JP6454548B2 - メタロセン錯体を調製するプロセス - Google Patents
メタロセン錯体を調製するプロセス Download PDFInfo
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- JP6454548B2 JP6454548B2 JP2014546361A JP2014546361A JP6454548B2 JP 6454548 B2 JP6454548 B2 JP 6454548B2 JP 2014546361 A JP2014546361 A JP 2014546361A JP 2014546361 A JP2014546361 A JP 2014546361A JP 6454548 B2 JP6454548 B2 JP 6454548B2
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- JP
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- Prior art keywords
- formula
- compound
- indenyl
- group
- ligand
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *B(C1=C(*)c2c(*)c(*)c(*)c(*)c2C1*)O* Chemical compound *B(C1=C(*)c2c(*)c(*)c(*)c(*)c2C1*)O* 0.000 description 3
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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/36—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing five carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/38—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing six carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
Description
式(2)
Pd触媒および塩基の存在下で、溶媒中において、式(8)の2−インデニルピナコリルボラン化合物を式(2)
を含むプロセスにも関する。
をさらに含む本発明のプロセスにも関する。
・ホウ酸ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)[C6H5N(CH3)2H]+[B(C6F5)4]-;
・コバルト酸(III)−ジメチルアニリニウムビス(7,8−ジカルバウンデカホウ酸);
・ホウ酸トリ(n−ブチル)アンモニウムテトラフェニル;
・ホウ酸トリフェニルカルベニウムテトラキス(ペンタフルオロフェニル);
・ホウ酸ジメチルアニリニウムテトラフェニル;
・トリス(ペンタフルオロフェニル)ボラン;および
・ホウ酸テトラキス(ペンタフルオロフェニル)
が挙げられる。
1.1 2,2’−ジブロモビフェニルの合成
1,2−ジブロモベンゼンからの2,2’−ジブロモビフェニルの合成が、反応1に図解されている:
2−ブロモインデンおよびピナコールボランからのボロン酸2−インデニル(2−インデニルピナコリルボラン)の合成が、下記の反応2により図解されている:
対応するフェニリデン架橋ビス(インデニル)配位子を形成するための2,2’−ジブロモビフェニルの2−インデニルピナコリルボラン(ボロン酸2−インデニル)との反応が、下記の反応3に図解されている:
ビス(インデニル)配位子からのジルコニウム錯体の合成が、ここに引用する欧州特許出願公開第1059300A1号明細書に記載されている。その合成の図解が、下記の反応4に与えられている。上述した2,2’−ビス(2−インデニル)ビフェニル配位子をn−ブチルリチウムで脱プロトン化し、その後、四塩化ジルコニウムと反応させて、目的の架橋メタロセン触媒2,2’−ビス(2−インデニル)ビフェニルZrCl2(触媒A)を得た。
同様に、類似の手法を1,2−ビス(2−インデニル)ベンゼンの合成(下記の反応5に図示した反応を参照のこと)について試験し、ホモカップリングした副生成物が形成せずに、所望の化合物が得られた。合成と結果が下記に記載されている。
上述した実施例において調製したジルコニウム錯体(触媒Aまたは触媒B)を使用して、エチレンを単独重合した。重合条件は以下の様に選択した:Al/Zr=2500、25mlのn−ペンタン、10バール(1MPa)のエチレン、60℃、1時間。重合活性を決定した(時間当たりの触媒モル当たりに製造されたkgのポリエチレン(PE))。その結果が、下記の表1に与えられている。
Claims (10)
- 架橋したビス(インデニル)配位子を調製するプロセスであって、
溶媒中において、ビス(トリフェニルホスフィン)パラジウムジクロリドおよび塩基の存在下で、式(1)
の2−インデニルボラン酸またはそのエステル(式中、R7およびR8の各々は、独立して、Hまたは1から6のC原子のアルキルを表すか、またはR7およびR8が、それらが結合するO原子と共に環を形成し、R1、R2、R3、R4の各々が、独立して、H、1〜20のC原子を有する炭化水素基、1〜6のC原子を有するアルコキシ基、アミノ、トリメチルシリル(Me3Si)、ジエチルボロ(Et2B)、ジメチルホスフィド(Me2P)、またはジフェニルホスフィド(Ph2P)を表し、R5、R6の各々が独立してHを表す)を、
式(2)
の臭素置換化合物(式中、Rは、ビフェニリデン基を表す)と反応させて、式(3)
の対応する架橋したビス(インデニル)配位子(式中、RおよびR1、R2、R3、R4、R5、R6が上述したものである)を形成する工程を含むプロセス。 - 前記塩基がトリエチルアミン(Et3N)である、請求項1記載のプロセス。
- 使用される前記溶媒がジオキサンである、請求項1または2記載のプロセス。
- R1、R2、R3、R4、R5、およびR6の全てがHを表す、請求項1から3いずれか1項記載のプロセス。
- 式(8)の2−インデニルピナコリルボラン化合物の調製において、前記Pd触媒として、ビス(トリフェニルホスフィン)パラジウムジクロリド((PPh3)2PdCl2)が使用される、請求項5記載のプロセス。
- 式(8)の2−インデニルピナコリルボラン化合物の調製において、前記塩基として、K3PO4が使用される、請求項5または6記載のプロセス。
- 式(8)の2−インデニルピナコリルボラン化合物の調製において使用される溶媒が、テトラヒドロフランである、請求項5から7いずれか1項記載のプロセス。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11009973.6 | 2011-12-19 | ||
EP11009973 | 2011-12-19 | ||
PCT/EP2012/005231 WO2013091836A1 (en) | 2011-12-19 | 2012-12-13 | Process for the preparation of metallocene complexes |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2015506916A JP2015506916A (ja) | 2015-03-05 |
JP2015506916A5 JP2015506916A5 (ja) | 2016-02-12 |
JP6454548B2 true JP6454548B2 (ja) | 2019-01-16 |
Family
ID=47428556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014546361A Expired - Fee Related JP6454548B2 (ja) | 2011-12-19 | 2012-12-13 | メタロセン錯体を調製するプロセス |
Country Status (5)
Country | Link |
---|---|
US (1) | US9234054B2 (ja) |
EP (1) | EP2800753B1 (ja) |
JP (1) | JP6454548B2 (ja) |
CN (2) | CN104093730A (ja) |
WO (1) | WO2013091836A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013091837A1 (en) | 2011-12-19 | 2013-06-27 | Saudi Basic Industries Corporation (Sabic) | Process for the preparation of metallocene complexes |
JP6600629B2 (ja) | 2013-08-20 | 2019-10-30 | サウディ ベーシック インダストリーズ コーポレイション | 2,2’−ビスインデニルビフェニル配位子の調製方法およびそのメタロセン錯体 |
JP6488307B2 (ja) * | 2013-08-30 | 2019-03-20 | サウディ ベーシック インダストリーズ コーポレイション | ポリオレフィン重合用の架橋メタロセン錯体 |
US9758540B1 (en) | 2016-05-25 | 2017-09-12 | Chevron Phillips Chemical Company Lp | Bicyclic bridged metallocene compounds and polymers produced therefrom |
US9758600B1 (en) * | 2016-05-25 | 2017-09-12 | Chevron Phillips Chemical Company Lp | Bicyclic bridged metallocene compounds and polymers produced therefrom |
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EP0426637B2 (en) | 1989-10-30 | 2001-09-26 | Fina Technology, Inc. | Preparation of metallocene catalysts for polymerization of olefins |
JP3115595B2 (ja) | 1990-07-24 | 2000-12-11 | 三井化学株式会社 | α―オレフィンの重合触媒及びそれを用いたポリ―α―オレフィンの製造方法 |
NL9101502A (nl) | 1991-09-06 | 1993-04-01 | Dsm Nv | Werkwijze voor het bereiden van een gebrugde metalloceenverbinding alsmede een katalysatorcomponent en een werkwijze voor de polymerisatie van een olefinen. |
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JPH08188610A (ja) * | 1995-01-12 | 1996-07-23 | Mitsui Petrochem Ind Ltd | 新規な遷移金属化合物、オレフィン重合用触媒成分、オレフィン重合用触媒およびオレフィンの重合方法 |
IT1275777B1 (it) * | 1995-07-06 | 1997-10-17 | Enichem Spa | Catalizzatore metallocenico per la (co)polimerizzazione delle olefine |
DE69904521T2 (de) * | 1998-03-09 | 2003-10-02 | Basell Polyolefine Gmbh | Verbrückte Zirconocene, deren Herstellung und deren Verwendung als Katalysatorkomponente für die Polymerisation von Olefinen |
IT1298616B1 (it) * | 1998-03-10 | 2000-01-12 | Enichem Spa | Complesso metallocenico pontato per la (co) polimerizzazione delle olefine |
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EP1059300A1 (en) * | 1999-06-11 | 2000-12-13 | Dsm N.V. | Indenyl compounds for the polymerisation of olefins |
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MXPA06000933A (es) * | 2003-07-25 | 2006-03-30 | Pfizer | Compuestos de aminopirazol y uso como inhibidores de chk1. |
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JP2008528580A (ja) * | 2005-01-27 | 2008-07-31 | アストラゼネカ・アクチエボラーグ | P2x7受容体の阻害剤である新規二環式芳香族化合物 |
EP1731535A1 (en) * | 2005-06-07 | 2006-12-13 | Saudi Basic Industries Corporation Inc. | Process for polymerization of olefins |
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WO2013091837A1 (en) | 2011-12-19 | 2013-06-27 | Saudi Basic Industries Corporation (Sabic) | Process for the preparation of metallocene complexes |
-
2012
- 2012-12-13 WO PCT/EP2012/005231 patent/WO2013091836A1/en active Application Filing
- 2012-12-13 US US14/366,690 patent/US9234054B2/en not_active Expired - Fee Related
- 2012-12-13 JP JP2014546361A patent/JP6454548B2/ja not_active Expired - Fee Related
- 2012-12-13 CN CN201280068063.XA patent/CN104093730A/zh active Pending
- 2012-12-13 EP EP12805597.7A patent/EP2800753B1/en not_active Not-in-force
- 2012-12-13 CN CN201711094062.3A patent/CN107721797A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
JP2015506916A (ja) | 2015-03-05 |
EP2800753B1 (en) | 2018-05-23 |
CN107721797A (zh) | 2018-02-23 |
EP2800753A1 (en) | 2014-11-12 |
CN104093730A (zh) | 2014-10-08 |
US20140343238A1 (en) | 2014-11-20 |
WO2013091836A1 (en) | 2013-06-27 |
US9234054B2 (en) | 2016-01-12 |
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