WO1997015581A1 - Zirkonocene und hafnocene mit borylierten cyclopentadienyl-liganden und das verfahren zu ihrer herstellung - Google Patents
Zirkonocene und hafnocene mit borylierten cyclopentadienyl-liganden und das verfahren zu ihrer herstellung Download PDFInfo
- Publication number
- WO1997015581A1 WO1997015581A1 PCT/EP1996/004572 EP9604572W WO9715581A1 WO 1997015581 A1 WO1997015581 A1 WO 1997015581A1 EP 9604572 W EP9604572 W EP 9604572W WO 9715581 A1 WO9715581 A1 WO 9715581A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zirconium
- cyclopentadienyl
- aryl
- boron
- bis
- Prior art date
Links
- 0 C1CC*CC1 Chemical compound C1CC*CC1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Definitions
- the present invention relates to a general synthetic method for the preparation of previously unknown zirconocenes and hafnocenes which carry a boron substituent directly on the cyclopentadienyl ligand. These compounds find a new use in the polymerization of olefins with cocatalysis of aluminum alkyl compounds.
- a large number of metallocene-based catalyst systems are known in the literature. Common to all is the need for a cocatalyst that converts the metallocene into an active form that is able to polymerize olefins. A zirconium cation is generated according to the generally accepted concept.
- MAO-free systems are based on the use of dialkyl metallocenes with "cationization reagents". Only "ligand-free” systems show good polymerization properties (R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325). Common cationization reagents are ammonium compounds (HW Turner, Eur. Pat. Appl.
- Borylated zirconocenes and hafnocenes are not described in the literature. Their synthesis does not succeed according to common methods of metallocene synthesis (DJ Cardin, MF Läppert, CL Raston, Chemistry of Organo-Zirconium and - Hafnium Compounds, Ellis Horwood Ltd., Chichester, 1986), because in the treatment of borylated cyclopentadienes with bases or metalation reagents Breakage of the BC bond occurs.
- the corresponding borylated zirconocenes and hafnocenes can be synthesized from simultaneously borylated and silylated precursors. There is no systematic access to the borylated and silylated cyclopentadienes.
- Alkoxyboranes or amine adducts of alkylboranes can be introduced via metalated precursors (BM Mikhailov, TK Baryshnikova, VS
- Halogen boranes are accessible via Si-B exchange and alkoxy boranes via Sn-B exchange (P. Jutzi, A. Seufert, J.
- Halogen boranes with other radicals obtained a Si-B-cyclopentadiene, which by
- cyclopentadienyl ligands can also be attached cyclopentadienyl ligands such as indenyl, tetrahydroindenyl, which in turn can carry substituents such as alkyl, aryl, benzyl radicals or heteroatoms such as halogens (F, Cl, Br, I), silicon and germanium.
- substituents such as alkyl, aryl, benzyl radicals or heteroatoms such as halogens (F, Cl, Br, I), silicon and germanium.
- the other cyclopentadienyl ligand can be the same as the first, but can also be boron-free and carry the same or different substituents as listed above.
- L 'can be another cyclopentadienyl ligand like the first, i.e. H. carry the same or different substituents, but it can also be boron-free.
- R 1 to R 4 can be different from R 5 to R s .
- R 4 and R 8 can also contain methyl, ethyl, allyl, phenyl, aryl, benzyl radicals and heteroatoms such as halogens (F, Cl , Br, I), silicon, germanium. If the bridge consists of only one boron, then R 1 to R 4 are equal to R 5 to R 8 .
- the substituent L on the boron of the cyclopentadienyl ligand or on the boron of the bridge can be alkyl, aryl, benzyl, fluorinated alkyl or aryl, halogens (F, Cl, Br, I), OH, alkoxy , where the residues can form part of a cycle.
- the substituents X on the transition metal can be a halogen or nitrogen.
- the same metallocene complexes can also be obtained by an alternative synthetic route.
- boron-substituted cyclopentadiene compounds with weakly nucleophilic bases such as. B. lithium bis (trimethylsilyl) amide deprotonated and then converted by transmetallation into the corresponding metallocenes.
- weakly nucleophilic bases such as. B. lithium bis (trimethylsilyl) amide deprotonated and then converted by transmetallation into the corresponding metallocenes.
- the corresponding borylated zirconocenes and hafnocenes can be synthesized from all borylated precursors. In these cases, the precursors no longer necessarily have to be silylated. In the case of zirconocenes and hafnocenes with a one-member boron bridge, complexes are also accessible which have differently substituted cyclopentadienyl rings.
- Zirconocenes and hafnocenes bridged differently can also be obtained by mild thermolysis of bisborylated zirconocene and hafnocene derivatives with alkoxy radicals on the boron:
- the R 'radicals can be any alkyl or aryl groups.
- zirconocenes and hafnocenes which can be prepared in this way are to be used as catalyst components in olefin polymerization, with an activity which is up to a factor of 10 greater than that of the parent compound Cp 2 ZrCl 2 of zirconocenes.
- the solid still contains 10-20% of the bis ( ⁇ 5 - (3-methyl-2,3-dihydro-benzoboroyl) cyclopentadienyl) (dichloro) zirconium (IV).
- the tan residue is recrystallized from a little hexane and the tan residue is dried again in an oil pump vacuum for 24 h. This process can be repeated several times, but it is never possible to remove all (chlorine) (trimethyl) tin.
- the bis (pentafluorophenyl) (3-trimethylsilylcyclopentadienyl) borane is also always contaminated by higher molecular weight compounds. Due to its temperature sensitivity, distillation is not possible. Yield: approx. 80 - 90% (NMR)
- a suspension of 4.02 g (12.2 mmol) of [bis (indenyl) (phenyl) borane] diüthium in 150 ml of toluene and 30 ml of diethyl ether is cooled to -78 ° C. and mixed with 2.85 g (12.2 mmol) of zirconium tetrachloride.
- the mixture is allowed to warm to room temperature in a cold bath and a brown-red suspension is obtained after 30 hours. After filtering off insolubles, the dark red filtrate is stored at -20 ° C for three days, whereby 908 mg (14%) of an orange-red powder can be isolated.
- the remaining solution is evaporated to dryness in an oil pump vacuum, and 2.45 g of the zirconocene dichloride (contaminated crude product) can be isolated as a red-brown powder.
- a suspension of 8.53 g (22.8 mmol) of the dilithium salt in 150 ml of toluene and 50 ml of diethyl ether is cooled to -78 ° C. and 5.31 g (22.8 mmol) of zirconium tetrachloride are added.
- the mixture is allowed to warm to room temperature in a cold bath and an orange suspension is obtained after 30 hours.
- the orange-colored filtrate is concentrated to dryness in an oil pump vacuum and 12.9 g (95%) of the zirconocene dichloride is obtained as a crude product as a yellow powder.
- a diastereomer can be significantly enriched by extraction with pentane:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96934773A EP0866795A1 (de) | 1995-10-25 | 1996-10-22 | Zirkonocene und hafnocene mit borylierten cyclopentadienyl-liganden und das verfahren zu ihrer herstellung |
JP9516266A JP2000500435A (ja) | 1995-10-25 | 1996-10-22 | ホウ素置換されたシクロペンタジエニル配位子を有するジルコノセンおよびハフノセンおよびその製造方法 |
US09/051,609 US5962718A (en) | 1995-10-25 | 1996-10-22 | Zirconocenes and hafnocenes with boron-substituted cyclopentadienyl-ligands and the method of producing them |
CA002235944A CA2235944A1 (en) | 1995-10-25 | 1996-10-22 | Zirconocenes and hafnocenes with borylated cyclopentadienyl ligands and method for preparation thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19539650.2 | 1995-10-25 | ||
DE19539650A DE19539650A1 (de) | 1995-10-25 | 1995-10-25 | Zirconocene und Hafnocene mit borylierten Cyclopentadienyl-Liganden und das Verfahren zu ihrer Herstellung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997015581A1 true WO1997015581A1 (de) | 1997-05-01 |
Family
ID=7775700
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/004572 WO1997015581A1 (de) | 1995-10-25 | 1996-10-22 | Zirkonocene und hafnocene mit borylierten cyclopentadienyl-liganden und das verfahren zu ihrer herstellung |
Country Status (6)
Country | Link |
---|---|
US (1) | US5962718A (de) |
EP (1) | EP0866795A1 (de) |
JP (1) | JP2000500435A (de) |
CA (1) | CA2235944A1 (de) |
DE (1) | DE19539650A1 (de) |
WO (1) | WO1997015581A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0811627A2 (de) * | 1996-06-03 | 1997-12-10 | Hoechst Aktiengesellschaft | Chemische Verbindung, neutral oder ionisch aufgebaut, geeignet als Katalysatorkomponente für die Olefinpolymerisation |
WO2001068719A1 (fr) * | 2000-03-14 | 2001-09-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Composant catalyseur a metal de transition pour la polymerisation, et procede de production de polymere a l'aide de ce composant |
US6420299B1 (en) | 1999-06-04 | 2002-07-16 | Dow Global Technologies Inc. | Boron-substituted cyclopentadienes and metal complexes thereof |
WO2002076999A1 (de) * | 2001-03-23 | 2002-10-03 | Bayer Aktiengesellschaft | Katalysatoren mit einer donor-akzeptor-wechselwirkung |
US6891004B2 (en) | 2000-03-14 | 2005-05-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Transition metal catalyst component for polymerization, and method for producing a polymer by means thereof |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5939503A (en) * | 1996-08-09 | 1999-08-17 | California Institute Of Technology | Group IV zwitterion ansa metallocene (ZAM) catalysts for α-olefin polymerization |
KR100628614B1 (ko) * | 1998-10-08 | 2006-09-26 | 더 다우 케미칼 캄파니 | 가교된 금속 착체 |
DE19858016A1 (de) * | 1998-12-16 | 2000-06-21 | Basf Ag | Neue Metallocenkomplexe |
JP2002332307A (ja) * | 2001-05-10 | 2002-11-22 | Denki Kagaku Kogyo Kk | 重合用遷移金属触媒成分、それを用いた重合体の製造方法 |
EP1428840A4 (de) * | 2001-08-07 | 2005-04-06 | Denki Kagaku Kogyo Kk | Polymerherstellungsverfahren |
WO2016037960A1 (en) * | 2014-09-10 | 2016-03-17 | Sabic Global Technologies B.V. | Boron-bridged 2-indenyl metallocene complexes for olefin polymerization |
US11186601B2 (en) | 2018-08-29 | 2021-11-30 | Exxonmobil Chemical Patents Inc. | Metallocene compounds having appended Lewis acids and polymerization therewith |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0277004A1 (de) * | 1987-01-30 | 1988-08-03 | Exxon Chemical Patents Inc. | Katalysatoren, Verfahren zur Herstellung derselben und Verfahren zu deren Anwendung |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5262498A (en) * | 1991-01-12 | 1993-11-16 | Hoechst Aktiengesellschaft | Metallocene (co)polymers, process for their preparation and their use as catalysts |
US5169818A (en) * | 1991-01-12 | 1992-12-08 | Hoechst Aktiengesellschaft | Metallocene (co)polymers, process for their preparation and their use as catalysts |
US5468889A (en) * | 1994-06-20 | 1995-11-21 | The University Of Toledo | Boryl zirconocene organic 1,1-dimetallic compounds |
-
1995
- 1995-10-25 DE DE19539650A patent/DE19539650A1/de not_active Withdrawn
-
1996
- 1996-10-22 JP JP9516266A patent/JP2000500435A/ja active Pending
- 1996-10-22 EP EP96934773A patent/EP0866795A1/de not_active Withdrawn
- 1996-10-22 US US09/051,609 patent/US5962718A/en not_active Expired - Fee Related
- 1996-10-22 CA CA002235944A patent/CA2235944A1/en not_active Abandoned
- 1996-10-22 WO PCT/EP1996/004572 patent/WO1997015581A1/de not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0277004A1 (de) * | 1987-01-30 | 1988-08-03 | Exxon Chemical Patents Inc. | Katalysatoren, Verfahren zur Herstellung derselben und Verfahren zu deren Anwendung |
Non-Patent Citations (3)
Title |
---|
BOCHMANN, M. ET AL.: "anionic and zwitterionic metallocene complexes derived from novel boratocyclopentadienyl ligands", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 20, 21 October 1995 (1995-10-21), pages 2081 - 2082, XP002022130 * |
CHEMICAL ABSTRACTS, vol. 124, no. 19, 6 May 1996, Columbus, Ohio, US; abstract no. 261220j, REETZ, M.T. ET AL.: "preparation and catalytic activity of boron-substituted zirconocenes" XP002022131 * |
CHIMIA, vol. 49, no. 12, 1995, pages 501 - 503 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0811627A2 (de) * | 1996-06-03 | 1997-12-10 | Hoechst Aktiengesellschaft | Chemische Verbindung, neutral oder ionisch aufgebaut, geeignet als Katalysatorkomponente für die Olefinpolymerisation |
EP0811627A3 (de) * | 1996-06-03 | 1999-12-22 | TARGOR GmbH | Chemische Verbindung, neutral oder ionisch aufgebaut, geeignet als Katalysatorkomponente für die Olefinpolymerisation |
US6255531B1 (en) | 1996-06-03 | 2001-07-03 | Targor Gmbh | Boron compounds and other compounds of group IIIa |
US6410665B1 (en) | 1996-06-03 | 2002-06-25 | Basell Polyolefine Gmbh | Chemical compound |
US6420299B1 (en) | 1999-06-04 | 2002-07-16 | Dow Global Technologies Inc. | Boron-substituted cyclopentadienes and metal complexes thereof |
JP2003501433A (ja) * | 1999-06-04 | 2003-01-14 | ザ ダウ ケミカル カンパニー | ホウ素置換シクロペンタジエンの4族金属錯体 |
WO2001068719A1 (fr) * | 2000-03-14 | 2001-09-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Composant catalyseur a metal de transition pour la polymerisation, et procede de production de polymere a l'aide de ce composant |
US6891004B2 (en) | 2000-03-14 | 2005-05-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Transition metal catalyst component for polymerization, and method for producing a polymer by means thereof |
WO2002076999A1 (de) * | 2001-03-23 | 2002-10-03 | Bayer Aktiengesellschaft | Katalysatoren mit einer donor-akzeptor-wechselwirkung |
Also Published As
Publication number | Publication date |
---|---|
US5962718A (en) | 1999-10-05 |
DE19539650A1 (de) | 1997-04-30 |
EP0866795A1 (de) | 1998-09-30 |
CA2235944A1 (en) | 1997-05-01 |
JP2000500435A (ja) | 2000-01-18 |
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