WO1995033776A1 - Nouveaux composes organometalliques, leurs procedes de preparation et procede de polymerisation d'hydrocarbures insatures a l'aide desdits composes organometalliques sous forme de catalyseurs, et nouveaux demi-produits et preparations de catalyseurs - Google Patents

Nouveaux composes organometalliques, leurs procedes de preparation et procede de polymerisation d'hydrocarbures insatures a l'aide desdits composes organometalliques sous forme de catalyseurs, et nouveaux demi-produits et preparations de catalyseurs Download PDF

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Publication number
WO1995033776A1
WO1995033776A1 PCT/NL1995/000202 NL9500202W WO9533776A1 WO 1995033776 A1 WO1995033776 A1 WO 1995033776A1 NL 9500202 W NL9500202 W NL 9500202W WO 9533776 A1 WO9533776 A1 WO 9533776A1
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WIPO (PCT)
Prior art keywords
group
formula
compound
compounds according
converted
Prior art date
Application number
PCT/NL1995/000202
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English (en)
Inventor
Michael Franz Lappert
Dimsheng Liu
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Specs And Biospecs B.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from NL9400919A external-priority patent/NL9400919A/nl
Priority claimed from NL9401515A external-priority patent/NL9401515A/nl
Application filed by Specs And Biospecs B.V. filed Critical Specs And Biospecs B.V.
Priority to AU25798/95A priority Critical patent/AU2579895A/en
Publication of WO1995033776A1 publication Critical patent/WO1995033776A1/fr

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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
    • 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 System
    • 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 System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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 System
    • C07F7/28—Titanium compounds
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • metallocenes There are numerous catalysts for the polymerization of alkenes.
  • the metallocenes have numerous advantages: they may be used for controlling the stereo- regularity and the distribution of the molecular weight while obtaining polymers which are "tailored" to certain applications, and they are soluble in hydrocarbons, whereby they form homogeneous catalytic systems.
  • the above compounds are suitable for use as catalysts for the polymerization (both homopolymerization and copolymeri- zation) of alkenes, for example etheen of propene.
  • the present novel cyclopentadienyl-free polymerization catalysts possess a usable and distinguishing catalytic activity and can be prepared in a very simple manner.
  • the compounds have the structure according to the general formula 1 of the formula sheet, and in particular according to formulas la, lb, or lc of the formula sheet, whereby the significance of the symbols used therein is as indicated in the claims.
  • the invention relates in particular to compounds according to formula 3a of the formula sheet, wherein Bu c represents a t . butyl group and R, may be a hydrogen atom or another substituent.
  • R represents a hydrogen atom of a p-methyl group are to be preferred thereby.
  • Another preferred compound is the one according to formula 4a of the formula sheet, wherein Bu " ' represents a t. butyl group.
  • the invention furthermore relates to methods for the poly- merization of unsaturated hydrocarbons, in particular ethene and propene, using the novel organo-metallic com ⁇ pounds according to the invention.
  • the invention relates to methods for the prepa- ration of the novel organo-metallic compounds, and also to the novel intermediate products produced during said process .
  • novel intermediate products have the structure according to formula 5a of the formula sheet, wherein the significance of R, R : and Q is as indicated before and wherein Y represents an alkali metal, preferably potassium.
  • the invention furthermore relates to catalytically active preparations, which contain the novel organo-metallic compounds according to the invention as the active consti ⁇ tuent, either in the form of a solution or bonded with a fixed carrier.
  • An advantage of the novel organo-metallic compounds accor ⁇ ding to the invention is that their catalytic action is better than that of the existing polymerization catalysts.
  • the invention provides organo-metal ⁇ lic compounds according to the formula (lb) , wherein Q represents -N-Si(CH 3 ) 3 or -C (H) -Si (CH 3 ) 3 ; R represents an alkylene group or an arylene group; R' represents a t.butyl group or a t.pentyl group; M represents Zr, Ti or Hf; and A represents a group that can be readily isolated.
  • Q is -N-Si (CH 3 ) 3 ;
  • R is an ethylene group or an o- phenylene group, which may or may not be substituted, whereby the possible substituent to the o-phenylene group is preferably present at location 3 or location 4;
  • R' is a t.butyl group;
  • M is Zr; and
  • A is a halogen atom.
  • the invention furthermore provides organo-metallic com- pounds according to formula (lc) of the formula sheet, wherein R 1 and R 5 are identical or different from each other and wherein each of said symbols represents a group C(C 1 -C 4 alkyl) 3 or Si ( C 1 -C 1 alkyl) 3 , wherein each of the alkyl groups may be substituted by one or more phenyl groups, or a group C-C 6 H 5 (C 1 -C 4 alkyl) 2 , a group C (C 6 H 5 ) 2 (C 1 -C 4 alkyl) or a group C(C ⁇ H 5 ) 3 , wherein C 6 H 5 is a phenyl group; R 2 repre ⁇ sents a tertiary alkyl group having its tertiary carbon atom bonded with the diketinimato system; R 3 represents a hydrogen atom or a C 1 -C 3 alkyl group; R 4 represents a phenyl group or
  • R : and R 5 are Si(CH 3 ) 3 or C(CH 3 ) 3 ;
  • R 2 is C(CH 3 ) 3 or C (CH 3 ) 2 C-,H 5 ;
  • R 3 is a hydrogen acorn;
  • R ** is C 6 H 5 (phenyl) or C 6 H 5 CH 3 -4 (a 4-tolyl group) ,- and
  • A is halogen.
  • R 1 and R 5 are both Si(CH 3 ) 3 ;
  • R 2 is C(CH 3 ) 3 ;
  • R 3 is hydrogen;
  • R 4 is C 6 H E ;
  • M is Zr; and
  • A is Cl .
  • Each of the above compounds can suitably function as a catalyst for the polymerization (both homopolymerization and copolymerization) of alkenes, for example ethene or propene.
  • PhCN (20.0 mmol) was added, by means of a syringe, to 5.7 g [Li/tmeda)] [CH(SiMe 3 ) C 6 H (19.93 mmol) in 30 ml. pentane at room temperature. The mixture was stirred for six hours and then filtrated, whereby a yellow solid was formed, namely [Li/tmeda) ] [CH(Ph) C (Ph)N(SiMe 3 ) ] . Yield 7.0 g (90%) .
  • P 6 [Zr ⁇ CH(C 6 H 5 Me- ⁇ )C(Bu c )N(SiMe 3 ) ⁇ ]
  • P 7 [Zr ⁇ CH(C 10 H 7 )C(Bu t )N(SiMe 3 ) ⁇ C1 3 ]
  • This compound was prepared in the manner described in an article by M.F. Lappert c.s., Inorg. Syth. , 1989, 26, 144.
  • the compound was converted with Bu c CN, providing [Li 2 (TMEDA) 2 ⁇ l .2-C 6 H 4 (CHCBu t NSi- (CH 3 ) 3 ) 2 ⁇ ] , which latter compound was in turn converted with potassium t.butoxide into the corresponding potassium deri ⁇ vative; reacting the potassium compound with ZrCl 4 resulted in the compound having the formula (2) , Zr[ ⁇ N(Si(CH 3 ) 3 )C(Bu t )CH ⁇ 2 C 6 H 4 -1.2]Cl 2 .
  • Zirconium(IV) chloride (0.37 g, 1.59 mmol) was added to a solution of the above-prepared potassium compound (0.86 g, 1.42 mmol) in toluene (approx. 25 ml) accompanied by stir ⁇ ring and chilling (-78°C) .
  • the mixture was slowly heated to room temperature, then heated at 70°C for 2 hours and furthermore stirred for another 12 hours.
  • the white preci ⁇ pitate was separated by filtration. Concentration of the filtrate resulted in pale yellow crystals of the final zirconium compound Zr ⁇ N(R) C (Bu c ) CH ⁇ 2 C 6 H 4 -1.2) Cl 2 (0.76 g, 93%) .
  • the molecular structure became apparent from the X- ray diffraction pattern of a single crystal, see table 5 and the structural formula (6b) below.
  • Ethene was polymerized, using the above-prepared zirconium compound in an amount of 15 mg and methyl aluminium oxane
  • the above Zr compound may be prepared by converting a compound according to formula (7) , wherein M' represents Li or K (D.S. Liu, D. Phil. Thesis, University of Hampshire) , with an equimolecular amount of C 6 H 5 CN. This reaction may be carried out in diethyl ether (Et 2 0) : [M ⁇ N(R)C(Bu')CHR ⁇ ] 2 + 2 P CN
  • the product obtained is converted into Et 2 0 with ZrCl 4 , thus obtaining the desired compound.
  • the desired compound may be obtained from [Zr ⁇ N(R)C(Bu c )CHR ⁇ Cl 3 ] , prepared from ZrCl 4 + 1/2 [K ⁇ N(R)C(Bu t )CHR ⁇ ] 2 (D.S. Liu, D. Phil. Thesis, University of Hampshire) and an equimolecular amount of C 6 H 5 CN.
  • the analogous hafnium compound was prepared according to a similar process.
  • the X-ray data of a single crystal of the title compound is included in table lc.
  • the structure may be represented by formula (9c) .
  • Hafniu (IV) chloride (1.12 g, 3.52 mmol) was added to a solution of [Li ⁇ N(R)C(Ph)C(H)C(Bu )NR ⁇ ] 2 (1.24 g, 1.76 mmol) in Et 2 0 (approx. 25 cm 3 ) at approx. -78°C while stirring took place. The mixture was slowly heated to approx. 25°C and stirred for another 12 hours. Volatile material was removed at 25°C/10 "2 torr. The residu was washed with hexane (approx. 10 cm 3 ) and then incorporated in CH 2 C1 2 by extrac ⁇ tion (approx. 40 cm 3 ) .
  • Tests with ethene at high pressure (40 bar) 100 ml tolue ⁇ ne, 5 ml of a 30% (wt. %) solution of MAO (methyl aluminium oxane; witco) in toluene acting as a co-catalyst and 5 ml of a 0.011 M solution of catalyst A or B in toluene were charged to an autoclave.
  • the autoclave was closed, heated to 50°C and pressurized with ethene of 40 bar, while quick stirring took place. The pressure was maintained at a constant 40 bar during the test.
  • Tests with propene at low pressure (1 bar) 20 ml toluene (distilled with Na) , 5 ml of a 30% (wt. %) solution of MAO in toluene and 5 ml of a 0.011 M solution of compound A or B in toluene were successively charged to a three-neck flask. The reaction mixture was stirred for 5 minutes at room temperature and then degased at a reduced pressure. Propene was added from a buffer vessel containing 21 of propene of 1 bar (1500 mol/mol A or B) , while quick stir ⁇ ring took place. The pressure reduction was monitored by means of a mercury manometer.
  • the polymerization process was terminated by the addition of a solution of 10% concen ⁇ trated HCl (aqueous) in methanol.
  • the polymer was collected and washed with HCl/methanol, water and methanol. After drying for 16 hours at 50°C the yield (in g) was determi ⁇ ned.

Abstract

L'invention concerne des composés organométalliques de formule (1; 1a, 1b, 1c) de la nomenclature, M représentant Zr, Ti ou Hf; Xn représentant un groupe pouvant être facilement isolé, n = 2 ou 3, par exemple un atome d'halogène; R1 et R5 représentant, de préférence, Si (CH¿3?)3 ou C(CH3)3; R2 représentant un groupe alkyle tertiaire tel que C(CH3)3; R?3¿ représentant un atome d'hydrogène ou un groupe alkyle inférieur; et R4 représentant un groupe phényle. Ces composés qui présentent une activité catalytique satisfaisante et sont simples à préparer, sont utiles pour la polymérisation d'alcènes tels que l'éthène ou le propène.
PCT/NL1995/000202 1994-06-07 1995-06-07 Nouveaux composes organometalliques, leurs procedes de preparation et procede de polymerisation d'hydrocarbures insatures a l'aide desdits composes organometalliques sous forme de catalyseurs, et nouveaux demi-produits et preparations de catalyseurs WO1995033776A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU25798/95A AU2579895A (en) 1994-06-07 1995-06-07 Novel organo-metallic compounds, methods for preparing same, and a method for the polymerization of unsaturated hydrocarbons using said organo-metallic compounds as catalysts, as well as novel semi-products and catalyst preparations

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
NL9400919 1994-06-07
NL9400919A NL9400919A (nl) 1994-06-07 1994-06-07 Nieuwe organometaalverbindingen en werkwijze voor het polymeriseren van alkenen onder toepassing van deze organonetaalverbindingen als katalysatoren.
NL9401515A NL9401515A (nl) 1994-09-19 1994-09-19 Nieuwe organometaalverbindingen en werkwijze voor het polymeriseren van alkenen onder toepassing van deze organometaalverbindingen als katalysatoren.
NL9401515 1994-09-19
NL9500085 1995-01-17
NL9500085 1995-01-17

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Publication Number Publication Date
WO1995033776A1 true WO1995033776A1 (fr) 1995-12-14

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997010248A1 (fr) * 1995-09-11 1997-03-20 Montell Technology Company B.V. Metallocenes de pentadienyle ouvert, precurseurs de ceux-ci et catalyseurs de polymerisation obtenus a partir de ceux-ci
WO1997035894A2 (fr) * 1996-03-27 1997-10-02 The Dow Chemical Company Allyle contenant des complexes metalliques et procede de polymerisation olefinique
EP0803520A1 (fr) * 1996-04-25 1997-10-29 Basf Aktiengesellschaft Catalyseurs de polymérisation contenant des ligands du type bèta-dicétiminate
WO1999041290A1 (fr) * 1998-02-12 1999-08-19 University Of Delaware Composes de catalyseur avec ligands anioniques beta-diiminate, et procedes de polymerisation d'olefines
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
US6180732B1 (en) 1993-09-24 2001-01-30 John A. Ewen Stereospecific metallocene catalysts with stereolocking α-cp substituents
US6265339B1 (en) 1996-07-04 2001-07-24 Basf Aktiengesellschaft Process for preparing carrier-borne transition metal catalysts
US6511936B1 (en) 1998-02-12 2003-01-28 University Of Delaware Catalyst compounds with β-diminate anionic ligands and processes for polymerizing olefins
US7612009B2 (en) 2003-02-21 2009-11-03 Dow Global Technologies, Inc. Process for homo-or copolymerization of conjugated olefines
CN103819588A (zh) * 2014-02-25 2014-05-28 山西大学 一种氮杂戊二烯金属配合物催化剂及其合成方法和应用

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Publication number Priority date Publication date Assignee Title
EP0418044A2 (fr) * 1989-09-14 1991-03-20 The Dow Chemical Company Composés complexes de métal, leur procédé de préparation et leur procédé d'utilisation
WO1992005203A1 (fr) * 1990-09-13 1992-04-02 Exxon Chemical Patents Inc. Catalsyeurs a support composes d'un metal de transition associe a un monocyclopentadienyle, employes pour polymeriser des olefines
WO1992012162A1 (fr) * 1990-12-27 1992-07-23 Exxon Chemical Patents Inc. Compose amido de metal de transition et systeme catalytique de production de polypropylene isotactique
DE4202889A1 (de) * 1992-02-01 1993-08-05 Solvay Deutschland Verfahren zur abscheidung von ein metall der ersten uebergangsmetallreihe oder aluminium enthaltenden schichten
DE4218199A1 (de) * 1992-06-03 1993-12-16 Basf Ag Substituierte Zirkona-aza-alkene und daraus hergestellte Diaminpolyene und Dioxopolyene
EP0590486A2 (fr) * 1992-09-24 1994-04-06 Idemitsu Kosan Company Limited Catalyseurs de polymérisation et procédé de production de polymères
EP0617052A2 (fr) * 1993-03-23 1994-09-28 Asahi Kasei Kogyo Kabushiki Kaisha Catalyseur de polymérisation d'oléfines possédant un ligand multidenté

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EP0418044A2 (fr) * 1989-09-14 1991-03-20 The Dow Chemical Company Composés complexes de métal, leur procédé de préparation et leur procédé d'utilisation
WO1992005203A1 (fr) * 1990-09-13 1992-04-02 Exxon Chemical Patents Inc. Catalsyeurs a support composes d'un metal de transition associe a un monocyclopentadienyle, employes pour polymeriser des olefines
WO1992012162A1 (fr) * 1990-12-27 1992-07-23 Exxon Chemical Patents Inc. Compose amido de metal de transition et systeme catalytique de production de polypropylene isotactique
DE4202889A1 (de) * 1992-02-01 1993-08-05 Solvay Deutschland Verfahren zur abscheidung von ein metall der ersten uebergangsmetallreihe oder aluminium enthaltenden schichten
DE4218199A1 (de) * 1992-06-03 1993-12-16 Basf Ag Substituierte Zirkona-aza-alkene und daraus hergestellte Diaminpolyene und Dioxopolyene
EP0590486A2 (fr) * 1992-09-24 1994-04-06 Idemitsu Kosan Company Limited Catalyseurs de polymérisation et procédé de production de polymères
EP0617052A2 (fr) * 1993-03-23 1994-09-28 Asahi Kasei Kogyo Kabushiki Kaisha Catalyseur de polymérisation d'oléfines possédant un ligand multidenté

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RESCONI L ET AL: "1-OLEFIN POLYMERIZATION AT BIS(PENTAMETHYLCYCLOPENTADIENYL)ZIRCONIUM AND -HAFNIUM CENTERS: ENANTIOFACE SELECTIVITY 000324868", MACROMOLECULES, vol. 25, no. 25, pages 6814 - 6817, XP000324868 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6180732B1 (en) 1993-09-24 2001-01-30 John A. Ewen Stereospecific metallocene catalysts with stereolocking α-cp substituents
WO1997010248A1 (fr) * 1995-09-11 1997-03-20 Montell Technology Company B.V. Metallocenes de pentadienyle ouvert, precurseurs de ceux-ci et catalyseurs de polymerisation obtenus a partir de ceux-ci
US6069237A (en) * 1995-09-11 2000-05-30 Montell Technology Company Bv Open-pentadienyl metallocenen ligands, polymerization catalysts/catalyst precursors and polymers therefrom
US5892076A (en) * 1996-03-27 1999-04-06 The Dow Chemical Company Allyl containing metal complexes and olefin polymerization process
WO1997035894A3 (fr) * 1996-03-27 1997-11-27 Dow Chemical Co Allyle contenant des complexes metalliques et procede de polymerisation olefinique
WO1997035894A2 (fr) * 1996-03-27 1997-10-02 The Dow Chemical Company Allyle contenant des complexes metalliques et procede de polymerisation olefinique
US5994255A (en) * 1996-03-27 1999-11-30 The Dow Chemical Company Allyl containing metal complexes and olefin polymerization process
US6034258A (en) * 1996-04-25 2000-03-07 Basf Aktiengesellschaft Polymerization catalysts containing β-diketiminate ligands
EP0803520A1 (fr) * 1996-04-25 1997-10-29 Basf Aktiengesellschaft Catalyseurs de polymérisation contenant des ligands du type bèta-dicétiminate
US6265339B1 (en) 1996-07-04 2001-07-24 Basf Aktiengesellschaft Process for preparing carrier-borne transition metal catalysts
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
WO1999041290A1 (fr) * 1998-02-12 1999-08-19 University Of Delaware Composes de catalyseur avec ligands anioniques beta-diiminate, et procedes de polymerisation d'olefines
US6511936B1 (en) 1998-02-12 2003-01-28 University Of Delaware Catalyst compounds with β-diminate anionic ligands and processes for polymerizing olefins
US6821921B2 (en) 1998-02-12 2004-11-23 Chevron Chemical Co. Catalyst compounds with β-diiminate anionic ligands and processes for polymerizing olefins
US7612009B2 (en) 2003-02-21 2009-11-03 Dow Global Technologies, Inc. Process for homo-or copolymerization of conjugated olefines
US8153545B2 (en) 2003-02-21 2012-04-10 Styron Europe Gmbh Process for homo—or copolymerization of conjugated olefins
CN103819588A (zh) * 2014-02-25 2014-05-28 山西大学 一种氮杂戊二烯金属配合物催化剂及其合成方法和应用
CN103819588B (zh) * 2014-02-25 2016-02-10 山西大学 一种氮杂戊二烯金属配合物催化剂及其合成方法和应用

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