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Patent US6380121 - 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. In one embodiment, the metallocenes of the present invention may be represented by the formula: wherein: M is a metal of Group 4, 5,...http://www.google.com/patents/US6380121?utm_source=gb-gplus-sharePatent US6380121 - Metallocene compositionsAdvanced Patent SearchPublication numberUS6380121 B1Publication typeGrantApplication numberUS 09/619,751Publication dateApr 30, 2002Filing dateJul 19, 2000Priority dateJun 30, 2000Fee statusPaidPublication number09619751, 619751, US 6380121 B1, US 6380121B1, US-B1-6380121, US6380121 B1, US6380121B1InventorsMatthew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr., Terry J. BurkhardtOriginal AssigneeExxonmobil Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (32), Non-Patent Citations (20), Referenced by (9), Classifications (27), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetMetallocene compositionsUS 6380121 B1Abstract This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization.
R5 and R6 are identical or different, are one of 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;
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 are 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 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; 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
R5 and R6 are identical or different, preferably identical, are one of a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-C10 alkyl group, preferably a C1-C4 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, preferably a C6-C8 aryl group, a C2-C10 alkenyl group, preferably a C2-C4 alkenyl group, a C7-C40-arylalkyl group, preferably a C7-C 10 arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a C8-C40 arylalkenyl group, preferably a C8-C12 arylalkenyl group, a �NR2 15, �SR15, �OR15, �OSiR3 15 or �PR2 15 radical,
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;
R(AlRO)xAIR2 for linear species and
(AlRO)xfor 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.
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-methyl4-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).
Example 4 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%).
Example 5 [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 and 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%)
lithium 4-(3′,5′-dimethylphenyl)2-isopropylindene 4-(3′,5′-dimethylphenyl)-2-methylindene (5.6 g, 24 mmol) was dissolved in 80 mL of pentane. To this solution was added 9.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield was 4.5 g (80%).
Supported Metallocene Catalyst System 5 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 2hours and thirty minutes. The supported catalyst was recovered as a dull purple, free flowing solid (5.06 g).
Example 6 rac-9-silafluorenebis(2-methylindenyl)zirconium dimethyl 9-Silafluorene, 9,9-bis-2-Methylindene Solid 2-Methylindenyl lithium (3.34 g, 24.52 mmol) was added to a stirred solution of 9,9-Dichloro,9-silafluorene (3.08 g, 12.26 mmol) in Et2O (ca. 25 mL) and the resultant mixture was stirred at room temperature for 2hours. The solvent was removed and the residue was extracted into CH2Cl2 (ca. 75 mL), filtered and the solvent removed giving a white powder which was washed with pentane (ca 50 mL) and dried under vacuum leaving 9-Silafluorene, 9,9-bis-2-Methylindene as a white powder (3.80 g, 71%).
Preparation of 9-Silafluorene,9,9-bis-2-Methylindenyl Zirconium Dimethyl A mixture of 9-Silafluorene, 9,9-bis-2-Methylindenyl dilithium.(Et2)0.5 (1.83 g, 3.69 mmol) and ZrCl4 (0.95 g, 4.08 mmol) in benzene (ca. 25 mL) was stirred for 80 minutes at room temperature producing an orange solid. The mixture was filtered and the orange solid was washed with hexane. Upon mixing with the benzene filtrate, the hexane wash produced a yellow solid and this mixture was filtered to remove the yellow solid. The solvents were removed from the resulting benzene-hexane filtrate producing an orange solid. The second orange solid was washed once with benzene and twice with pentane and dried under vacuum. A slurry of this orange solid in benzene (ca. 10 mL) was treated with CH3MgBr (0.8 mL of a 3.0 M solution in Et2O) and the mixture was stirred for 15 minutes at room temperature. Dioxane (ca. 2-3 mL) was added to the mixture which was filtered to produce a clear yellow filtrate. The solvents were removed from the filtrate under vacuum giving pure rac-9-Silafluorene,9,9-bis-2-Methylindenyl Zirconium Dimethyl (0.035 g, 1.7%).
Polymerization Using rac-9-silafluorenebis(2-methylindenyl)zirconium dimethyl as Catalyst Precursor�Isotactic Polypropylene Homopolymer Procedure A solution of triisobutylaluminum (TIBAL) scavenger (0.3 mL of a 10% by volume solution in toluene) in toluene ( 0.7 mL) was added to a dry clean two liter autoclave under a nitrogen purge. The autoclave was filled with 300 mL of liquid propylene and heated to 60� C. The catalyst, formed by reacting the catalyst precursor and the trityltetrakisperfluorophenylborate activator in equimolar amounts in toluene (ca. 1-1.5 mL) for a period of five minutes, was flushed into the autoclave with 100 mL of propylene. The polymerizations were carried out for fifteen minutes after which the reactor was cooled and the excess propylene was vented. The polymer was removed and dried.
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(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.Catalyst composition 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 blendsWO2013041619A1Sep 20, 2012Mar 28, 2013Lummus Novolen Technology GmbhProcess for recycling of free ligand from their corresponding metallocene complexes* Cited by examinerClassifications U.S. Classification502/103, 502/117, 502/155, 526/943, 502/152, 526/160International ClassificationC08F210/06, C08F110/06, C07F17/00, C08F10/00, C08F4/02, C08F4/60, C08F4/659, C08F110/02, C08F210/16Cooperative ClassificationY10S526/943, C08F4/65912, C08F210/06, C08F210/16, C08F110/02, C08F10/00, C08F4/65916, C07F17/00, C08F110/06, C08F4/65908European 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:012658/0080Effective date: 20010124Owner name: EXXONMOBIL CHEMICAL PATENTS INC. 13501 KATY FREEWAFree format text: CHANGE OF NAME;ASSIGNOR:EXXON CHEMICAL PATENTS INC. /AR;REEL/FRAME:012658/0080Oct 23, 2000ASAssignmentOwner name: EXXON CHEMICAL PATENTS INC., TEXASFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KUCHTA, MATTHEW C.;STEHLING, UDO M.;LI, ROBERT T.;AND OTHERS;REEL/FRAME:011255/0267;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