WO2013168626A1 - ポリオレフィン類合成用触媒 - Google Patents
ポリオレフィン類合成用触媒 Download PDFInfo
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- WO2013168626A1 WO2013168626A1 PCT/JP2013/062538 JP2013062538W WO2013168626A1 WO 2013168626 A1 WO2013168626 A1 WO 2013168626A1 JP 2013062538 W JP2013062538 W JP 2013062538W WO 2013168626 A1 WO2013168626 A1 WO 2013168626A1
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 70
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
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- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 87
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- -1 cationic organometallic compound Chemical class 0.000 claims description 55
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- 238000000034 method Methods 0.000 claims description 33
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 26
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- 229910052763 palladium Inorganic materials 0.000 claims description 15
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- 229940066769 systemic antihistamines substituted alkylamines Drugs 0.000 claims description 3
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- FXJNIEVFINNQGJ-UHFFFAOYSA-N C(C)(C)(C)C1=C(C=CC=C1)[PH2]=O Chemical compound C(C)(C)(C)C1=C(C=CC=C1)[PH2]=O FXJNIEVFINNQGJ-UHFFFAOYSA-N 0.000 description 10
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- XTDXBZMKUMZNMH-UHFFFAOYSA-N dec-1-en-3-one Chemical compound CCCCCCCC(=O)C=C XTDXBZMKUMZNMH-UHFFFAOYSA-N 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
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- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XOJNEFQLMRCOMS-UHFFFAOYSA-N ditert-butyl(phenyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1 XOJNEFQLMRCOMS-UHFFFAOYSA-N 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
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- 229940006461 iodide ion Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IBRGPZKSIDNEFH-UHFFFAOYSA-N nonadec-1-en-3-one Chemical compound CCCCCCCCCCCCCCCCC(=O)C=C IBRGPZKSIDNEFH-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- IVUSOGDLVUEEQB-UHFFFAOYSA-N oxido(dioxo)-$l^{5}-stibane Chemical compound [O-][Sb](=O)=O IVUSOGDLVUEEQB-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YFURFLWAOAZPGU-UHFFFAOYSA-N pentadec-1-en-3-one Chemical compound CCCCCCCCCCCCC(=O)C=C YFURFLWAOAZPGU-UHFFFAOYSA-N 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000011403 purification operation Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- DPZNOMCNRMUKPS-UHFFFAOYSA-N resorcinol dimethyl ether Natural products COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- ZEWQUBUPAILYHI-UHFFFAOYSA-N trifluoperazine Chemical compound C1CN(C)CCN1CCCN1C2=CC(C(F)(F)F)=CC=C2SC2=CC=CC=C21 ZEWQUBUPAILYHI-UHFFFAOYSA-N 0.000 description 1
- 229960002324 trifluoperazine Drugs 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 description 1
- IIKBAAIJWTZALX-UHFFFAOYSA-N tris[3,5-bis(trifluoromethyl)phenyl] borate Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(OB(OC=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)OC=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)=C1 IIKBAAIJWTZALX-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- 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
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
- C07F9/5308—Acyclic saturated phosphine oxides or thioxides substituted by B, Si, P or a metal
- C07F9/5312—Acyclic saturated phosphine oxides or thioxides substituted by B, Si, P or a metal substituted by a phosphorus atom
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
-
- 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
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- 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
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
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- 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
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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
- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
Definitions
- the present invention uses a novel organometallic compound, a production method thereof, a catalyst for synthesizing polyolefins containing the compound (a catalyst composition for vinyl monomer polymerization and copolymerization of a nonpolar olefin and a polar olefin), and the catalyst.
- the present invention relates to a method for producing a (co) polymer.
- Polyolefins typified by polyethylene and polypropylene are used for general purposes but are not suitable for all applications.
- Polyolefins are essentially non-polar, which limits their usefulness due to poor physical properties such as adhesion, dye persistence, printability and affinity.
- it is known that such properties can be remarkably improved in functional polyolefins obtained by incorporating a small amount of polar functional groups into polyolefins.
- Non-Patent Documents 1 and 2, etc. the most direct method is to copolymerize an olefin monomer with an industrially useful polar vinyl monomer as shown by the following formula.
- Coordination insertion polymerization Coordination addition polymerization
- olefins and polar vinyl monomers with transition metal catalysts have been proposed as a powerful synthesis method for functional polyolefins having a defined polymer structure, molecular weight distribution, and comonomer incorporation. It was.
- the late transition metal complex that catalyzes the coordinate insertion polymerization of olefins and polar vinyl monomers the most successful to date is the one coordinated with ⁇ -diimine or phosphine-sulfonate ion (Patent Document 1).
- Highly linear polymer microstructures can generally be obtained with palladium and nickel catalysts coordinated with phosphine-sulfonate ions.
- palladium and nickel catalysts coordinated with ⁇ -diimine catalyze the formation of highly branched polymers.
- those coordinated with phosphine-sulfonate ions are more polar vinyl monomers such as vinyl acetate, acrylonitrile, vinyl chloride and vinyl ether than catalysts coordinated with ⁇ -diimine. It has been reported that it exhibits very high activity in copolymerization with (Non-patent Documents 5 and 6).
- transition metal complexes in which phosphine-sulfonate ions are coordinated have not yet been put into practical use.
- the method of copolymerizing ethylene and methyl acrylate using the nickel complex which has an imino amide ligand is proposed (patent document 2), this method has not reached practical use, either.
- An object of the present invention is to provide a polyolefin polymerization catalyst composition containing a novel organometallic compound, which has higher activity with respect to a conventional transition metal complex coordinated with a phosphine-sulfonate ion.
- R 1a R 1b , R 2a and R 2b may be the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, 3 to Represents a substituted or unsubstituted cycloalkyl group having 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group, wherein R 1a and R 1b , R 2a and R 2b are bonded to form a ring;
- a 1 may be an arylene group, a monocyclic heteroarylene group, a divalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, or
- R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 2 An alkenyl group having 10 to 10 carbon atoms, or A 2 (A 2 is an arylene group, monocyclic heteroarylene group, monocyclic cycloalkylene group, monocyclic cycloalkenylene group, monocyclic heterocycloalkylene group, Represents a monocyclic heterocycloalkenylene group, a heterocyclic ring or a C2-C4 alkylene group.), R 4 represents a neutral electron-donating ligand, R 3 and R 4 may be crosslinked, and when R 3 and R 4 are crosslinked, L is a single bond or a divalent group selected from an alkylene group, a haloalkylene group, an alkenylene group, and an alkynylene group
- the ligand R 4 is (I) selected from pyridine, substituted pyridines, nitrile compounds, ammonia, alkylamines, substituted alkylamines, arylamines or substituted arylamines, or (ii) formula (1) Wherein W represents C or S, Z is selected from O, S, NH or NR a (R a represents an alkyl group or an aryl group), and Y may or may not be present.
- R 5 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, —OR 3.
- R 1a , R 1b , R 2a and R 2b each independently represents a branched alkyl group having 3 to 6 carbon atoms.
- R 1a and R 1b are both an isopropyl group or a t-butyl group.
- R 2a and R 2b are both t-butyl groups.
- a 1 represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted methylene group.
- Formula (V) (In the formula, M, R 1a , R 1b , R 2a , R 2b , A 2 , R 5 , X ⁇ represent the same meaning as described in the preceding paragraphs 1 to 3, and R 11 does not exist or is on the benzene ring.
- Organometallic compounds [15] The organometallic compound as described in 14 above, wherein A 2 is a substituted or unsubstituted phenylene group or naphthylene group. [16] Formula (VI) (Wherein, M, R 1a , R 1b , R 2a , R 2b , R 5 , R 11 , X ⁇ represent the same meanings as described in the preceding paragraphs 1 to 3 and 14) The organometallic compound described.
- X ⁇ is selected from SbF 6 ⁇ , BPh 4 ⁇ , BArF 4 ⁇ , BF 4 ⁇ and PF 6 ⁇ .
- M is palladium.
- a vinyl monomer polymerization catalyst composition comprising the organometallic compound as described in any one of 1 to 21 above.
- the polar olefin is represented by formula (VII) Wherein R 13 represents a hydrogen atom or a methyl group, and R 14 represents —COOR 15 , —CN, —OCOR 15 , —OR 15 , —CH 2 —OCOR 15 , —CH 2 OH, —CH 2 —N (R 16 ) 2 or —CH 2 —Hal (R 15 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 18 carbon atoms, R 16 represents a hydrogen atom, 1 to 5 Represents an alkyl group having 5 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkoxycarbonyl group, and Hal represents a halogen atom.) 25.
- R 14 is —CH 2 —OCOR 15 , —CH 2 OH, —CH 2 —N (R 16 ) 2, or —CH 2 —Hal (R 15 , R 16 , Hal is as defined in the above item 25 26.
- R 1a , R 1b , R 2a and R 2b may be the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, 3 Represents a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted biphenyl group or substituted or unsubstituted aryl group having ⁇ 14 carbon atoms, R 1a and R 1b , R 2a and R 2b are bonded
- a 1 may form a ring structure, and A 1 is an arylene group, a monocyclic heteroarylene group, a heterocyclic ring, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, Represents a alkenylene group having 2 to 8 carbon atoms or a cycloalkenylene group having 3 to 10 carbon atoms.
- BPMO Bisphosphine monooxide represented by the formula (3)
- M represents an element belonging to Group 10 of the periodic table
- a 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, or a monocyclic heterocyclo group.
- R 5 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms
- OR c R c is An alkyl group or an aryl group
- NR d 2 wherein R d represents an alkyl group or an aryl group
- Xb represents a halogen
- the catalyst composition containing the novel organometallic compound of the present invention has high activity in coordination insertion polymerization of ethylene and a polar vinyl monomer.
- a highly linear polymer can be obtained, and further, a copolymer in which polar monomers are randomly distributed in the polymer chain can be obtained.
- the catalyst composition containing the novel organometallic compound of the present invention is extremely useful because it enables the production of industrially useful functional polyolefins.
- FIG. 13 C-NMR chart of the product of Example 5 FIG. 13 C-NMR chart of the product of Example 10.
- FIG. 13 C-NMR chart of the product of Example 18. FIG.
- the organometallic compound of the present invention is a compound obtained by forming a complex with a central metal M composed of a group 10 element of the periodic table as a ligand of bisphosphine monooxide (BPMO) represented by the formula (I).
- BPMO bisphosphine monooxide
- R 1a , R 1b , R 2a and R 2b may be the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms.
- R 1a and R 1b , R 2a and R 2b may combine to form a ring structure.
- a 1 represents an arylene group, a monocyclic heteroarylene group, a divalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or 2 to 8 carbon atoms. Or an alkenylene group having 3 to 10 carbon atoms.
- Examples of A 1 include orthophenylene group, 1,2-naphthylene group, 1,8-naphthylene group, 1,2-cyclohexylene group, 1,2-cyclopentylene group, 1,2-vinylene group, , 2-cyclohexenylene group, 1,2-cyclopentenylene group, methylene group, unsubstituted or alkyl group, alkoxy group, amino group, ethylene group which may be substituted by ester group, and the like.
- an orthophenylene group, a 1,2-naphthylene group, a 1,8-naphthylene group, or a methylene group is preferable, and an orthophenylene group and a methylene group are more preferable.
- One embodiment of the present invention is an organometallic compound represented by the formula (II).
- R 3 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or represents a divalent group represented by A 2
- a 2 is an arylene group, a monocyclic heteroarylene Represents a group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, a monocyclic heterocycloalkenylene group, a heterocyclic ring or a C2-C4 alkylene group.
- R 4 represents a neutral electron donating ligand.
- Neutral electron donating ligands include pyridine, substituted pyridine, quinoline, substituted quinoline, nitrile compound, ammonia, alkylamine, substituted alkylamine, arylamine, substituted arylamine, sulfoxide, alkylphosphine, substituted alkylphosphine, Examples include aryl phosphine, substituted aryl phosphine, alkyl phosphite, substituted alkyl phosphite, aryl phosphite, substituted aryl phosphite, aliphatic ether, substituted aliphatic ether, cyclic ether, and substituted cyclic ether.
- pyridine 2,6-dimethylpyridine, 4- (N, N-dimethylamino) pyridine (DMAP); quinoline, 2-methylquinoline; trialkylamine having 1 to 10 carbon atoms, N, N , N ′, N′-tetramethylethylenediamine (TMEDA); dialkylamine aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline; acetonitrile, benzonitrile; dimethyl sulfoxide (DMSO); trimethylphosphine, triisopropylphosphine, Examples include tributylphosphine, tri (t-butyl) phosphine, triphenylphosphine, tris (o-tolyl) phosphine, trifurylphosphine; diethyl ether; tetrahydrofuran, 1,4-dioxane; 1,2-dimethoxyethane.
- DMAP N, N-d
- R 4 is selected from pyridine, substituted pyridines, nitrile compounds, ammonia, alkylamines, substituted alkylamines, arylamines or substituted arylamines, preferably pyridine or substituted pyridines.
- the ligand R 4 has the formula (1) Indicated by In the formula (1), W represents a carbon atom (C) or a sulfur atom (S), Z represents an oxygen atom (O), S, NH or NR a (R a represents an alkyl group or an aryl group). And Y is selected from O, S, NH, or NR b (R b represents an alkyl or aryl group), and R 5 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. OR c (R c represents an alkyl group or an aryl group), or NR d 2 (R d represents an alkyl group or an aryl group).
- R 3 and R 4 may be cross-linked.
- L is selected from a single bond or an alkylene group, a haloalkylene group, an alkenylene group, and an alkynylene group.
- a divalent group is represented and R 3 and R 4 are not crosslinked, L does not exist.
- R 4 may not be present.
- the organometallic compound represented by the formula (II) is a tricoordinate organometallic compound represented by the formula (IIa).
- X ⁇ represents a counter ion of the cationic organometallic complex.
- the counter ion represented by X ⁇ may be any monovalent anion.
- X ⁇ may be a polyvalent anion as long as the number of charges per atom of the central metal (M) is monovalent.
- X ⁇ is preferably SbF 6 ⁇ , BPh 4 ⁇ , BArF 4 ⁇ , BF 4 ⁇ or PF 6 ⁇ .
- organometallic compounds represented by the formula (II) of the present invention one preferred embodiment is an organometallic compound represented by the formula (III).
- R 6 represents an alkyl group, alkenyl group or aryl group having 1 to 10 carbon atoms.
- R 7 , R 8 and R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
- a 1 is preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted methylene group.
- organometallic compounds represented by the formula (III) of the present invention one preferred embodiment is an organometallic compound represented by the following formula (IIIa).
- M, R 1a , R 1b , R 2a , R 2b , R 7 , R 8 , R 9 and X ⁇ represent the same meaning as described above.
- R 10 represents 1 to 4 alkyl groups having 1 to 10 carbon atoms that are not present or substituted with any substitutable hydrogen in the benzene ring, and two or more R 10 are the same It may or may not be.
- the organometallic compound represented by the formula (IIIc) is also one of the preferred embodiments of the organometallic compound represented by the formula (III).
- R 1a , R 1b , R 2a , R 2b , R 7 , R 8 , R 9 and X ⁇ represent the same meaning as described above.
- R 13a and R 13b each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and may be the same or different.
- R 13a and R 13b may be bonded to form a crosslinked structure.
- R 1a , R 1b , R 2a , and R 2b are each independently a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms.
- the branched alkyl group having 3 to 5 carbon atoms is more preferable.
- R 1a , R 1b , R 2a and R 2b are particularly preferably each independently an isopropyl group or a t-butyl group. Further, it is particularly preferable that R 1a and R 1b are isopropyl groups, and R 2a and R 2b are t-butyl groups.
- both R 13a and R 13b in the formula (IIIc) are a hydrogen atom or a methyl group. More preferably.
- M is an element belonging to Group 10 of the periodic table, preferably nickel or palladium, and more preferably palladium.
- organometallic compounds represented by the formula (II) of the present invention another preferred embodiment is an organometallic compound represented by the formula (IV).
- M, R 1a , R 1b , R 2a , R 2b , A 1 and X ⁇ represent the same meaning as described above.
- the portion represented by the formula (1) forms a closed ring structure in the molecule.
- the complex was stabilized by using a strong Lewis base such as pyridine, but this prevented the vinyl monomer from being inserted into and coordinated with the metal. Tended to be.
- a weak Lewis base such as pyridine
- the vinyl monomer can be easily inserted and coordinated with the metal, and a complex is formed by forming a closed ring structure in the molecule. Can be stabilized.
- W represents C or S
- Z is selected from O, S, NH or NR a
- Y is , If present, selected from O, S, NH or NR b (R b represents an alkyl group or an aryl group)
- R 5 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms
- OR c R c represents an alkyl group or an aryl group
- NR d 2 or SR d R d represents an alkyl group or an aryl group
- M, R 1a , R 1b , R 2a , R 2b , R 5 , A 1 , A 2 , X ⁇ represent the same meaning as described above.
- a 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, a monocyclic heterocycloalkenylene group, a heterocyclic ring, or C2 Is a C4 alkylene group.
- orthophenylene group 1,2-naphthylene group, 1,8-naphthylene group, 1,2-cyclohexylene group, 1,2-cyclopentylene group, unsubstituted or alkyl group, alkoxy group,
- An ethylene group (—CH 2 —CH 2 —), a propylene group (—CH 2 —CH 2 —CH 2 —), a butylene group (—CH 2 —CH 2 —CH 2 ), which may be substituted by an amino group or an ester group -CH 2- ) and the like.
- a 1 represents an arylene group, a monocyclic heteroarylene group, a heterocyclic ring, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, 2 to 8
- An alkenylene group having a carbon atom or a cycloalkenylene group having 3 to 10 carbon atoms, which is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted methylene group Is preferred.
- organometallic compounds represented by the formula (IV) of the present invention one preferred embodiment is an organometallic compound represented by the formula (V).
- M, R 1a , R 1b , R 2a , R 2b , A 2 , R 5 and X ⁇ represent the same meaning as described above.
- R 11 is absent or represents an alkyl group having 1 to 10 carbon atoms that is substituted with any substitutable hydrogen in the benzene ring, and two or more R 11 are the same or different. May be.
- a 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, or a monocyclic heterocycloalkenylene.
- Group, heterocycle or C2-C4 alkylene group preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group.
- organometallic compound represented by the formula (IV) of the present invention another preferred embodiment is an organometallic compound represented by the following formula (VI).
- M, R 1a , R 1b , R 2a , R 2b , R 5 , R 11 and X ⁇ represent the same meaning as described above.
- R 12 represents an alkyl group having 1 to 10 carbon atoms that is not present or substituted with any substitutable hydrogen in the benzene ring, and two or more R 12 are the same or different. May be.
- R 1a , R 1b , R 2a and R 2b are each independently preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A branched alkyl group of 3 to 5 is more preferable.
- R 1a , R 1b , R 2a , and R 2b are particularly preferably each independently an isopropyl group or a t-butyl group. Furthermore, it is particularly preferable that R 1a and R 1b are isopropyl groups, and R 2a and R 2b are t-butyl groups.
- M is an element belonging to Group 10 of the periodic table, preferably nickel or palladium, and more preferably palladium.
- An organometallic compound in which A 1 is phenylene, which is an example of the organometallic compound represented by the formula (III) of the present invention, can be synthesized by the following scheme 1, for example.
- organometallic compounds represented by the formulas (II) to (VI) of the present invention are shown below.
- Specific examples of organometallic compounds represented by the following formula (IIIb) are shown in Table I when R 10 is not present in the formula (IIIa) (when the benzene ring has no substituent as R 10 ).
- H is a hydrogen atom
- Me is a methyl group
- Et is an ethyl group
- n-Pr is an n-propyl group
- i-Pr is an isopropyl group
- tert-Bu is a t-butyl group
- NeoPen is a neopentyl group
- CyHex Represents a cyclohexyl group
- CyPen represents a cyclopentyl group
- 1-Ada represents a 1-adamantyl group
- Biph represents a 2 ′-[2,6-bis (dimethoxy)] biphenyl group.
- HIPT represents a group represented by the following formula.
- the organometallic compounds represented by the formulas (II) to (VI) of the present invention can be suitably used as a polymerization catalyst for vinyl monomers.
- the catalyst composition containing the organometallic compound represented by the formulas (II) to (VI) of the present invention can be used for homopolymerization of nonpolar olefins, and for copolymerization of nonpolar olefins and polar olefins. It can also be used as a catalyst.
- organometallic compounds represented by the formulas (II) to (VI) of the present invention can be used as they are for the polymerization as the catalyst composition as they are without being isolated.
- the catalyst composition of the present invention can be used for homopolymerization of nonpolar olefins.
- Nonpolar olefins include, for example, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1,5-hexadiene, 1,7-octadiene, It is selected from ⁇ -olefins such as cyclopentadiene and norbornadiene, and combinations thereof.
- a suitable non-polar olefin may be ethylene.
- the catalyst composition of the present invention can be used for the copolymerization of the nonpolar olefin and the polar olefin.
- Polar olefins that can be used are, for example, vinyl formate, vinyl acetate, vinyl n-propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl 2-ethylhexanoate, vinyl benzoate, isopropenyl acetate
- Vinyl esters such as vinyl chloride; methyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, phenyl vinyl ether; methyl acrylate, ethyl acrylate, acrylic acid acrylic esters such as n-propyl, n-butyl acrylate, dodecyl acrylate, phenyl acryl
- the polar olefin may be an allyl compound containing a polar group.
- allyl compounds containing polar groups include allyl acetate, allyl trifluoroacetate, allyl alcohol, allyl methyl ether, allyl ethyl ether, allyl n-propyl ether, allyl n-butyl ether, allyl t-butyl ether, allyl phenyl ether.
- the polar olefin may be a vinyl ketone monomer.
- vinyl ketones include 1-pentadecene-3-one, 1-hepten-3-one, 1-decene-3-one, 3-buten-2-one, 1-nonadecene-3-one, and 1-octene-3.
- -One 1-hepten-3-one, 1-hexen-3-one, 1-penten-3-one, and 1-phenyl-2-propen-1-one.
- the polar olefin may be an N-vinyl monomer.
- N-vinyl monomers N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide; N-vinylacetamide; N-vinylphthalimide; N-methylvinylacetamide; N-vinylcaprolactam; 5-ethyl-5-methyl- May be selected from 3-vinylhydantoin; N-vinylpyrrolidone; 5-methyl-5-phenyl-3-vinylhydantoin; N-vinylcarbazole; N, N-dimethylacrylamide; and 5-pentamethylene-3-vinylhydantoin .
- the polar olefin may be a polar norbornene-type monomer, vinylphosphonic acid, or an ester thereof.
- the polar olefin in the present invention is vinyl acetate, vinyl benzoate, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, allyl acetate, allyl trifluoroacetate, allyl alcohol, allyl methyl ether, allyl ethyl ether, allyl n.
- the method for producing a copolymer of a nonpolar olefin and a polar olefin of the present invention can be carried out at a reaction temperature of 30 ° C. or higher and 150 ° C. or lower.
- the pressure of the polymerization varies according to the catalyst component activity and the selected non-polar and polar olefins. Typically gaseous monomers such as ethylene require high pressure.
- the polymerization pressure is 0.50 atm or more and 200 atm or less.
- the molar ratio of the polar olefin monomer of the present invention to the organometallic complex is 20: 1 to 500,000: 1.
- the molar ratio of the non-polar olefin monomer to the organometallic complex of the present invention is 5000000: 1 or more, such as 6000000: 1 or less, 8000000: 1 or less, Or even more.
- the amount of the diluent is 0.0 or more and 10,000 or less when expressed as the volume (ml) of the diluent per millimole of the organometallic complex of the present invention.
- the organometallic compound of the present invention can be supported on a carrier and used for polymerization.
- the carrier in this case is not particularly limited, and examples thereof include inorganic carriers such as silica gel and alumina, and organic carriers such as polystyrene, polyethylene, and polypropylene.
- examples of the method for supporting a metal complex include a physical adsorption method in which a carrier is impregnated with a solution of the metal complex and drying, and a method in which a metal complex and a carrier are chemically bonded and supported.
- the polymerization method is not particularly limited, and polymerization can be performed by a generally used method. That is, process methods such as a solution polymerization method, a suspension polymerization method, and a gas phase polymerization method are possible, but a solution polymerization method and a suspension polymerization method are particularly preferable.
- the polymerization mode can be a batch mode or a continuous mode. Further, it can be carried out by single-stage polymerization or multi-stage polymerization.
- the polymerization time can be appropriately adjusted depending on the process mode, polymerization activity, etc., and can be as short as several minutes or as long as several thousand hours.
- the atmosphere in the polymerization system is preferably filled with an inert gas such as nitrogen or argon other than the polymerization monomer so that air, oxygen, moisture, etc. are not mixed in order to prevent a decrease in the activity of the catalyst.
- an inert solvent in addition to the polymerization monomer.
- the inert solvent is not particularly limited, but is an aliphatic hydrocarbon such as pentane, hexane, or heptane, an alicyclic hydrocarbon such as cyclopentane, cyclohexane, or cycloheptane, an aromatic hydrocarbon such as benzene, toluene, or xylene, or chloroform.
- Halogenated aliphatic hydrocarbons such as methylene chloride, carbon tetrachloride, dichloroethane and tetrachloroethane, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, aliphatic esters such as methyl acetate and ethyl acetate, benzoic acid And aromatic esters such as methyl and ethyl benzoate.
- the product (co) polymer is post-treated by a known operation and treatment method (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.) and is simply Be released.
- a known operation and treatment method for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.
- the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
- the measuring method used for the synthesis example, the Example, and the comparative example is as follows.
- HRMS High-resolution mass spectrometry
- Synthesis Example 2 Synthesis of Compound 2 ([Methylpalladium (1-diphenylphosphino-2-di (t-butyl) phosphinylbenzene) (2,6-lutidine)] [hexafluoroantimonate]) as free BPMO
- Compound 2 was obtained by the same procedure as Compound 1 except that o- (Ph 2 P) C 6 H 4 (P (O) t-Bu 2 ) was used. The yield was 57%.
- Synthesis Example 4 Synthesis of Compound 4 ([Methylpalladium (1-diisopropylphosphino-2-di (t-butyl) phosphinylbenzene) (2,6-lutidine)] [hexafluoroantimonate]) as free BPMO
- Compound 4 was obtained by the same procedure as Compound 1 except that o- (i-Pr 2 P) C 6 H 4 (P (O) t-Bu 2 ) was used. The yield was 72%.
- Compound A (acetanilide palladium chloride dimer) was synthesized by the method described in the literature (Chem. Eur. J. 2010, 16, 4010-4017).
- reaction solution obtained by reacting the solution with n-butyllithium (1.64 M pentane solution, 1.3 ml, 2.1 mmol) was added at ⁇ 78 ° C. and stirred for 30 minutes. After slowly warming to room temperature, the mixture was stirred at room temperature for 1 hour. The reaction was stopped with water, the reaction mixture was concentrated under reduced pressure, the residue was dissolved in methylene chloride, and the solution was filtered through celite. After the solvent was distilled off, purification operation was performed by silica gel column chromatography using methylene chloride / methanol (30: 1) as a developing solvent and recrystallization from THF / hexane to obtain 0.30 g of compound 9a.
- Synthesis Example 11 Synthesis of Compound 11 (Chloromethylpalladium [1-bis (2-methylphenyl) phosphino-2-di (t-butyl) phosphinylbenzene])
- Compound 11 was synthesized. That is, a solution of compound 11a (0.10 g, 0.22 mmol) synthesized from compound 9a and (cod) PdMeCl (0.064 g, 0.24 mmol) in methylene chloride (2 ml) was added at room temperature for 1 hour under an argon atmosphere. Stir. The reaction solution was filtered through celite (dry diatomaceous earth), and the filtrate was concentrated under reduced pressure. The residue was reprecipitated from methylene chloride and diethyl ether to obtain 0.10 g of Compound 11. The yield was 74%.
- the reaction mixture was filtered through celite (dry diatomaceous earth), tetrakis (3,5-bis (trifluoromethyl) phenylborate sodium (0.15 g, 0.18 mmol) was added to the filtrate, and the mixture was stirred again at room temperature.
- the liquid was filtered through Celite (dry diatomaceous earth), and then the solvent of the filtrate was distilled off to obtain 0.23 g of Compound 14. The yield was 96%.
- Synthesis Example 15 Synthesis of Compound 15 (Chloromethylpalladium [1-bis (2,4-dimethoxyphenyl) phosphino-2-di (t-butyl) phosphinylbenzene]) In the same manner as in Synthesis Examples 9 and 11 Compound 15 was synthesized.
- Synthesis Example 16 Compound 16 ([methylpalladium (1-bis (2,4-dimethoxyphenyl) phosphino-2-di (t-butyl) phosphinylbenzene) (2,6-lutidine)]] [tetrakis (3 Synthesis of 5-bis (trifluoromethyl) phenylborate]) Compound 16 was synthesized in the same manner as in Synthesis Examples 10 and 12.
- Example 10 Copolymerization of ethylene and vinyl acetate
- Compound 4, toluene, ethylene (3 MPa) and vinyl acetate were added in the amounts shown in Table 2, and the polymerization reaction was carried out at the temperatures and times shown in the same table.
- a 13 C-NMR chart of the product of Example 10 is shown in FIG.
- Example 11 The catalyst was changed to Compound 6, and the polymerization reaction was performed under the conditions described in Table 2 in the same procedure as in Example 10.
- Example 12 In a stainless steel oclave, Compound 4, toluene, ethylene (3 MPa) and allyl acetate were added in the amounts shown in Table 2, and the polymerization reaction was carried out at the temperatures and times shown in the same table. A 13 C-NMR chart of the product of Example 12 is shown in FIG.
- Example 13 The catalyst was changed to Compound 6, and the polymerization reaction was carried out under the conditions described in Table 2 in the same procedure as in Example 12.
- Example 14 Copolymerization of ethylene and allyl chloride
- Compound 4, toluene, ethylene (3 MPa) and allyl chloride were charged in the amounts shown in Table 2 into a stainless steel oclave, and a polymerization reaction was carried out at the temperatures and times shown in the same table.
- the 13 C-NMR chart of the product of Example 14 is shown in FIG.
- Example 15 The catalyst was changed to Compound 6, and the polymerization reaction was carried out under the conditions described in Table 2 in the same procedure as in Example 14.
- Example 16 Copolymerization of ethylene and acrylonitrile
- Compound 4, toluene, ethylene (3 MPa) and acrylonitrile were charged in the amounts shown in Table 2 into a stainless steel oclave, and a polymerization reaction was carried out at the temperatures and times shown in the same table.
- the 13 C-NMR chart of the product of Example 16 is shown in FIG.
- Example 17 The catalyst was changed to Compound 6, and the polymerization reaction was carried out under the conditions described in Table 2 in the same procedure as in Example 16.
- Example 18 Copolymerization of ethylene and butyl vinyl ether
- Compound 4, toluene, ethylene (3 MPa) and butyl vinyl ether were charged in the amounts shown in Table 2 into a stainless steel oclave, and a polymerization reaction was carried out at the temperatures and times shown in the same table.
- a 13 C-NMR chart of the product of Example 18 is shown in FIG.
- Example 19 The catalyst was changed to Compound 6, and the polymerization reaction was carried out under the conditions described in Table 2 in the same procedure as in Example 16.
- Examples 20-24 Ethylene homopolymerization was carried out in the same manner except that the catalysts of Examples 1 to 9 were changed to compounds 7, 10, 12, and 14. The polymerization conditions are shown in Table 3, and the results are shown in Table 4.
- Examples 25-28 The catalysts of Examples 12 and 13 were changed to compounds 7, 10, and 14, and ethylene and allyl acetate were copolymerized in the same manner, or under conditions in which ethylene pressure, scale, or reaction time was changed.
- the polymerization conditions are shown in Table 5, and the results are shown in Table 6.
- Example 29 In copolymerization of ethylene and allyl acetate using Compound 6 as a catalyst, scale-up and a long-time reaction were performed. That is, compound 6 (0.029 g, 0.020 mmol), toluene (225 ml), and allyl acetate (75 ml) were added to a 500 ml autoclave, charged with ethylene to 4.0 MPa, and then stirred at 80 ° C. for 91 hours. did. After cooling to room temperature, the reaction solution was added to methanol (1.5 L). The precipitated polymer was collected by filtration and dried under reduced pressure. The yield was 14.9 g, and the catalytic activity was calculated as 8.2 kgmol ⁇ 1 h ⁇ 1 .
- the weight average molecular weight (Mw) was 67,000
- the number average molecular weight (Mn) was 32,000
- Mw / Mn was calculated to be 2.1 based on polystyrene.
- Example 30 Ethylene homopolymerization was carried out using a reaction solution obtained by previously reacting Compound 8 and sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate as a catalyst solution. Under a nitrogen atmosphere, Compound 8 (5.1 mg, 0.010 mmol) and tetrakis [3,5-bis (trifluoromethyl) phenyl] sodium borate (9.7 mg, 0.011 mmol) in a toluene (30 ml) solution, The mixture was stirred at room temperature for 30 minutes, and this solution was used as a catalyst solution.
- the precipitated polymer was collected by filtration and dried under reduced pressure. The yield was 5.4 g and the catalytic activity was calculated to be 540 kg mol ⁇ 1 h ⁇ 1 .
- the molecular weight of the obtained polymer was calculated to have a weight average molecular weight (Mw) of 485,000, a number average molecular weight (Mn) of 211,000 and Mw / Mn of 2.3, based on polystyrene.
- the uptake amount of allyl acetate was calculated to be 1.4 mol% by 1 H-NMR using 1,1,2,2-tetrachloroethane-d2 as a solvent.
- Example 31 Using a catalyst solution prepared in the same manner as described in Example 30, ethylene and allyl acetate were copolymerized. That is, a toluene (30 ml) solution of compound 8 (5.1 mg, 0.010 mmol) and sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (9.7 mg, 0.011 mmol) under a nitrogen atmosphere. The whole amount of the catalyst solution obtained by stirring at room temperature for 30 minutes, toluene (26.3 ml), and allyl acetate (18.8 ml) were added to a 120 ml autoclave and charged with ethylene to 4.0 MPa. , And stirred at 80 ° C. for 5 hours.
- the reaction solution was added to methanol (300 ml).
- the precipitated polymer was collected by filtration and dried under reduced pressure.
- the yield was 0.23 g, and the catalytic activity was calculated to be 4.7 kgmol ⁇ 1 h ⁇ 1 .
- the molecular weight of the obtained polymer the weight average molecular weight (Mw) was 58,000, the number average molecular weight (Mn) was 28,000, and Mw / Mn was calculated to be 2.1 based on polystyrene.
- the amount of allyl acetate incorporated was calculated to be 1.1 mol% by 1 H-NMR using 1,1,2,2-tetrachloroethane-d2 as a solvent.
- Examples 32-37 Compound 10, Compound 16, and the following formula synthesized by the same synthesis method as Compound 16 Using the compound 17 represented by the following formula, homopolymerization of ethylene, copolymerization of ethylene and allyl acetate, copolymerization of ethylene and butyl vinyl ether, and copolymerization of ethylene and methyl acrylate were carried out.
- the polymerization conditions are shown in Table 7, and the polymerization results are shown in Table 8.
- the novel metal compound of the present invention is very useful as a catalyst for copolymerization of ethylene and various polar monomers.
- the catalyst composition containing the novel metal compound of the present invention is used, a highly linear polymer can be obtained, and further, a copolymer in which polar monomers are randomly distributed in the polymer chain can be obtained.
- the catalyst composition of the present invention is extremely useful industrially because it enables the production of industrially useful functional polyolefins.
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Abstract
Description
また、イミノアミド配位子を有するニッケル錯体を用いてエチレンとメチルアクリレートとを共重合する方法も提案されているが(特許文献2)、この方法も実用化には至っていない。
[1] 式(I)
で示されるビスホスフィンモノオキサイド(BPMO)、及びBPMOと錯体形成している周期律表第10族の元素からなる中心金属Mを含む有機金属化合物。
[2] 式(II)
で示される前項1に記載の有機金属化合物。
[3]配位子R4が、
(i)ピリジン、置換ピリジン、ニトリル化合物、アンモニア、アルキルアミン、置換アルキルアミン、アリールアミンまたは置換アリールアミンから選択されるか、または
(ii)式(1)
[4]式(III)
で示される前項1~3のいずれか1項に記載の有機金属化合物。
[5]式(IIa)
で示される前項1~3のいずれか1項に記載の有機金属化合物。
[6]A1が、置換または無置換のフェニレン基、置換または無置換のナフチレン基、または置換または無置換のメチレン基である前項4または5に記載の有機金属化合物。
[7]R1a、R1b、R2a、R2bが、それぞれ独立して、炭素数3~6の分岐アルキル基を表す前項4~6のいずれか1項に記載の有機金属化合物。
[8]R1a及びR1bが、ともにイソプロピル基またはt-ブチル基である前項1~7のいずれか1項に記載の有機金属化合物。
[9]R2a及びR2bが、ともにt-ブチル基である前項1~8のいずれか1項に記載の有機金属化合物。
[10]Xが、SbF6、BPh4、BArF4(ArF4=[3,5-(CF3)2C6H3]4)、BF4またはPF6から選択される前項4~9のいずれか1項に記載の有機金属化合物。
[11]Mがパラジウムである前項4~10のいずれか1項に記載の有機金属化合物。
[12]式(IV)
で示される前項1~3のいずれか1項に記載の有機金属化合物。
[13]A1が、置換または無置換のフェニレン基、置換または無置換のナフチレン基、または置換または無置換のメチレン基を表す前項12に記載の有機金属化合物。
[14]式(V)
[15]A2が、置換または無置換のフェニレン基またはナフチレン基である前項14に記載の有機金属化合物。
[16]式(VI)
[17]R1a、R1b、R2a、R2bが、それぞれ独立して、炭素数3~14の分岐アルキル基である前項12~16のいずれか1項に記載の有機金属化合物。
[18]R1a及びR1bが、ともにイソプロピル基である前項12~17のいずれか1項に記載の有機金属化合物。
[19]R2a及びR2bが、ともにt-ブチル基である前項12~18のいずれか1項に記載の有機金属化合物。
[20]X-が、SbF6 -、BPh4 -、BArF4 -、BF4 -、PF6 -から選択される前項12~19のいずれか1項に記載の有機金属化合物。
[21]Mがパラジウムである前項12~20のいずれか1項に記載の有機金属化合物。
[22]前項1~21のいずれか1項に記載の有機金属化合物を含むビニル系モノマー重合用触媒組成物。
[23]前項1~21のいずれか1項に記載の有機金属化合物を含む非極性オレフィンと極性オレフィンとの共重合用触媒組成物。
[24]前項1~21のいずれか1項に記載の有機金属化合物を含む触媒組成物の存在下で、重合条件下に非極性オレフィンと極性オレフィンを反応させる工程を含む、共重合体の製造方法。
[25]極性オレフィンが式(VII)
で示される前項24に記載の共重合体の製造方法。
[26]R14が、-CH2-OCOR15、-CH2OH、-CH2-N(R16)2または-CH2-Hal(R15、R16、Halは、前項25の記載と同じ意味を表す。)である前項25に記載の共重合体の製造方法。
[27](1)式(I)
(2)生成した(BPMO)(1,5-シクロオクタジエン)MR6Xa錯体を、M2X(M2は、Ag、Li、Na、Kから選択される1価の金属イオンを表し、Xは、SbF6、BPh4、BArF4、BF4、PF6から選択される対アニオンを表す。)で示される金属塩及び式(2)
[28](1)式(I)
で示されるビスホスフィンモノオキサイド(BPMO)と式(3)
(2)(1)の工程の反応混合物にM2X(M2は、Ag、Li、Na、Kから選択される1価の金属イオンを表し、Xは、SbF6、BPh4、BArF4、BF4、PF6から選択される対アニオンを表す。)で示される金属塩を添加する工程を含む、式(IVa)
式(I)において、R1a、R1b、R2a、R2bは、同じであっても異なっていてもよく、それぞれ独立して、1~14の炭素原子を有する置換または無置換のアルキル基、3~14の炭素原子を有する置換または無置換のシクロアルキル基、置換または無置換のビフェニル基(C6H5-C6H4-)、または置換または無置換のアリール基を表し、好ましくは1~14の炭素原子を有する置換または無置換のアルキル基である。
また、R1a及びR1b、R2a及びR2bは結合して、環構造を形成してもよい。
R3は、1~10の炭素原子を有するアルキル基、1~10の炭素原子を有するアルケニル基、またはA2で示される2価の基を表し、A2はアリーレン基、単環式ヘテロアリーレン基、単環式シクロアルキレン基、単環式シクロアルケニレン基、単環式へテロシクロアルキレン基、単環式へテロシクロアルケニレン基、複素環またはC2~C4のアルキレン基を表す。
本発明の一つの実施形態において、R4は、ピリジン、置換ピリジン、ニトリル化合物、アンモニア、アルキルアミン、置換アルキルアミン、アリールアミンまたは置換アリールアミンから選択され、好ましくは、ピリジンまたは置換ピリジンである。
式(1)において、Wは炭素原子(C)または硫黄原子(S)を表し、Zは酸素原子(O)、S、NHまたはNRa(Raはアルキル基またはアリール基を表す。)から選択され、Yは、O、S、NH、またはNRb(Rbはアルキルまたはアリール基を表す。)から選択され、R5は、1~10の炭素原子を有する置換または無置換のアルキル基、ORc(Rcはアルキル基またはアリール基を表す。)、またはNRd 2(Rdはアルキル基またはアリール基を表す。)である。
X-は、カチオン性有機金属錯体の対イオンを表す。X-で示される対イオンは、1価のアニオンであればどのようなものでもよい。さらに中心金属(M)1原子あたりの電荷数が1価になるようであれば、X-は多価のアニオンであってもよい。具体的には、硫酸イオン(SO4 2-)、硝酸イオン(NO3 -)、炭酸イオン(CO3 2-)、過塩素酸イオン(ClO4 -)、塩化物イオン(Cl-)、臭化物イオン(Br-)、ヨウ化物イオン(I-)等のハロゲン化物イオン、テトラフルオロボレート(BF4 -)、ブロモトリフルオロボレート(BBrF3 -)、クロロトリフルオロボレート(BClF3 -)、トリフルオロメトキシボレート(BF3(OCH3)-)、トリフルオロエトキシボレート(BF3(OC2H5)-)、トリフルオロアリロキシボレート(BF3(OC3H5)-)、テトラフェニルボレート(B(C6H5)4 -)、テトラキス(3,5-ビス(トリフルオロメチル)フェニル)ボレート(B(3,5-(CF3)2C6H3)4 -=BArF4 ―)、ブロモトリフェニルボレート(BBr(C6H5)3 -)、クロロトリフェニルボレート(BCl(C6H5)3 -)、メトキシトリフェニルボレート(B(OCH3)(C6H5)3 -)、エトキシトリフェニルボレート(B(OC2H5)(C6H5)3 -)、アリロキシトリフェニルボレート(B(OC3H5)(C6H5)3 -)、テトラキス(ペンタフルオロフェニル)ボレート(B(C6F5)4 -)、ブロモトリス(ペンタフルオロフェニル)ボレート(BBr(C6F5)3 -)、クロロトリス(ペンタフルオロフェニル)ボレート(BCl(C6F5)3 -)、メトキシトリス(ペンタフルオロフェニル)ボレート(B(OCH3)(C6F5)3 -)、エトキシトリス(ペンタフルオロフェニル)ボレート(B(OC2H5)(C6F5)3 -)、アリロキシトリス(ペンタフルオロフェニル)ボレート(B(OC3H5)(C6F5)3 -)等のボレートイオン、メタンスルホネート(CH3SO3 -)、トリフルオロメタンスルホネート(CF3SO3 -)、ノナフルオロブタンスルホネート(C4F9SO3 -)、ベンゼンスルホネート(C6H5SO3 -)、p-トルエンスルホネート(p-CH3-C6H4SO3 -)等のスルホネートイオン、酢酸イオン(CH3CO2 -)、トリフルオロ酢酸イオン(CF3CO2 -)、トリクロロ酢酸イオン(CCl3CO2 -)、プロピオン酸イオン(C2H5CO2 -)、安息香酸イオン(C6H5CO2 -)等のカルボキシレートイオン、ヘキサフルオロホスフェート(PF6 -)等のホスフェートイオン、ヘキサフルオロアルセネートイオン(AsF6 -)等のアルセネートイオン、ヘキサフルオロアンチモネート(SbF6 -)等のアンチモネートイオン、ヘキサフルオロシリケート(SiF6 -)等のシリケートアニオン等が挙げられる。これら対イオンの中でも、X-がSbF6 -、BPh4 -、BArF4 -、BF4 -またはPF6 -であることが好ましい。
R6は、1~10の炭素原子を有するアルキル基、アルケニル基またはアリール基を表す。
R7、R8、R9は、それぞれ独立して、水素原子、1~4の炭素原子を有するアルキル基またはアルコキシ基を表す。
R10は、存在しないか、ベンゼン環中の置換可能な任意の水素と置換される1~10の炭素原子を有する1~4個のアルキル基を表し、2個以上存在するR10は同じであっても異なっていてもよい。
R13a及びR13bは、それぞれ独立して、水素原子、1~10の炭素原子を有するアルキル基、または6~12の炭素原子を有するアリール基を表し、同じであっても異なっていてもよい。また、R13aとR13bは結合して、架橋構造を形成していてもよい。
本発明においては、式(III)において、R1a、R1b、R2a、R2bは、それぞれ独立して、イソプロピル基またはt-ブチル基であることが特に好ましい。また、R1a及びR1bがイソプロピル基であり、R2a、R2bがt-ブチル基であることがとりわけ好ましい。
R11は、存在しないか、ベンゼン環中の置換可能な任意の水素と置換される1~10の炭素原子を有するアルキル基を表し、2個以上存在するR11は同じであっても異なっていてもよい。
R12は、存在しないか、ベンゼン環中の置換可能な任意の水素と置換される1~10の炭素原子を有するアルキル基を表し、2個以上存在するR12は同じであっても異なっていてもよい。
式(IIIa)において、R10が存在しない場合(ベンゼン環にR10として置換基がない場合)について、以下の式(IIIb)で示される有機金属化合物の具体例を表Iに示す。
本発明においては、極性オレフィンは、極性ノルボルネン型モノマー、ビニルホスホン酸、及びそのエステルであってもよい。
核磁気共鳴装置(日本電子(株)製、JNM-ECP500及びJNMECS400)を用い、1H NMR、13C-NMR、及び31P NMRを測定した。ポリマー中の極性モノマー含有率と共重合体の分岐の度合いは、Cr(acac)3(acac=Acetylacetonate;CH3COCHCOCH3)を緩和剤として加え、13C-NMRで定量した。分子量はサイズ排除クロマトグラフィー(TOSOH(株)製、HLC-8121GPC/HT)にTSKgel GMHHR-H(S)HTを接続し、ポリスチレンを基準として見積もったのち、Mark-Houwinkパラメーターをポリスチレン(K=1.75×10-2cm3/g、α=0.67)、直線状低密度ポリエチレン(K=5.90×10-2cm3/g、α=0.69)と用いて補正した。元素分析は東京大学理学部元素分析センターで行った。高分解能質量分析(HRMS)は日本電子(株)製JMS-T100LPを用い、electrospray ionization time-of-flight(ESI-TOF)法で、ポリエチレングリコールを標準に用いて測定した。
化合物2:R1=Ph、R2=t-Bu
化合物3:R1=i-Pro、R2=Ph
化合物4:R1=i-Pro、R2=t-Bu(表Iの化合物No.11に対応)
遊離BPMO(ビスホスフィンモノオキサイド)としてo-(Ph2P)C6H4(P(O)Ph2)(1-ジフェニルホスフィノ-2-ジフェニルホスフィニルベンゼン)(139mg,0.301mmol)の塩化メチレン(2ml)溶液と(cod)PdMeCl(cod=1,5-シクロオクタジエン80mg、0.30mmol)の塩化メチレン(2ml)溶液を25℃で5分間混合した後、トルエンとヘキサンを加えて中間体の((o-(Ph2P)C6H4(P(O)Ph2)PdMeCl錯体175mgを得た。この固体と2,6-ルチジン(0.033ml,0.28mmol)を塩化メチレン5mlに溶かし、ヘキサフルオロアンチモン酸銀(97mg,0.28mmol)と25℃で10分間反応させた。塩化銀をセライトろ過で取り除いたのち、溶媒を留去し、トリフルオロメチルベンゼンに溶かしてエーテルを加え、生じた沈殿を集めて乾燥させ、塩化メチレンから再結晶することで標題の化合物1を空気及び湿気に安定な淡橙色の結晶として175mg得た。収率は49%であった。
遊離BPMOとしてo-(Ph2P)C6H4(P(O)t-Bu2)を用いた以外は化合物1と同様の手順により、化合物2を得た。収率は57%であった。
遊離BPMOとしてo-(i-Pr2P)C6H4(P(O)Ph2)を用いた以外は化合物1と同様の手順により、化合物3を得た。収率は49%であった。
遊離BPMOとしてo-(i-Pr2P)C6H4(P(O)t-Bu2)を用いた以外は化合物1と同様の手順により、化合物4を得た。収率は72%であった。
化合物6:X=BArF4(表IIの化合物No.262に対応)
遊離BPMOとしてo-(i-Pr2P)C6H4(P(O)t-Bu2)(142mg,0.401mmol)と化合物A(110mg、0.199mmol)を塩化メチレン7mlに溶かし、25℃で3時間撹拌後、この溶液を-78℃に冷却したフラスコ中のヘキサフルオロアンチモン酸銀(0.31g,0.90mmol)にゆっくりと注いだ。25℃で30分間激しく撹拌した後、塩化銀をセライトろ過により除去し、濃縮後トルエンを注いで沈殿を得た。この沈殿をさらに塩化メチレンから再結晶し、空気及び湿気に安定な淡橙色の結晶として化合物5を得た。収率は73%であった。
ヘキサフルオロアンチモン酸銀に代えてNaBArF4を用いて、化合物5の合成と同様の手順により、化合物6を得た。収率は96%であった。
化合物4を原料として、化合物7を合成した。すなわち、アルゴン雰囲気下、[メチルパラジウム(1-ジイソプロピルホスフィノ-2-ジ(t-ブチル)ホスフィニルベンゼン)(2,6-ルチジン)][ヘキサフルオロアンチモネート](化合物4;0.24g、0.30mmol)とテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウム(0.26g、0.30mmol)の塩化メチレン(8ml)懸濁液を、室温で20分撹拌させた。反応液をセライト(乾燥珪藻土)でろ過し、そのろ液を減圧濃縮した。残渣の黄色固体をヘキサンで洗浄した後に、減圧乾燥を行い、化合物7を0.41g得た。収率は95%であった。
合成例4に記載の化合物4の合成における合成中間体である、式
アルゴン雰囲気下、ジ(t-ブチル)フェニルホスフィンオキシドのリチオ化体と三塩化リンから合成される化合物9b(0.37g、1.0mmol)のTHF(7ml)溶液に、2-ブロモアニソール(0.34g、2.0mmol)のTHF(14ml)溶液とn-ブチルリチウム(1.64Mペンタン溶液、1.3ml、2.1mmol)を反応させた反応液を、-78℃で加え、30分撹拌した。室温までゆっくり昇温した後、室温で1時間撹拌した。水で反応を停止し、反応液を減圧濃縮後、残渣を塩化メチレンに溶解させ、その溶液をセライトろ過した。溶媒を留去後、塩化メチレン/メタノール(30:1)を展開溶媒とするシリカゲルカラムクロマトグラフィー及びTHF/ヘキサンからの再結晶による精製操作を行い、化合物9aを0.30g得た。
さらに、アルゴン雰囲気下、得られた化合物9a(0.14g、0.30mmol)と(cod)PdMeCl(0.088g、0.33mmol)の塩化メチレン(3ml)溶液を、室温で1時間撹拌させた。反応液を、セライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレンとジエチルエーテルから再沈殿操作を行い、化合物9を0.15g得た。収率は81%であった。
アルゴン雰囲気下、化合物9(0.050g、0.078mmol)、2,6-ジメチルピリジン(0.013g、0.12mmol)、及びテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウム(0.069g、0.078mmol)の塩化メチレン(2ml)懸濁液を、室温で1時間撹拌した。反応液をセライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレンとペンタンから再沈殿操作を行い、化合物10を0.10g得た。収率は83%であった。
合成例9に記載の方法と同様の方法で、化合物11を合成した。すなわち、アルゴン雰囲気下、化合物9aから合成された化合物11a(0.10g、0.22mmol)と(cod)PdMeCl(0.064g、0.24mmol)の塩化メチレン(2ml)溶液を、室温で1時間撹拌した。反応液を、セライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレンとジエチルエーテルから再沈殿操作を行い、化合物11を0.10g得た。収率は、74%であった。
合成例7に記載の方法と同様の方法で、化合物12を合成した。すなわち、アルゴン雰囲気下、化合物11(0.082g、0.14mmol)、2,6-ジメチルピリジン(0.029g、0.27mmol)、及びテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウム(0.12g、0.14mmol)の塩化メチレン(3ml)懸濁液を、室温で1.5時間撹拌した。反応液をセライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレンとペンタンから再沈殿操作を行い、化合物12を0.19g得た。収率は90%であった。
アルゴン雰囲気下、ジ(t-ブチル)ホスフィノメチルリチウム(0.083g、0.50mmol)とジメチルホスフィン酸クロリド(0.083g、0.50mmol)の反応から定量的に得られる化合物13aと、(cod)PdMeCl(0.13g、0.50mmol)の塩化メチレン(10ml)溶液を室温で撹拌した。反応液をセライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレンとヘキサンから再結晶精製を行い、化合物13を0.071g得た。収率は36%であった。
アルゴン雰囲気下、化合物13(0.071g、0.18mmol)、2,6-ジメチルピリジン(0.019g、0.18mmol)、及びヘキサフルオロアンチモン酸銀(0.062g、0.18mmol)の塩化メチレン(3ml)懸濁液を、室温で撹拌した。反応液をセライト(乾燥珪藻土)でろ過した後、ろ液にテトラキス(3,5-ビス(トリフルオロメチル)フェニルホウ酸ナトリウム(0.15g、0.18mmol)を加え、再度室温で撹拌した。反応液をセライト(乾燥珪藻土)でろ過した後、ろ液の溶媒を留去し、化合物14を0.23g得た。収率は96%であった。
合成例9及び11と同様の手法で化合物15を合成した。すなわち、アルゴン雰囲気下、ジ(t-ブチル)フェニルホスフィンオキシドのリチオ化体と三塩化リンから合成される化合物9b(0.37g、1.0mmol)のTHF(7ml)溶液に、1-ブロモ‐2,4-ジメトキシベンゼン(0.43g、2.0mmol)のTHF(14ml)溶液とn-ブチルリチウム(1.64Mペンタン溶液、1.3ml、2.1mmol)を反応させた反応液を、-78℃で加え、30分撹拌した。室温までゆっくり昇温した後、室温で1時間撹拌した。水で反応を停止し、反応液を減圧濃縮後、残渣を塩化メチレンに溶解させ、その溶液をセライトろ過した。溶媒を留去後、塩化メチレン/ヘキサンからの再結晶による精製操作を行い、化合物15aを0.40g得た。
さらに、アルゴン雰囲気下、得られた化合物15a(0.10g、0.18mmol)と(cod)PdMeCl(0.054g、0.20mmol)の塩化メチレン(2ml)溶液を、室温で2時間撹拌させた。反応液を、セライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレン/ジエチルエーテルからの再結晶による精製操作を行い、化合物15を0.098g得た。化合物9bからの収率は55%であった。
合成例10及び12と同様の手法で化合物16を合成した。すなわち、アルゴン雰囲気下、化合物15(0.098g、0.14mmol)、2,6-ジメチルピリジン(0.023g、0.27mmol)、及びテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウム(0.12g、0.14mmol)の塩化メチレン(4ml)懸濁液を、室温で40分撹拌した。反応液をセライト(乾燥珪藻土)でろ過し、ろ液を減圧下濃縮した。残渣に対して、塩化メチレンとペンタンから再沈殿操作を行い、化合物12を0.15g得た。収率は66%であった。
実施例1~9:
50mlのステンレスオートクレーブを120℃で十分に乾燥させた後、乾燥器中で室温まで冷却し、化合物1~6それぞれ6.0μモル(6.0Mの塩化メチレン溶液を1.0ml)(実施例1~4、6、8)及び化合物4~6それぞれ0.75μモル(0.75Mの塩化メチレン溶液を1.0ml)(実施例5、7、9)を加えて塩化メチレンを減圧留去した。ここに、トルエン(15ml)を加えて触媒を溶かし、エチレン(3MPa)を圧入して80℃(または100℃)で1時間または3時間反応させた。
その結果を表1に示す。
また、触媒前駆体を変更した化合物5及び6でも非常に高い触媒活性を示している。
実施例5の生成物の13C-NMRチャートを図1に示す。
実施例10:
ステンレススチールのオートクレーブ中に、化合物4、トルエン、エチレン(3MPa)及び酢酸ビニルを表2に記載の量で投入し、同表に記載の温度及び時間で重合反応を行った。実施例10の生成物の13C-NMRチャートを図2に示す。
触媒を化合物6に変更し、実施例10と同様の手順で、表2に記載の条件で重合反応を行った。
実施例12:
ステンレススチールのオークレーブ中に、化合物4、トルエン、エチレン(3MPa)及び酢酸アリルを表2に記載の量で投入し、同表に記載の温度及び時間で重合反応を行った。実施例12の生成物の13C-NMRチャートを図3に示す。
触媒を化合物6に変更し、実施例12と同様の手順で、表2に記載の条件で重合反応を行った。
実施例14:
ステンレススチールのオークレーブ中に、化合物4、トルエン、エチレン(3MPa)及び塩化アリルを表2に記載の量で投入し、同表に記載の温度及び時間で重合反応を行った。実施例14の生成物の13C-NMRチャートを図4に示す。
触媒を化合物6に変更し、実施例14と同様の手順で、表2に記載の条件で重合反応を行った。
実施例16:
ステンレススチールのオークレーブ中に、化合物4、トルエン、エチレン(3MPa)及びアクリロニトリルを表2に記載の量で投入し、同表に記載の温度及び時間で重合反応を行った。実施例16の生成物の13C-NMRチャートを図5に示す。
触媒を化合物6に変更し、実施例16と同様の手順で、表2に記載の条件で重合反応を行った。
実施例18:
ステンレススチールのオークレーブ中に、化合物4、トルエン、エチレン(3MPa)及びブチルビニルエーテルを表2に記載の量で投入し、同表に記載の温度及び時間で重合反応を行った。実施例18の生成物の13C-NMRチャートを図6に示す。
触媒を化合物6に変更し、実施例16と同様の手順で、表2に記載の条件で重合反応を行った。
実施例12及び13の触媒を化合物7、10、及び14に変更して、同様の方法、あるいはエチレン圧、スケール、または反応時間を変更した条件で、エチレンと酢酸アリルの共重合を行った。重合条件を表5に、結果を表6に示す。
触媒として化合物6を使用したエチレンと酢酸アリルとの共重合において、スケールアップ及び長時間反応を行った。すなわち、化合物6(0.029g、0.020mmol)、トルエン(225ml)、及び酢酸アリル(75ml)を500mlオートクレーブ中に加え、4.0MPaになるまでエチレンを充填した後、80℃で91時間撹拌した。室温まで冷却後、反応液をメタノール(1.5L)に加えた。析出した重合体をろ過によって回収し、減圧乾燥を行った。収量は14.9gであり、触媒活性は8.2kgmol-1h-1と算出された。得られた重合体の分子量は、ポリスチレン基準で、重量平均分子量(Mw)が67,000、数平均分子量(Mn)が32,000であり、Mw/Mnが2.1と算出された。
化合物8とテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウムを予め反応させた反応液を触媒液として使用して、エチレンの単独重合を行った。窒素雰囲気下、化合物8(5.1mg、0.010mmol)とテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウム(9.7mg、0.011mmol)のトルエン(30ml)溶液中、室温で30分撹拌し、この液を触媒液とした。このとき、式(II)中のR4が存在しない場合の有機金属化合物、すなわち式
続いて、上記の触媒液全量及びトルエン(45ml)を120mlオートクレーブ内に加え、3.0MPaになるまでエチレンを充填した後、80℃で1時間撹拌した。室温まで冷却後、反応液をメタノール(300ml)に加えた。析出した重合体をろ過によって回収し、減圧乾燥を行った。収量は5.4gであり、触媒活性は540kgmol-1h-1と算出された。得られた重合体の分子量は、ポリスチレン基準で、重量平均分子量(Mw)が485,000、数平均分子量(Mn)が211,000であり、Mw/Mnが2.3と算出された。酢酸アリルの取り込み量は、1,1,2,2-テトラクロロエタン-d2を溶媒とする1H-NMRにより、1.4mol%と算出した。
実施例30に記載された方法と同様の方法で調製した触媒液を使用して、エチレンと酢酸アリルの共重合を行った。すなわち、窒素雰囲気下、化合物8(5.1mg、0.010mmol)とテトラキス[3,5-ビス(トリフルオロメチル)フェニル]ホウ酸ナトリウム(9.7mg、0.011mmol)のトルエン(30ml)溶液中、室温で30分撹拌して得られた触媒液全量、トルエン(26.3ml)、及び酢酸アリル(18.8ml)を、120mlオートクレーブ内に加え、4.0MPaになるまでエチレンを充填した後、80℃で5時間撹拌した。室温まで冷却後、反応液をメタノール(300ml)に加えた。析出した重合体をろ過によって回収し、減圧乾燥を行った。収量は0.23gであり、触媒活性は4.7kgmol-1h-1と算出された。得られた重合体の分子量は、ポリスチレン基準で、重量平均分子量(Mw)が58,000、数平均分子量(Mn)が28,000であり、Mw/Mnが2.1と算出された。酢酸アリルの取り込み量は、1,1,2,2-テトラクロロエタン‐d2を溶媒とする1H-NMRにより、1.1mol%と算出した。
化合物10、化合物16、及び化合物16と同様の合成手法で合成される下記式
Claims (28)
- 式(I)
で示されるビスホスフィンモノオキサイド(BPMO)、及びBPMOと錯体形成している周期律表第10族の元素からなる中心金属Mを含む有機金属化合物。 - 式(II)
で示される請求項1に記載の有機金属化合物。 - 配位子R4が、
(i)ピリジン、置換ピリジン、ニトリル化合物、アンモニア、アルキルアミン、置換アルキルアミン、アリールアミンまたは置換アリールアミンから選択されるか、または
(ii)式(1)
- A1が、置換または無置換のフェニレン基、置換または無置換のナフチレン基、または置換または無置換のメチレン基である請求項4または5に記載の有機金属化合物。
- R1a、R1b、R2a、R2bが、それぞれ独立して、炭素数3~6の分岐アルキル基を表す請求項4~6のいずれか1項に記載の有機金属化合物。
- R1a及びR1bが、ともにイソプロピル基またはt-ブチル基である請求項1~7のいずれか1項に記載の有機金属化合物。
- R2a及びR2bが、ともにt-ブチル基である請求項1~8のいずれか1項に記載の有機金属化合物。
- Xが、SbF6、BPh4、BArF4(ArF4=[3,5-(CF3)2C6H3]4)、BF4またはPF6から選択される請求項4~9のいずれか1項に記載の有機金属化合物。
- Mがパラジウムである請求項4~10のいずれか1項に記載の有機金属化合物。
- A1が、置換または無置換のフェニレン基、置換または無置換のナフチレン基、または置換または無置換のメチレン基を表す請求項12に記載の有機金属化合物。
- A2が、置換または無置換のフェニレン基またはナフチレン基である請求項14に記載の有機金属化合物。
- R1a、R1b、R2a、R2bが、それぞれ独立して、炭素数3~14の分岐アルキル基である請求項12~16のいずれか1項に記載の有機金属化合物。
- R1a及びR1bが、ともにイソプロピル基である請求項12~17のいずれか1項に記載の有機金属化合物。
- R2a及びR2bが、ともにt-ブチル基である請求項12~18のいずれか1項に記載の有機金属化合物。
- X-が、SbF6 -、BPh4 -、BArF4 -、BF4 -、PF6 -から選択される請求項12~19のいずれか1項に記載の有機金属化合物。
- Mがパラジウムである請求項12~20のいずれか1項に記載の有機金属化合物。
- 請求項1~21のいずれか1項に記載の有機金属化合物を含むビニル系モノマー重合用触媒組成物。
- 請求項1~21のいずれか1項に記載の有機金属化合物を含む非極性オレフィンと極性オレフィンとの共重合用触媒組成物。
- 請求項1~21のいずれか1項に記載の有機金属化合物を含む触媒組成物の存在下で、重合条件下に非極性オレフィンと極性オレフィンを反応させる工程を含む、共重合体の製造方法。
- R14が、-CH2-OCOR15、-CH2OH、-CH2-N(R16)2または-CH2-Hal(R15、R16、Halは、請求項25の記載と同じ意味を表す。)である請求項25に記載の共重合体の製造方法。
- (1)式(I)
(2)生成した(BPMO)(1,5-シクロオクタジエン)MR6Xa錯体を、M2X(M2は、Ag、Li、Na、Kから選択される1価の金属イオンを表し、Xは、SbF6、BPh4、BArF4、BF4、PF6から選択される対アニオンを表す。)で示される金属塩及び式(2)
- (1)式(I)
で示されるビスホスフィンモノオキサイド(BPMO)と式(3)
(2)(1)の工程の反応混合物にM2X(M2は、Ag、Li、Na、Kから選択される1価の金属イオンを表し、Xは、SbF6、BPh4、BArF4、BF4、PF6から選択される対アニオンを表す。)で示される金属塩を添加する工程を含む、式(IVa)
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CN105152970A (zh) * | 2015-06-25 | 2015-12-16 | 中国科学技术大学 | 大位阻二亚胺钯催化剂及其配体、制备方法和用途 |
WO2015200849A3 (en) * | 2014-06-27 | 2016-04-07 | The Trustees Of Princeton University | Transition metal catalysts for olefin polymerization |
WO2019021890A1 (ja) | 2017-07-25 | 2019-01-31 | 昭和電工株式会社 | ガスバリア性樹脂組成物及びその用途 |
WO2019093364A1 (ja) | 2017-11-09 | 2019-05-16 | 国立大学法人東京大学 | オレフィン重合用触媒及び極性基含有オレフィン系重合体の製造方法 |
WO2019163442A1 (ja) | 2018-02-20 | 2019-08-29 | 国立大学法人東京大学 | 極性基含有アリルモノマー共重合体の製造方法 |
WO2019207969A1 (ja) | 2018-04-25 | 2019-10-31 | 国立大学法人東京大学 | 極性基を有するアリルモノマー共重合体の製造方法 |
WO2020175482A1 (ja) | 2019-02-25 | 2020-09-03 | 国立大学法人 東京大学 | オレフィン重合用触媒及び極性基含有オレフィン系重合体の製造方法 |
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US10414837B2 (en) * | 2014-10-28 | 2019-09-17 | The University Of Tokyo | Method for producing polar group-containing olefin polymer |
CN105061505A (zh) * | 2015-09-16 | 2015-11-18 | 中国科学技术大学 | 催化剂配体、催化剂及其制备方法和应用 |
CN108383932A (zh) * | 2018-03-14 | 2018-08-10 | 陕西理工大学 | 一种化工合成用催化剂的制备方法 |
CN111116810B (zh) * | 2018-10-31 | 2023-01-17 | 中国石油化工股份有限公司 | 一种烯烃-烯烃醇共聚物的制备方法 |
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EP2848623B1 (en) | 2017-09-27 |
EP3190120A1 (en) | 2017-07-12 |
JPWO2013168626A1 (ja) | 2016-01-07 |
US20150099857A1 (en) | 2015-04-09 |
CN104271585B (zh) | 2017-08-04 |
KR20150011805A (ko) | 2015-02-02 |
EP2848623A1 (en) | 2015-03-18 |
JP6208657B2 (ja) | 2017-10-04 |
EP2848623A4 (en) | 2016-08-10 |
CN104271585A (zh) | 2015-01-07 |
EP3190120B1 (en) | 2021-11-17 |
KR101715658B1 (ko) | 2017-03-13 |
US9303101B2 (en) | 2016-04-05 |
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