindene SiMe2Cl2 (1.2 g, 9.4 mmol) was dissolved in 80 mL of THF. While stirring, lithium 4-(3,5-dimethylphenyl)-2-methylindenide (4.5 g, 18.7 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 was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (4.23 g, 87%).
Example 7 dimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-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%).
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).
Coupling reaction: A 100 mL flask was charged with 8.2 g 4-chloro-2-methylindene (49.8 mmol) and 1.14 g 1,2-bis(diphenylphosphino)ethane nickel(II)chloride (2.16 mmol). At room temperature the Grignard-salt suspension from above was poured to the indene/nickel catalyst suspension. The suspension was stirred for 16 hours at gentle reflux temperature. While stirring, 5 ml water and 10 mL 10% aqueous HCl were added. The THF phase was separated, the water phase washed with Et2O, and the combined organic phases dried with MgSO4. Purification by column chromatography followed after evaporation of the solvent. Silica was used as the stationary phase and pentane as the solvent. Later the solvent was changed to a pentane/Et2O mixture (98:2). All fractions containing product were combined, the solvent completely evaporated. Yield was 15.35 g, 43.8 mmol (83.5%). The product is a mixture of two diastereomers. 1H-NMR (CHCl3=7.24 ppm): δ7.67-7.63 (m, 2�3H), 7.37-7.10 (m, 2�3H), 6.61 (s, 1H), 6.53 (d, 1H), 3.36 (s, 2H), 3.34 (s, 2H), 2.13 (s, 2�3H), 0.29 (s, 2�18H).
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�2H), 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 H2 0 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%).
Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl),2-isopropylindene SiMe2Cl2 (0.69 g, 5.4 mmol) was dissolved in 80 mL of THF. While stirring, lithium 4-(3′,5′-dimethylphenyl)-2-isopropylindenide (2.9 g, 11 mmol) was added as a dry powder and the contents allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to removed LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (2.1 g, 67%).
Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindene]ZrCl2 Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindene] (2.1 g, 3.6 mmol) was dissolved in 60 mL of Et2O. While stirring, 2.9 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 (0.83 g, 3.6 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue taken up in toluene and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to −35� C. to induce crystallization. 0.24 g (6.0%) of pure racemic compound was obtained.
Example 10 [9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconium dichloride 2,2′-Dibromobiphenyl To a stirred solution of o-dibromobenzene (47.3 g, 0.2 mol) in 450 mL of anhydrous THF was added 76.4 mL of n-BuLi (1.0M in Et2O). The o-dibromobenzene solution was cooled in a dry ice/acetone bath. The yellow-green reaction mixture was allowed to warm to 5� C. and was then hydrolyzed with 100 mL of 5% hydrochloric acid. The resulting layers were separated and the aqueous layer extracted 4 times with 4�20 mL portions of diethyl ether. The ether washings were combined with the original organic layer, the whole was dried over sodium sulfate, filtered, and concentrated by distillation until the distillation temperature reached 70� C. The residue was treated with 50 mL of absolute ethanol and cooled to give 2,2′-dibromobiphenyl. Yield was 2.32 g (7.4%).
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 9,9-dichloro-9-silafluorene (1.4 g, 11 mmol) was dissolved in 80 mL of THF. To this solution was slowly added lithium 4-(3′,5′-dimethylphenyl)-2-methylindene (3.0 g, 11 mmol) as a dry powder and the solution was stirred overnight. After this time, the solvent was removed in vacuo and the residue was taken up in diethyl ether. The solution was filtered through frit to remove LiCl and the solvent was removed in vacuo and used as a crude product (2.1 g) for the next step.
]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%).
Total Ethylene
C2 =/C3 = flow
rates (l/min.)
dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl) zirconium dimethyl/NCA
racemic dimethylsiladiyl-
bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl) zirconium dimethyl/NCA
MFR (g/
Metalloeene
dimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)
156.5minor 172.8
dimethylsiladiylbis(4-(3′,5′-bis-trimethylsilyl-phenyl)-2-methylindenyl)
Ethytene
dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindenyl]
i51.97
i5.43
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