JP2015525268A - アミジナートおよびグアニジナート錯体、連鎖移動重合触媒としてのそれらの使用、ならびに当該方法により得られる長鎖アルコール - Google Patents
アミジナートおよびグアニジナート錯体、連鎖移動重合触媒としてのそれらの使用、ならびに当該方法により得られる長鎖アルコール Download PDFInfo
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- BDAJBOIAMYRWFR-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)sulfanylbenzene Chemical compound CC1=CC=CC=C1SC1=CC=CC=C1C BDAJBOIAMYRWFR-UHFFFAOYSA-N 0.000 description 1
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- AQZNRRFSIZDARL-UHFFFAOYSA-H Cl[Zr](Cl)(Cl)(Cl)(Cl)Cl Chemical compound Cl[Zr](Cl)(Cl)(Cl)(Cl)Cl AQZNRRFSIZDARL-UHFFFAOYSA-H 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
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- 150000004714 phosphonium salts Chemical class 0.000 description 1
- MEKRYGUOYPBYAS-UHFFFAOYSA-K piperidin-1-ide trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3]N1CCCCC1 MEKRYGUOYPBYAS-UHFFFAOYSA-K 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/122—Metal aryl or alkyl compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- 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
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/202—Ethylene glycol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
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- C07C31/20—Dihydroxylic alcohols
- C07C31/205—1,3-Propanediol; 1,2-Propanediol
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
- B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/46—C-H or C-C activation
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- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
Description
R1およびR2は、互いに独立して、炭化水素部分、特にC1−C40、好ましくはC1−C18であり、さらに(N原子に直接隣接していない)1以上の窒素、酸素および/またはケイ素原子を含む任意に置換された炭化水素部分であり、さらに任意に互いにまたはZ1および/もしくはZ3と連結している。
・炭化水素部分、特にC1−C40、好ましくはC3−C22、最も好ましくはC8−C18またはより好ましくはC10−C22であり、任意に互いにまたはZ2と連結しており、Z1およびZ3は任意にさらに(N原子に直接隣接していない)1以上の窒素、酸素および/またはケイ素原子を含み、
・好ましくはアルキル、特にC1−C40、好ましくはC3−C22、最も好ましくはC8−C18であり、または、アリール部分、特にC6−C22、最も好ましくはC8−C18であり、任意においてさらにヒドロカルビル基、特にC1−C12、好ましくはC2−C6、特にアルキル、アルケニルまたはアリール基によって置換されており、Z1およびZ3は任意においてさらに(N原子に直接隣接していない)1以上の窒素、酸素および/またはケイ素原子を含み、
・置換フェニル、特にトリル、特に2位および/または6位置換であり、モノ−、ジ−もしくはトリ−イソプロピルフェニル、特に2,6−ジイソプロピルフェニル、モノ−、ジ−もしくはトリ−t−ブチルフェニル、特に2,6−ジ−t−ブチルフェニル、モノ−、ジ−もしくはトリ−(C1−C4)アルコキシフェニル、特に2,6−ジ−(C1−C4)アルコキシフェニル、または、モノ−もしくはジ−(C1−C4)アルキルアミノフェニル、特に2,6−ジ−(C1−C4)アルキルアミノフェニルである。
・炭化水素部分、特にC1−C40、好ましくはC3−C22、最も好ましくはC8−C18であり、任意に互いにまたはZ2と連結しており、Z1およびZ3は任意にさらに(N原子に直接隣接していない)1以上の窒素、酸素および/またはケイ素原子を含み、
・好ましくはアルキル、特にC1−C40、好ましくはC3−C22、最も好ましくはC8−C18であり、または、アリール部分、特にC6−C22、最も好ましくはC8−C18であり、任意にさらにヒドロカルビル基、特にC1−C12、好ましくはC2−C6、特にアルキル、アルケニルまたはアリール基によって置換されており、Z1およびZ3は任意にさらに(Z1およびZ3ではN原子に直接隣接していない、Z2ではC原子に直接隣接していない)1以上の窒素、酸素および/またはケイ素原子を含み、
・最も好ましくはフェニル、置換フェニル、特にトリル、特に2位および/または6位置換であり、モノ−、ジ−もしくはトリ−イソプロピルフェニル特に2,6−ジ−イソプロピルフェニル、モノ−、ジ−もしくはトリ−t−ブチルフェニル特に2,6−ジ−t−ブチルフェニル、モノ−、ジ−もしくはトリ−(C1−C4)アルコキシフェニル特に2,6−ジ−(C1−C4)アルコキシフェニル、または、モノ−もしくはジ−(C1−C4)アルキルアミノフェニル特に2,6−ジ−(C1−C4)アルキルアミノフェニルである。
Mは、Ti、ZrまたはHf、好ましくはTiまたはZrであり、
Xは、それぞれのmで独立して、ハロゲン、好ましくはCl、ヒドロカルビル、特にC1−C40、好ましくはC1−C4、特にメチル、ヒドリド、アルコキシド、任意に置換されたアミド(amido)であって、上に規定されるR1およびR2を有するNR1R2、好ましくはジエチルアミド、ジメチルアミドもしくはメチルエチルアミド、または、テトラヒドロフランであり、
mは、1から4であり、
Z1、Z2およびZ3は、上に規定されるものである。
・{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N,N−ジメチル−グアニジナト}金属(IV)クロリド
・{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N,N−ジエチル−グアニジナト}金属(IV)クロリド
・{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N,N−ペンタメチレン−グアニジナト}金属(IV)クロリド
・{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N−シクロヘキシル−N−メチル−グアニジナト}金属(IV)クロリド
・{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N−シクロヘキシル−N−メチル−グアニジナト}金属(IV)クロリド
・[ジエチルアンモニウム][N,N’−ビス(2,6−ジイソプロピルフェニル)−ベンズアミジナト−テトラクロロ]metalat(IV)
・[ジエチルアンモニウム][N,N’−ビス(2,6−ジイソプロピルフェニル)−4−(ジメチルアミノ)ベンズアミジナト−テトラクロロ]metalat(IV)
・[ジエチルアンモニウム][N,N’−ビス(2,6−ジイソプロピルフェニル)−4−メトキシベンズアミジナト−テトラクロロ]metalat(IV)
・[ジエチルアンモニウム][N,N’−ビス(2,6−ジイソプロピルフェニル)−4−(2,5−ジメチル−1H−ピロール−1−イル)ベンズアミジナト−テトラクロロ]metalat(IV)
・[N,N’−ビス(2,6−ジイソプロピルフェニル)−4−(ジメチルアミノ)ベンズアミジナト−ジエチルアミド]金属(IV)クロリド
・[N,N’−ビス(2,6−ジイソプロピルフェニル)−4−(2,5−ジメチル−1H−ピロール−1−イル)ベンズアミジナト−ジエチルアミド]金属(IV)クロリド
ここで、金属は、チタン、ジルコニウムまたはハフニウムである。Z1とZ3とが異なっている金属触媒も可能である(3c、3d、4c、4d)。
・MX4(それぞれのXは、独立して、ハロゲン{F、Cl、Br、I}、ヒドリド{H}、ヒドロカルビル{R、例えばベンジル}、アルコキシド{OR}またはアミド{NR1R2}であり得る)
・MX4L2(それぞれのXは、独立して、ハロゲン{F、Cl、Br、I}、ヒドリド{H}、ヒドロカルビル{R、例えばベンジル}、アルコキシド{OR}またはアミド{NR1R2}であり得、Lは、任意の2電子供与体リガンド、例えばテトラヒドロフランもしくはジエチルエーテル等のエーテル、アセトニトリルまたはトリヒドロカルビルホスフィン、と同等である)
・M(acac)4(acacは、2,4−ペンタンジオナト、1,1,1,5,5,5−ヘキサフルオロ−2,4−ペンタンジオナト、または、2,2,6,6,−テトラメチル−3,5−ヘプタンジオナトである)
・M(O2CR)4(O2CRは、任意のカルボン酸アニオン、例えば2−エチルヘキサン酸塩である)
・ビス(2,6−ジイソプロピルフェニル)カルボジイミドまたはジシクロヘキシルカルボジイミド等の、ジヒドロカルビルカルボジイミド
・ビス(2−メトキシフェニル)カルボジイミド等の、ジヘテロヒドロカルビルカルボジイミド
・例えば、リチウム1,3−ジヒドロカルビルアミダートまたはリチウム1,3−ジヒドロカルビルグアニダートの、アミド化塩またはグアニジン化塩
・N,N’−ビス(2,6−ジイソプロピルフェニル)ベンズイミドアミドまたは2,3−ビス(2,6−ジイソプロピルフェニル)−1,1−ジヒドロカルビルグアニジン等の、アミジンまたはグアニジン
・トリヒドロカルビルアルミニウム(ヒドロカルビルは、例えばメチル、エチル、プロピル、イソプロピル、n−ブチル、イソブチル、ペンチル、ネオペンチル、イソペンチルまたはこれらの混合物であり、好ましくはトリ(メチルおよび/またはエチル)アルミニウムである)
・ジヒドロカルビル亜鉛(ヒドロカルビルは、例えばメチル、エチル、プロピル、イソプロピル、n−ブチル、イソブチル、ペンチル、ネオペンチル、イソペンチルまたはこれらの混合物であり、好ましくはジ(メチルおよび/またはエチル)亜鉛である)
・上記のような、トリヒドロカルビルアルミニウムおよびジヒドロカルビル亜鉛の混合物
・オリゴマーまたはポリマーヒドロカルビルアルモキサン、好ましくはオリゴマーまたはポリマーメチルアルモキサン(トリイソブチルアルミニウムまたはイソブチルアルモキサンとのメチルアルモキサンの反応によって修飾された修飾メチルアルモキサンを含む)
・アルキルが好ましくはC1−C3アルキルである、ジアルキルアルミニウムハロゲン化物またはアルキルアルミニウムジハロゲン化物等の、ヒドロカルビルアルミニウムハロゲン化物
・ヒドロカルビルアルミニウムセスキハロゲン化物、好ましくはメチルアルミニウムセスキハロゲン化物
・または、これらの混合物
a)高温度は、特にチタニウム触媒では、より低い分子量をもたらす。
b)錯体に対してより高いAl/Zn比は、一般的に、より低い分子量をもたらす。
c)より短い反応時間は、特にZrを含む錯体では、より低い分子量をもたらし得る。
d)高モノマー濃度は、より高い分子量をもたらす。
e)トリエチルアルミニウムで行われた重合は、他の有機アルミニウム助触媒と比較して、より低い分子量生成物をもたらした。
Me −メチル(CH3)
Et −エチル(CH3CH2)
i−Pr −イソ−プロピル(Me2CH)
i−Bu −イソ−ブチル(Me2CHCH2)
Cy −シクロヘキシル(C6H11)
Oct −オクチル(C8H17)
MAO −メチルアルミニウムオキサン[(MeAlO)n・(Me3Al)1/3n]
d−MAO −ドライ−メチルアルミノキサン[(MeAlO)n]
TMA −トリメチルアルミニウム(Me3Al)
TEA −トリエチルアルミニウム(Et3Al)
TIBA −トリ−イソ−ブチルアルミニウム(i−Bu3Al)
TOA −トリオクチルアルミニウム(Oct3Al)
Pi −ピペリジン−1−イル(C5H10N)
{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N,N−ジエチル−グアニジナト}チタン(IV)クロリド{[Et2NC(2,6−Pri 2C6H3N)2]TiCl3;錯体A}の合成
{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N−メチル−N−シクロヘキシル−グアニジナト}チタン(IV)クロリド{[Me(Cy)NC(2,6−Pri 2C6H3N)2]TiCl3;錯体B}の合成
{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N,N−ペンタメチレン−グアニジナト}チタニウム(IV)クロリド{[PiC(2,6−Pri 2C6H3N)2]TiCl3;錯体C}の合成
{N’,N’’−ビス[2,6−ジ(メチル)フェニル]−sec−ブチル−アミニジナト}チタニウム(IV)クロリド[{secBuC(N−2,6−Me2C6H3)2}TiCl4][Et2NH2];錯体Dの合成
エチレン重合(runs 1−15)
エチレン重合(runs 16−28)
エチレン重合実験(runs 29−37)
{N’,N’’−ビス[2,6−ジ(1−メチルエチル)フェニル]−N,N−ジエチル−グアニジナト}−(ジエチルアミド)ジルコニウム(VI)クロリド{[Et2NC(2,6−Pri 2C6H3N)2](Et2N)ZrCl2(THF);錯体D;異性体の混合物}の合成
エチレン重合実験(runs 38−48)
Claims (22)
- a)金属がTi、ZrまたはHfであり、金属毎に次の式からなる1つのリガンドを有し、前記リガンドが前記金属に結合している、触媒としての金属錯体であって、
Z1、Z2およびZ3は、独立して炭化水素部分またはヘテロ原子含有炭化水素部分であり、前記ヘテロ原子が存在する場合には前記ヘテロ原子はN原子に直接隣接しておらず、Z1、Z2およびZ3は互いに独立して任意にそれぞれの他の1以上と連結している、金属錯体と、
b)助触媒としての有機アルミニウム化合物、助触媒としての有機亜鉛化合物、または、その両方、と、
を含み、
前記助触媒に対する前記触媒の原子比は、前記組成物における、全てのAlおよびZn原子の合計に対する全てのTi、ZrおよびHf原子の合計で、1:2000から1:1000000(Ti、ZrおよびHf原子の合計:AlおよびZn原子の合計)である、触媒組成物。 - 前記金属は、TiまたはZrである、請求項1に記載の組成物。
- 前記金属錯体は、遷移金属前駆体およびリガンド前駆体からin situで形成される、請求項1ないし3のいずれか1項に記載の組成物。
- Z2は、窒素、酸素およびケイ素から選択される1以上のヘテロ原子を任意に含むC1−C40の炭化水素部分であるか、または、
Z2は、R1およびR2が、互いに独立して、窒素、酸素およびケイ素から選択される1以上のヘテロ原子を任意に含むC1−C40の炭化水素部分であるNR1R2である、請求項1ないし4のいずれか1項に記載の組成物。 - Z1およびZ3は、互いに独立して、芳香族部分、オルト置換芳香族部分およびジ−オルト置換芳香族部分、好ましくはフェニル、オルト置換フェニルおよびジ−オルト置換フェニルから選択される、請求項1ないし5のいずれか1項に記載の組成物。
- Z1およびZ3の少なくとも1つが、好ましくは両方が、互いに独立して、オルト−メチルフェニル、ジ−オルト−メチルフェニル、オルト−エチルフェニル、ジ−オルト−エチルフェニル、オルト−イソプロピルフェニル、ジ−オルト−イソプロピルフェニル、オルト−t−ブチルフェニルまたはジ−オルト−t−ブチルフェニル、好ましくはジ−オルト−イソプロピルフェニルもしくはジ−オルト−t−ブチルフェニルである、請求項1ないし6のいずれか1項に記載の組成物。
- 活性化剤としてホウ素含有化合物をさらに含み、
前記ホウ素含有化合物は、好ましくは、トリス(ペンタフルオロフェニル)ボラン、テトラキス(ペンタフルオロフェニル)ボレート、トリス(テトラフルオロフェニル)ボランおよびテトラキス(テトラフルオロフェニル)ボレートからなる群から選択される1以上のメンバーを含む、請求項1ないし7のいずれか1項に記載の組成物。 - 前記助触媒は、C1−C12のトリヒドロカルビルアルミニウム、メチルアルミノキサンまたはそれらの混合物、好ましくはトリエチルアルミニウムである、請求項1ないし8のいずれか1項に記載の組成物。
- 前記助触媒は、R=C1−C8であるジヒドロカルビル亜鉛(ZnR2)、好ましくはジエチル亜鉛からなる群から選択される、請求項1ないし8のいずれか1項に記載の組成物。
- 前記助触媒は、請求項9のアルミニウム化合物および請求項10の亜鉛化合物の混合物であり、比率は、好ましくは100:1から1:100である、請求項1ないし10のいずれか1項に記載の組成物。
- 前記助触媒に対する前記触媒の比率は、前記組成物における、全てのAlおよびZn原子の合計に対する全てのTi、ZrおよびHf原子の合計で、1:10000から1:1000000、好ましくは1:10000から1:100000、および、最も好ましくは1:10000から1:40000である、請求項1ないし11のいずれか1項に記載の組成物。
- アルコールまたはオレフィンを製造するための方法であって、
AlまたはZn末端オリゴマーまたはポリマー炭化水素を得るために、エチレン、プロピレン、または、エチレンおよびプロピレンを、請求項1ないし12のいずれか1項に記載の触媒組成物と接触させること、を含み、
好ましくは、オレフィン系末端炭化水素に対するAlまたはZn末端オリゴマーまたはポリマー炭化水素の比率が、10:1(AlまたはZn末端オリゴマーまたはポリマー炭化水素:オレフィン系末端炭化水素)より大きく、最も好ましくは100:1(AlまたはZn末端オリゴマーまたはポリマー炭化水素:オレフィン系末端炭化水素)より大きく、
さらに、
a)オレフィンを得るために、炭化水素残基を脱離すること、または、
b)アルコールを得るために、酸素または酸素源を用いる変換により前記AlまたはZn末端オリゴマーまたはポリマー炭化水素を変換し、酸化されたオリゴマーまたはポリマーを加水分解すること、を含む方法。 - 前記アルコールは、100から1000000g/mol、特に150から10000g/mol、または、最も特に100から400g/mol、もしくは、代替として300から1000g/molの分子量(Mw)を有するアルコールであり、任意に前記分子量とは独立して、前記アルコールの80mol%より多くは末端OH基を有するアルコールである、アルコールを製造するための、請求項13に記載の方法。
- 前記オレフィンは、100から1000000g/mol、好ましくは150から10000g/mol、または、最も好ましくは100から400g/mol、もしくは、代替として300から1000g/molの分子量(Mw)を有するオレフィンである、オレフィンを製造するための、請求項13に記載の方法。
- 前記酸素または酸素源は、酸素を含む気体、好ましくは空気である、アルコールを製造するための、請求項13に記載の方法。
- 100から1000000g/mol、好ましくは150から10000g/mol、または、最も好ましくは100から400g/mol、もしくは、代替として300から1000g/molの分子量(Mw)を有する、請求項13ないし15のいずれか1項に記載の方法から得ることができる、アルコールまたはオレフィン。
- 互いに独立して鎖長のガウス分布、および/または、0.1−20重量パーセント、好ましくは5−15重量パーセントのパラフィン含有量を有する、請求項17に記載のアルコール。
- 5重量パーセント未満、特に1重量パーセント未満のオレフィンを含む、請求項17または18に記載のアルコール。
- 金属がTi、ZrまたはHfであり、前記金属に結合する、金属毎に次の式からなる1つのリガンドを有する金属錯体であって、
Z1およびZ3は、独立してそれぞれ8以上の炭素原子を有する炭化水素部分またはヘテロ原子含有炭化水素部分であり、前記ヘテロ原子が存在する場合には前記ヘテロ原子はN原子に直接隣接しておらず、Z1およびZ3は互いに独立して任意にそれぞれと連結しており、
Z2は、独立して炭化水素部分またはヘテロ原子含有炭化水素部分であり、前記ヘテロ原子が存在する場合には前記ヘテロ原子はN原子に直接隣接しておらず、Z2は、好ましくは、R1およびR2が、互いに独立して、1以上のヘテロ原子を任意に含むC1−C40の炭化水素部分であるNR1R2である、金属錯体。 - Z1およびZ3は、2位において両方分枝または置換されている、請求項20または21に記載の金属錯体。
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