WO2012029432A1 - カルボキシラート金属錯体及びオレフィン重合用触媒 - Google Patents
カルボキシラート金属錯体及びオレフィン重合用触媒 Download PDFInfo
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- WO2012029432A1 WO2012029432A1 PCT/JP2011/066663 JP2011066663W WO2012029432A1 WO 2012029432 A1 WO2012029432 A1 WO 2012029432A1 JP 2011066663 W JP2011066663 W JP 2011066663W WO 2012029432 A1 WO2012029432 A1 WO 2012029432A1
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- metal complex
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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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
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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
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- 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
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Definitions
- the present invention relates to a novel Group 10 metal complex of the periodic table, an olefin polymerization catalyst comprising the same as a main component, and a polymer production method using the catalyst.
- Non-Patent Document 1 shows a polymerization mechanism and a catalyst deactivation mechanism in the polymerization of vinyl acetate using a metal complex of Group 10 of the periodic table. Has been.
- ⁇ -acetoxy elimination after insertion of vinyl acetate into the metal-alkyl bond has been proposed. This is because the metal-acetoxy complex produced by ⁇ -acetoxy elimination is It has been shown that it has no polymerization activity and in general olefin insertion into the metal-oxygen bond cannot occur.
- Non-patent Document 2 shows the copolymerization of ethylene and methyl acrylate using a catalyst obtained by previously reacting a zero-valent late metal complex with a ligand. ing.
- a metal-hydride complex is formed and a polymerization reaction is started.
- the thermal stability of the metal-hydride complex is low, the decomposition reaction of the catalyst species proceeds and the polymerization activity is considered to be low.
- Non-Patent Document 3 describes the copolymerization of ethylene and vinyl acetate using an isolated metal-methyl complex catalyst. -When a methyl complex catalyst is used, the polymerization activity is much improved compared to the metal-hydride complex formed in the system. However, in general, metal-alkyl complexes have a problem in stability because they tend to be decomposed by impurities during polymerization, and have problems for industrial use.
- An object of the present invention is to provide a Group 10 metal complex in the periodic table that is more stable than conventional post-periodic metal catalysts for olefin polymerization, a catalyst for olefin polymerization mainly comprising the same, and a method for producing a polymer using the catalyst Is to provide.
- olefin represents a hydrocarbon compound having an ethylenic carbon-carbon double bond regardless of the presence or absence of a polar group.
- R 2 and R 3 each independently represent a hydrogen atom, Carbon that may be substituted with one or more functional groups selected from an alkoxy group, an aryloxy group, an acyloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group
- R 2 and R 3 may combine to form a ring structure
- Y represents a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group.
- the carboxylate metal complex represented by the general formula (C1) is represented by the general formula (C2).
- R 4 s are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or Represents a halogen atom, and M, R 1 , R 2 , R 3 , L, and n have the same meaning as described in [1].)
- M, R 1 , R 2 , R 3 , L, and n have the same meaning as described in [1].
- the compound represented by the general formula (1) (In the formula, R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
- the olefin represented by the formula (1) is polymerized alone or in combination of two or more, or the olefin represented by the general formula (1) and the general formula (2) (Wherein R 6 represents a hydrogen atom or a methyl group, R 7 represents —COOR 8 , —CN, —OCOR 8 , —CH 2 —OCOR 8 , —CH 2 OH, —CH 2 —N (R 9 )) 2 or —CH 2 —Hal (R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, R 9 represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic group having 6 to 18 carbon atoms) Represents an aromatic substituent or an aromatic substituent or an aromatic substituent or an aromatic substituent or an aromatic substituent or an aromatic substituent or an
- the novel metal group of Group 10 of the present invention in which all of the coordination atoms are heteroatoms, is stable and useful as a catalyst component for olefin polymerization, and is a homopolymer of olefins or of two or more olefins. Can be used for copolymerization for a long time.
- FIG. 1 is an X-ray structural analysis diagram of a metal complex 1 prepared in Example 1.
- FIG. 3 is an X-ray structural analysis diagram of a metal complex 2 prepared in Example 2.
- FIG. 1 is an X-ray structural analysis diagram of a metal complex 1 prepared in Example 1.
- FIG. 3 is an X-ray structural analysis diagram of a metal complex 2 prepared in Example 2.
- FIG. 1 is an X-ray structural analysis diagram of a metal complex 1 prepared in Example 1.
- FIG. 3 is an X-ray structural analysis diagram of a metal complex 2 prepared in Example 2.
- the metal complex of the present invention has the general formula (C1) Indicated by
- M represents a metal atom of Group 10 of the periodic table
- X represents a phosphorus atom (P) or an arsenic atom (As)
- R 1 represents a hydrogen atom, or a halogen atom, an alkoxy group, an aryloxy group, It represents an acyloxy group and a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from amino groups.
- R 2 and R 3 are each independently selected from a hydrogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group.
- It represents a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups, and R 2 and R 3 may combine to form a ring structure.
- Y represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted with one or more functional groups selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group.
- L represents a neutral electron-donating ligand, and n is 0, 1/2, 1, or 2.
- “hydrocarbon” includes saturated and unsaturated aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.
- M represents an element of Group 10 of the periodic table.
- the elements belonging to Group 10 of the periodic table include nickel (Ni), palladium (Pd), and platinum (Pt). Ni and Pd are preferable, and Pd is more preferable.
- the Y—S ( ⁇ O) 2 —O— moiety is an oxygen atom having a high electronegativity and is coordinated to the metal atom M by one electron.
- R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group.
- the hydrocarbon group include an alkyl group, an aryl group, and a cycloalkyl group.
- the halogen atom in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and an amino group is preferably fluorine.
- the alkoxy group preferably has 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
- the aryloxy group those having 6 to 24 carbon atoms are preferable, and examples thereof include a phenoxy group.
- the acyloxy group those having 1 to 10 carbon atoms are preferable, and examples thereof include an acetoxy group and a pivaloxy group.
- amino group those having 1 to 10 carbon atoms are preferable, and a dimethylamino group, a diethylamino group, and diisopropylamino.
- Groups. R 1 is more preferably a methyl group, a trifluoromethyl group, or a phenyl group from the viewpoint of availability and cost.
- the neutral electron-donating ligand L represents a neutral electron donating ligand.
- the neutral electron-donating ligand L is a compound having an electron-donating group and capable of stabilizing the metal complex by coordinating two electrons to the metal atom M. Can be separated.
- Examples of the neutral electron donating ligand include dimethyl sulfoxide (DMSO) having a sulfur atom.
- trialkylamine, dialkylamine, pyridine, 2,6-dimethylpyridine, quinoline, 2-methylquinoline, aniline, 2,6-dimethylaniline, 2,6- Examples include diisopropylaniline, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), 4- (N, N-dimethylamino) pyridine (DMAP), acetonitrile, and benzonitrile.
- Examples of those having a phosphorus atom include trimethylphosphine, triisopropylphosphine, tributylphosphine, tri (t-butyl) phosphine, triphenylphosphine, tris (o-tolyl) phosphine, and trifurylphosphine.
- Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. From the viewpoint of the synthesis method, those having a nitrogen atom and those having a phosphorus atom are preferred, and those having a nitrogen atom are particularly preferred.
- N represents the coordination number of the neutral electron-donating ligand L to the metal atom M, and is 0, 1/2, 1, or 2.
- n 1/2, it means that one divalent electron-donating ligand is coordinated to two metal complexes.
- n is preferably 1/2 or 1 in order to stabilize the metal complex.
- n 0, it means that there is no ligand.
- X is a phosphorus atom (P) or an arsenic atom (As), which is coordinated with M by two electrons.
- X is preferably P from the standpoint of availability and catalyst cost.
- R 2 and R 3 are each independently selected from a hydrogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group
- the alkoxy group is preferably one having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
- the aryloxy group those having 6 to 24 carbon atoms are preferable, and examples thereof include a phenoxy group.
- Examples of the silyl group include a trimethylsilyl group, and examples of the amino group include an amino group, a methylamino group, and a dimethylamino group.
- R 2 and R 3 may be the same or different.
- R 2 and R 3 may be bonded to form a ring structure.
- Carbon in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups and amino groups of R 2 and R 3
- Examples of the hydrocarbon group having 1 to 30 atoms include an alkyl group, an aryl group, a cycloalkyl group, and a furyl group.
- a halogen atom, an alkoxy group, an aryl in a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group
- R 2 and R 3 are more preferably an alkyl group, a cycloalkyl group and an aryl group, and most preferably an isopropyl group and a cyclohexyl group.
- Y represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted with one or more functional groups selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and an amino group (crosslinked structure) ).
- the hydrocarbon group of ⁇ 70 includes an alkylene group and an arylene group. Particularly preferred is an arylene group.
- the cross-linked structure Y is a cross-linked site that bonds X and a sulfur atom (S). Specific examples of the crosslinked structure Y in which X is a P atom are shown below.
- a plurality of R 10 may be the same or different, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. Represents.
- the substituents R 2 and R 3 may be bonded to the Y site to form a ring structure. Specific examples include the following structures.
- metal complexes represented by the general formula (C1) those represented by the following general formula (C2) are particularly preferable.
- R 4 s independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or a halogen atom.
- M, R 1 , R 2 , R 3 , L, and n represent the same meaning as in formula (C1).
- Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and an octyl group.
- Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
- Examples of the aryloxy group having 6 to 18 carbon atoms include a phenoxy group.
- Examples of the halogen atom include chlorine and fluorine.
- R 1 is preferably a methyl group, and both R 2 and R 3 are preferably a cyclohexyl group or an isopropyl group.
- Each of the four R 4 is preferably a hydrogen atom.
- L is preferably dimethyl sulfoxide, pyridine, 2,6-dimethylpyridine (lutidine), quinoline, 2-methylquinoline, or N, N, N ′, N′-tetramethylethylenediamine, particularly 2,6-dimethylpyridine ( Lutidine) is preferred.
- n is preferably 1/2 or 1, particularly preferably 1.
- M is preferably Ni or Pd, and particularly preferably Pd.
- the method for synthesizing the metal complexes (C1) and (C2) of the present invention is not particularly limited, and can be synthesized by a known method or a combination thereof. That is, it can be synthesized by reacting a zero-valent or divalent M source, a ligand in the general formula (C1) or (C2), and a neutral electron-donating ligand L.
- zero-valent M sources examples include tris (dibenzylideneacetone) dipalladium and tetrakis (triphenylphosphine) palladium as palladium sources, and tetracarbonylnickel and bis (1,5-cyclooctadiene) nickel as nickel sources. And tetrakis (triphenylphosphine) nickel.
- the divalent M source includes (1,5-cyclooctadiene) palladium chloride, (1,5-cyclooctadiene) (methyl) palladium chloride, (allyl) palladium chloride, palladium chloride, palladium bromide as a palladium source.
- Nickel sources include (allyl) nickel chloride, (allyl) Nickel bromide, nickel chloride, nickel acetate Bis (acetylacetonato) nickel (II), (1,2-dimethoxyethane) dichloronickel (II), (1,2-dimethoxyethane) dibromonickel (II), nickel trifluoromethanesulfonate (II), etc. Is mentioned.
- the metal complex represented by the general formula (C1) and the general formula (C2) includes a corresponding M-hydride complex or M-alkyl complex (both are referred to as “(C3)”) and an allyl ester (2-1 ) Can also be synthesized.
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 1 , R 2 , R 3 , X, Y, M, L, and n have the same meaning as described above.
- the above formula represents a method for synthesizing the metal complex (C1)
- the metal complex (C2) can also be synthesized by the same method.
- the metal complexes represented by the general formulas (C1) and (C2) can also be synthesized by reacting the corresponding M-halogen complex (C4) with the carboxylate metal salt (2-2).
- R 12 represents a halogen atom
- M ′ represents a metal atom
- R 1 , R 2 , R 3 , X, Y, M, L, and n represent the same meaning as described above.
- the above formula represents a method for synthesizing the metal complex (C1)
- the metal complex (C2) can also be synthesized by the same method.
- the halogen atom represented by R 12 include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable from the viewpoint of economy.
- carboxylate metal salt (2-2) that can be used in this synthesis method include silver acetate, silver trifluoroacetate, silver propionate, silver 2-ethylhexanoate, lithium acetate, lithium trifluoroacetate, propionic acid.
- Examples include lithium, lithium 2-ethylhexanoate, sodium acetate, sodium trifluoroacetate, sodium propionate, sodium 2-ethylhexanoate, potassium acetate, potassium trifluoroacetate, potassium propionate, and potassium 2-ethylhexanoate.
- the metal complex represented by the general formula (C1) or the general formula (C2) 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 olefin which is the first monomer used in the method for producing a polymer of the present invention, has the general formula (1) Indicated by
- R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- R 5 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- Specific examples of the olefin of the general formula (1) include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and styrene. Among these, ethylene and propylene are particularly preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
- the olefin containing a polar group which is the second monomer used for the polymerization in the present invention is represented by the general formula (2). Indicated by
- R 6 represents a hydrogen atom or a methyl group.
- R 7 is —COOR 8 , —CN, —OCOR 8 , —CH 2 —OCOR 8 , —CH 2 OH, —CH 2 —N (R 9 ) 2 or —CH 2 —Hal (R 8 is a hydrogen atom or carbon
- R 9 represents a hydrocarbon group having 1 to 5 atoms
- R 9 represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic substituent having 6 to 18 carbon atoms, or an alkoxycarbonyl group
- Hal represents a halogen atom Represents an atom).
- R 8 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
- R 9 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a benzyl group, a t-butoxycarbonyl group, or a benzyloxycarbonyl group.
- Hal is preferably a chlorine atom or a bromine atom.
- vinyl compound having a polar group represented by the general formula (2) examples include vinyl acetate, allyl acetate, allyl alcohol, methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, acrylonitrile, allylamine, and N-allyl.
- examples include aniline, Nt-butoxycarbonyl-N-allylamine, N-benzyloxycarbonyl-N-allylamine, N-benzyl-N-allylamine, allyl chloride, allyl bromide and the like.
- vinyl acetate, allyl acetate, methyl methacrylate, methyl acrylate, or acrylonitrile is particularly preferable. These can be used alone or in combination of two or more.
- ethylene and vinyl acetate, ethylene and allyl acetate, ethylene and allyl alcohol, ethylene and methyl methacrylate, ethylene and methyl acrylate, ethylene and acrylonitrile, ethylene and allyl chloride, ethylene in terms of polymer performance and economy And allylamine are preferred.
- one or more third monomers may be copolymerized in addition to the monomers represented by the general formulas (1) and (2).
- the third monomer include ethyl vinyl ether, propyl vinyl ether, norbornene, and carbon monoxide.
- 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 molar ratio of the metal complex catalyst represented by the general formula (C1) or (C2) to the total amount of monomers is a monomer / metal complex ratio in the range of 1 to 10,000,000, preferably 10 to 1,000,000.
- the range of 100 to 100,000 is more preferably used.
- the charge ratio of the monomers represented by the general formula (1) and the general formula (2) is appropriately adjusted according to the composition ratio of the target copolymer. The same applies when the third monomer is used.
- the polymerization temperature is not particularly limited. Usually, it is carried out in the range of ⁇ 30 to 200 ° C., preferably 0 to 180 ° C., more preferably 20 to 150 ° C.
- the polymerization pressure in which the pressure of the olefin represented by the general formula (1) occupies most of the internal pressure is within the range of normal pressure to 20 MPa, preferably within the range of normal pressure to 10 MPa.
- 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.) to obtain a simple product. Be released.
- the (co) polymer can be formed into a pellet shape, a film shape, a sheet shape, or the like under the conditions of a normal thermoplastic resin.
- the obtained (co) polymer can be made into a product by itself such as injection molding, extrusion molding or film molding. Alternatively, it can be used as a modifier for surface properties such as adhesion and printability, a compatibilizer between nonpolar polyolefin and other highly polar resins, and a dispersant such as pigment by adding to polyolefin. Alternatively, applications such as paints, inks, adhesives, binders, plasticizers, lubricants, lubricating oils, surfactants and the like can also be mentioned.
- metal complex 1 and metal complex 2 obtained in the examples were determined by X-ray crystal structure analysis using a CCD single crystal X-ray diffractometer (Mercury CCD) manufactured by Rigaku Corporation.
- the reflection intensity was corrected by the Lorentz effect.
- the structure was solved by the direct method with SIR-97 and optimized with SHELXL-97. Atoms other than hydrogen were optimized anisotropically and hydrogen atoms were placed using the AFIX instruction.
- the number average molecular weight and the weight average molecular weight are measured by Tosoh Corp., TSKgel GMHHR-H (S) HT column (7.8 mm ID x 30 cm in series) and a high temperature GPC device manufactured by Tosoh Corp. This was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C.) using HLC-8121GPC / HT and polystyrene as a molecular weight standard substance.
- Metal complex 1c was synthesized according to the following reaction scheme.
- Metal complex 2c was synthesized according to the following reaction scheme.
- metal complex 2c was obtained in the same manner using metal complex 2b (33.7 g, 58.5 mmol) instead of metal complex 1b. The yield was 27.6 g (94%).
- Example 1 Synthesis of metal complex 1 Under a nitrogen atmosphere, a suspension of metal complex 1c (0.12 g, 0.20 mmol) in toluene (10 mL) / allyl acetate (10 mL) was heated to 80 ° C. and stirred for 1 hour. After the reaction solution was concentrated, methylene chloride (10 mL) was added to the residue, and the precipitate was removed by filtration using a syringe filter. Hexane (15 mL) was slowly added to the filtrate for recrystallization. The precipitated crystals were collected by filtration, washed with hexane, and dried under reduced pressure to obtain metal complex 1. The yield was 0.083 g (66%). Furthermore, the obtained metal complex 1 produced a single crystal from methylene chloride / hexane, and the structure was determined by X-ray crystal structure analysis. An X-ray structural analysis diagram of the metal complex 1 is shown in FIG.
- Example 2 Synthesis of metal complex 2
- the metal complex 2c was synthesized by the same method as in Example 1 using the metal complex 2c. That is, in a nitrogen atmosphere, a suspension of compound 2c (1.2 g, 2.4 mmol) in toluene (94 mL) / allyl acetate (94 mL) was heated to 80 ° C. and stirred for 2 hours. After the reaction solution was concentrated, methylene chloride (10 mL) was added to the residue, and the precipitate was removed by filtration using a syringe filter. Hexane (15 mL) was slowly added to the filtrate for recrystallization.
- the precipitated crystals were collected by filtration, washed with t-butyl methyl ether and hexane, and then dried under reduced pressure to obtain metal complex 2.
- the yield was 1.1 g (83%).
- the obtained metal complex 2 produced a single crystal from acetone / hexane, and the structure was determined by X-ray crystal structure analysis.
- An X-ray structural analysis diagram of the metal complex 2 is shown in FIG.
- Reference Example 1 Stability comparison of metal complex 2c and metal complex 2 in the presence of acetic acid
- a comparative experiment was conducted on the stability of metal complex 2c and metal complex 2 in the presence of acetic acid. That is, the metal complex 2c (0.0037 mmol) and the metal complex 2 (0.0037 mmol) were filled in each NMR tube (inner diameter 5 mm), and a heavy toluene solution of acetic acid (0.062 M, 0.6 mL, 0.037 mmol). And 1 H-NMR measurement was performed. The NMR tube was heated at 80 ° C. for 10 hours, and 1 H-NMR measurement was performed again.
- the peak of acetic acid is observed at 1.59 ppm and 9.80 ppm, and can be distinguished from the peaks of the metal complex 2, the metal complex 2c, and the lutidine.
- Protic acids such as acetic acid and acrylic acid are present as impurities in the polar group-containing olefin, which is a polymerization monomer.
- the result of Reference Example 1 shows that the metal complex of the present invention is very stable against the impurities, and it is difficult for decomposition to occur during the polymerization reaction.
- Example 3 Ethylene homopolymerization (Preparation of polymer 1) Under a nitrogen atmosphere, a toluene solution (75 mL) of metal complex catalyst 2 (0.50 mmol) was added to a 120 mL autoclave. After filling ethylene to an internal pressure of 3.0 MPa, the autoclave was stirred at 80 ° C. for 15 minutes. After cooling to room temperature, the reaction solution was added to methanol (400 mL). The resulting polymer was collected by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 1. The yield was 0.24 g, the number average molecular weight was 19,000, the weight average molecular weight was 42,000, and Mw / Mn was 2.2.
- Example 4 Copolymerization of allyl acetate and ethylene (Preparation of polymer 2) Under a nitrogen atmosphere, a toluene solution (37.5 mL) of metal complex catalyst 2 (0.10 mmol) was added to a 120 mL autoclave containing allyl acetate (37.5 mL, 34.9 g, 350 mmol). After filling ethylene to an internal pressure of 3.0 MPa, the autoclave was stirred at 80 ° C. for 5 hours. After cooling to room temperature, the reaction solution was added to methanol (400 mL). The resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 2.
- methanol 400 mL
- the yield was 2.7 g, the number average molecular weight was 12,000, the weight average molecular weight was 25,000, and Mw / Mn was 2.1.
- the allyl acetate content in the polymer 2 was determined to be 3.1% in terms of molar fraction by 13 C-NMR using a reverse gated decoupling method.
- Example 5 Copolymerization of allyl acetate and ethylene (Preparation of polymer 3) Under a nitrogen atmosphere, a toluene solution (37.5 mL) of metal complex catalyst 2 (0.010 mmol) was added to a 120 mL autoclave containing allyl acetate (37.5 mL, 34.9 g, 350 mmol). After filling ethylene to an internal pressure of 3.0 MPa, the autoclave was stirred at 80 ° C. for 25 hours. After cooling to room temperature, the reaction solution was added to methanol (400 mL). The resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 3.
- methanol 400 mL
- the yield was 2.2 g, the number average molecular weight was 12,000, the weight average molecular weight was 28,000, and Mw / Mn was 2.3.
- the allyl acetate content in the copolymer was determined to be 3.4% by mole fraction by 13 C-NMR using a reverse gated decoupling method.
- toluene (3.75 mL) and allyl acetate (7.5 mL, 7.0 g, 70 mmol) were added to the catalyst solution.
- the autoclave was stirred at 80 ° C. for 15 hours.
- methanol (about 20 mL) was added to the autoclave.
- the resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain a polymer.
- the yield was 1.7 g, the number average molecular weight was 4,000, the weight average molecular weight was 9,000, and Mw / Mn was 2.7.
- the allyl acetate content in the copolymer was determined to be 2.7% in terms of mole fraction by 13 C-NMR using a reverse gated decoupling method.
- Example 6 Copolymerization of allyl acetate and ethylene (Preparation of polymer 4) Under a nitrogen atmosphere, a toluene solution (188 mL) of metal complex catalyst 2 (0.050 mmol) was added to a 500 mL autoclave containing allyl acetate (188 mL, 174 g, 1740 mmol). After filling ethylene to an internal pressure of 3.0 MPa, the autoclave was stirred at 80 ° C. for 50 hours. After cooling to room temperature, the reaction solution was added to methanol (1000 mL). The resulting copolymer was collected by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 4.
- the yield was 23 g, the number average molecular weight was 12,000, the weight average molecular weight was 28,000, and Mw / Mn was 2.3.
- the allyl acetate content in the copolymer was determined to be 3.4% by mole fraction by 13 C-NMR using a reverse gated decoupling method.
- Example 7 Synthesis of metal complex 3 Under an argon atmosphere, bis (1,5-cyclooctadiene) nickel (0.14 g, 0.50 mmol), 2- (dicyclohexylphosphino) benzenesulfonic acid (Compound 1a, 0.21 g, 0.60 mmol), 2, 6-Dimethylpyridine (0.11 g, 1.0 mmol) and THF (30 mL) were allowed to stir at room temperature for 5 hours. Allyl acetate (1 mL, 0.93 g, 9.3 mmol) was added to the reaction solution, and further reacted. After the reaction solution was filtered, the filtrate was concentrated under reduced pressure to obtain 0.12 g (43%) of an orange powder. It was confirmed to be metal complex 3 by 31 P-NMR spectrum. 31 P-NMR (162 MHz, CD 2 Cl 2 ): ⁇ 16.6 (s).
- Example 8 Ethylene homopolymerization (Preparation of polymer 5) Toluene (6 mL) was added to a 50 mL autoclave containing metal complex catalyst 3 (0.050 mmol) under a nitrogen atmosphere. After filling ethylene to an internal pressure of 3.0 MPa, the autoclave was stirred at 80 ° C. for 7 hours. After cooling to room temperature, methanol (20 mL) was added to the autoclave. The resulting polymer was collected by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 5. The yield was 0.12 g, the number average molecular weight was 2,800, the weight average molecular weight was 9,800, and Mw / Mn was 3.5.
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Abstract
Description
一般的に、配位重合に用いる触媒系として、金属-水素結合、または金属-炭素結合をもつ金属錯体が使用されてきた。
J. Am. Chem. Soc., 127, 5132 (2005)(非特許文献1)には、周期律表第10族の金属錯体を使用した酢酸ビニルの重合における重合機構と触媒失活機構が示されている。特に、触媒失活機構の1つとして、金属-アルキル結合への酢酸ビニル挿入後のβ-アセトキシ脱離を提唱しているが、これは、β-アセトキシ脱離により生成する金属-アセトキシ錯体が重合活性を有しないことを示しており、一般に金属-酸素結合へのオレフィン挿入は起こり得ないと認識されていた。
[1]一般式(C1)
で示されるカルボキシラート金属錯体。
[2]一般式(C1)で示されるカルボキシラート金属錯体が、一般式(C2)
で示される[1に記載のカルボキシラート金属錯体。
[3]一般式(C2)中のMが、NiまたはPdである[2]に記載のカルボキシラート金属錯体。
[4]一般式(C2)中のR1が、ハロゲン原子で置換されていてもよい炭素原子数1~30の炭化水素基である[2]または[3]に記載のカルボキシラート金属錯体。
[5]一般式(C2)中のR1がメチル基またはトリフルオロメチル基である[4]に記載のカルボキシラート金属錯体。
[6]一般式(C2)中のR1がメチル基である[5]に記載のカルボキシラート金属錯体。
[7]一般式(C2)中のR2及びR3がともにイソプロピル基またはシクロヘキシル基である[2]~[6]のいずれかに記載のカルボキシラート金属錯体。
[8]一般式(C2)中のR4がすべて水素原子である[2]~[7]のいずれかに記載のカルボキシラート金属錯体。
[9]一般式(C2)中のLが2,6-ジメチルピリジンであり、nが1である[2]~[8]のいずれかに記載のカルボキシラート金属錯体。
[10][1]~[9]のいずれかに記載のカルボキシラート金属錯体を主成分とするオレフィン重合用触媒。
[11][1]~[9]のいずれかに記載のカルボキシラート金属錯体を触媒として使用し、一般式(1)
で示されるオレフィンを単独であるいは2種以上を組み合わせて重合するか、または前記一般式(1)で示されるオレフィンと一般式(2)
で示される極性基含有オレフィンとを共重合することを特徴とする重合体の製造方法。
なお、本明細書では「炭化水素」は飽和、不飽和の脂肪族炭化水素、脂環式炭化水素、及び芳香族炭化水素を含む。
Mは周期律表第10族の元素を表す。周期律表第10族の元素としては、ニッケル(Ni)、パラジウム(Pd)、白金(Pt)が挙げられるが、Ni及びPdが好ましく、Pdがより好ましい。
中性の電子供与性配位子としては、硫黄原子を有するものとしてジメチルスルホキシド(DMSO)が挙げられる。窒素原子を有するものとして、炭素原子数1~10のトリアルキルアミン、ジアルキルアミン、ピリジン、2,6-ジメチルピリジン、キノリン、2-メチルキノリン、アニリン、2,6-ジメチルアニリン、2,6-ジイソプロピルアニリン、N,N,N’,N’-テトラメチルエチレンジアミン(TMEDA)、4-(N,N-ジメチルアミノ)ピリジン(DMAP)、アセトニトリル、ベンゾニトリルなどが挙げられる。リン原子を有するものとして、トリメチルホスフィン、トリイソプロピルホスフィン、トリブチルホスフィン、トリ(t-ブチル)ホスフィン、トリフェニルホスフィン、トリス(o-トリル)ホスフィン、トリフリルホスフィンなどが挙げられる。酸素原子を有するものとして、ジエチルエーテル、テトラヒドロフラン、1,4-ジオキサン、1,2-ジメトキシエタンなどが挙げられる。合成手法の観点から、窒素原子を有するもの、リン原子を有するものが好ましく、特に窒素原子を有するものが好ましい。
R12が表すハロゲン原子としては、塩素原子、臭素原子、またはヨウ素原子が挙げられ、経済性の面から塩素原子または臭素原子が好ましい。
第3のモノマーとしては、エチルビニルエーテル、プロピルビニルエーテル、ノルボルネン、一酸化炭素などが挙げられる。
重合方法は特に制限されるものではなく、一般に使用される方法で重合可能である。すなわち、溶液重合法、懸濁重合法、気相重合法などのプロセス法が可能であるが、特に溶液重合法、懸濁重合法が好ましい。また重合様式は、バッチ様式でも連続様式でも可能である。また、一段重合でも、多段重合でも行うこともできる。
一般式(1)で示されるオレフィンの圧が内部圧力の大半を占める重合圧力については、常圧から20MPaの範囲内、好ましくは常圧から10MPaの範囲内で行われる。
(共)重合体は、通常の熱可塑性樹脂の条件で、ペレット状、フィルム状、シート状などに成形することができる。
実施例で得た金属錯体1及び金属錯体2の構造は、リガク(株)製CCD型単結晶X線回折装置(Mercury CCD)を用いたX線結晶構造解析により決定した。X線としてはMoのKα線(λ=0.71069Å)を用い、2θ=50°までの反射を用いた。反射強度はローレンツ効果により補正した。構造はSIR-97による直接法により解き、SHELXL-97により最適化した。水素以外の原子は異方的に最適化し、水素原子はAFIX instructionを用いて配置した。
実施例で得た重合体の構造は、日本電子(株)製JNM-ECS400を用いた各種NMR解析により決定した。一般式(2)で示される極性基含有オレフィンに由来するモノマーユニットの含有率と共重合体末端構造は、溶媒として1,2,4-トリクロロベンゼン(0.55mL)及び緩和試薬としてCr(acac)3(10mg)を用い、120℃において、逆ゲート付きデカップリング法を用いた13C-NMR(9.0マイクロ秒の90°パルス、スペクトル幅:31kHz、緩和時間:10秒、取り込み時間:10秒、FIDの積算回数5,000~10,000回)によって決定した。
アルゴン雰囲気下、ベンゼンスルホン酸(東京化成工業製、0.66g,4.2mmol)のテトラヒドロフラン(THF)溶液(20mL)に、n-ブチルリチウム(関東化学製、1.65Mヘキサン溶液,5.1mL,8.4mmol)を0℃で加え、室温で2.5時間撹拌した。反応容器を-78℃に冷却した後にクロロジシクロヘキシルホスフィン(Sigma-Aldrich社製,0.89g,3.8mmol)を-78℃で加え、室温で24時間撹拌した。反応をトリフルオロ酢酸(東京化成工業製、0.50M THF溶液,8.4mL,4.2mmol)で停止した後に、生じた沈殿をろ過によって回収し減圧下乾燥し、2-(ジシクロヘキシルホスフィノ)ベンゼンスルホン酸(2-(dicyclohexylphosphino)benzenesulfonic acid)(化合物1a)を得た。収量は0.66g(85%)であった。
13C-NMR(101MHz,CDCl3):δ 25.0 (s), 25.6-26.2 (m), 28.8 (br), 30.3 (br), 34.6 (br d, 1JPC = 40 Hz), 113.4 (br d, 1JPC = 87 Hz), 128.8 (d, JPC = 9 Hz), 130.1 (d, JPC = 9 Hz), 135.4 (br), 137.1 (br), 150.5 (br);
31P-NMR(162MHz,CDCl3):δ 52.8 (d, 1JPH = 370 Hz) (90%), 20.8 (d, 1JPH = 530 Hz) (10%);
Anal. calcd for C18H27O3PS, C, 60.99; H, 7.68. found: C, 60.90; H, 7.55。
アルゴン雰囲気下、化合物1a;2-(ジシクロヘキシルホスフィノ)ベンゼンスルホン酸(0.43g,1.2mmol)とジイソプロピルエチルアミン(和光純薬工業製、1.1mL,6.0mmol)の塩化メチレン溶液(16mL)に、(COD)PdMeCl(文献:「Inor. Chem., 1993, 32, 5769-5778」に従って合成。COD=1,5-シクロオクタジエン、0.32g,1.2mmol)の塩化メチレン溶液(6mL)を加え、室温で1時間撹拌した。溶液を濃縮した後に、ろ過により沈殿物を取り除き、溶液をヘキサン中に加えた。生じた沈殿をろ過によって回収し、ヘキサンで洗浄した後に減圧下乾燥し、金属錯体1bを得た。収量は0.66g(85%)であった。
13C-NMR(101MHz,CDCl3):δ -7.3 (s, PdCH3), 12.0 (s, HNCH2CH3), 17.9 (s, HNCH(CH3)2), 19.2 (s, HNCH(CH3)2), 26.0 (s), 26.9-27.4 (m), 28.7 (s), 29.4 (d, JPC = 4 Hz), 35.6 (d, 1JPC = 25 Hz), 42.4 (s, HNCH2CH3), 54.6 (s, HNCH(CH3)2), 125.5 (d, 1JPC = 33 Hz), 128.3 (d, JPC = 7 Hz), 128.9 (d, JPC = 6 Hz), 130.3 (s), 132.5 (s), 150.9 (d, 2JPC = 11 Hz);
31P-NMR(162MHz,CDCl3):δ 31.7;
Anal. calcd for C27H49ClNO3PPdS, C, 50.62; H, 7.71; N, 2.19. found: C, 50.49; H, 8.00, N, 2.12。
アルゴン雰囲気下、炭酸カリウム(0.42g,3.0mmol)と2,6-ルチジン(東京化成工業製、0.33g,3.1mmol)の塩化メチレン懸濁液(2mL)に、金属錯体1b(0.19g,0.30mmol)の塩化メチレン溶液(4mL)を加え、室温で1時間撹拌した。溶媒を減圧下留去して残った固体をジエチルエーテルで洗浄した後に、塩化メチレンで抽出した。抽出液をセライト(乾燥珪藻土)でろ過し、ゆっくりとヘキサン(40mL)中に加えた。生じた沈殿をろ過によって回収し、ヘキサンで洗浄した後に減圧下乾燥し、金属錯体1cを得た。収量は0.12g(70%)であった。
13C-NMR(101MHz,CDCl3):δ -9.4 (d, 2JPC = 4.8 Hz, PdCH3), 26.3 (s, CH3 of lutidine), 26.9-27.5 (m), 28.6 (s), 29.6 (d, JPC = 3 Hz), 35.5 (d, 1JPC = 26 Hz), 122.5 (s),122.5 (s), 124.6 (d, 1JPC = 35 Hz), 128.9 (d, JPC = 7 Hz), 129.0 (d, JPC = 6 Hz), 130.7 (s), 132.4 (s), 138.1 (s). 151.0 (d, 2JPC = 12 Hz), 159.0 (s);
31P-NMR(162MHz,CDCl3):δ 27.5;
Anal. calcd for C26H38NO3PPdS, C, 53.65; H, 6.58; N, 2.51. found: C, 53.51; H, 6.74; N, 2.40。
上記化合物1aの合成において、クロロジシクロヘキシルホスフィンの代わりにクロロジイソプロピルホスフィン(Sigma-Aldrich製,19.0g,125mmol)を用いたほかは同様にして2-(ジイソプロピルホスフィノ)ベンゼンスルホン酸(2-(diisopropylphosphino)benzenesulfonic acid)(化合物2a)を得た。収量は26.8g(78%)であった。
13C-NMR(101MHz,CDCl3):δ19.4 (s), 24.5-27.7 (m), 114.4 (br d, J = 93 Hz), 129.1 (d, J = 8.6 Hz), 130.3 (d, J = 12.5 Hz), 134.7-137.1 (m), 150.7 (br s);
31P-NMR(162MHz,CDCl3):δ62.5 (d, 1JPH = 380 Hz) (83%), 31.0 (d, 1JPH = 460 Hz) (17%)。
上記化合物1bの合成において、化合物1aの代わりに化合物2a(2-(ジシクロヘキシルホスフィノ)ベンゼンスルホン酸)(16.3g,59.3mmol)を用い同様にして金属錯体2bを得た。収量は33.7g(99%)であった。
13C-NMR(101MHz,CDCl3):δ-7.79 (s), 12.16 (s), 17.91 (s), 18.54 (s), 19.21-19.28 (m), 25.93 (d, J = 25.9 Hz), 42.58 (s), 54.69 (s), 125.25 (s), 125.58 (s), 128.8 (d, J = 6.7 Hz), 129.13 (d, J = 5.8 Hz), 130.58 (s), 132.48 (s), 150.89 (d, J = 10.5 Hz);
31P-NMR(162MHz,CDCl3):δ38.4 (s)。
上記金属錯体1cの合成において、金属錯体1bの代わりに金属錯体2b(33.7g,58.5mmol)を用い同様にして金属錯体2cを得た。収量は27.6g(94%)であった。
13C-NMR(101MHz,CDCl3):δ-10.10 (d, J = 4.8 Hz), 18.44 (s), 19.29 (d, J = 4.8 Hz), 25.91 (d, J = 25.9 Hz), 26.20 (s), 122.72 (d, J = 3.8 Hz), 124.56 (d, J = 35.5 Hz), 129.19 (t, J = 6.7 Hz), 131.03 (d, J = 1.9 Hz), 132.39 (s), 138.30 (s), 151.13 (d, J = 10.5 Hz), 159.17 (s);
31P-NMR(162MHz,CDCl3):δ34.4 (s);
Anal. calcd for C20H30NO3PPdS, C, 47.86; H, 6.02; N, 2.79. found: C, 47.92; H, 5.98; N, 2.51。
13C-NMR(101MHz,CDCl3):δ 22.7(s), 24.7 (s), 26.1 (s), 27.1-27.3 (m),28.1 (d, 1Jpc = 19 Hz), 34.7 (d, 1Jpc = 25 Hz),121.7 (s), 122.1 (s), 122.8 (d, Jpc = 3 Hz), 128.7 (d, Jpc = 7 Hz), 130.1 (d, Jpc = 6 Hz),131.9 (s),132.1 (s),138.7 (s), 148.9 (d, Jpc = 10 Hz), 160.1 (s), 176.7 (s).
31P-NMR(162MHz,CDCl3):δ 17.0 (s)
13C-NMR(101MHz,CDCl3):δ 17.7 (s), 17.8 (s), 22.5 (s), 24.5 (s, CH3 of lutidine), 25.0 (d, 1JPC = 26.5 Hz), 121.4 (d, 1JPC = 39.8 Hz), 122.6 (s), 128.5 (d, JPC = 5.7 Hz), 129.8 (d, JPC = 5.8 Hz), 131.6 (s), 131.8 (s), 138.5 (s), 148.5 (d, 2JPC = 8.3 Hz), 159.8 (s), 176.7 (s)。
金属錯体2cと金属錯体2の酢酸存在下での安定性の比較実験を実施した。すなわち、金属錯体2c(0.0037mmol)及び金属錯体2(0.0037mmol)をそれぞれのNMRチューブ(内径5mm)に充填し、酢酸の重トルエン溶液(0.062M、0.6mL、0.037mmol)を加え、1H-NMR測定をした。このNMRチューブを80度で10時間に加熱した後、再度1H-NMR測定を行った。金属錯体2cを含む反応液には、金属錯体2c由来のピーク以外に、金属錯体2由来のピーク(δ1.74ppm,3.44ppm,8.22ppm)及び分解して中心金属から解離した2,6-ジメチルピリジン(ルチジン)由来のピーク(δ2.38ppm)が観測された。これらの存在比率は、ルチジンベースの積算値から、金属錯体2c(81.7%)、金属錯体2(10.6%)、解離ルチジン(7.7%)と算出した。一方、金属錯体2を含む反応液には、金属錯体2由来のピーク以外は錯体由来のピークが観測されなかった。なお、酢酸のピークは、1.59ppm及び9.80ppmに観測され、上記の金属錯体2、金属錯体2c、及びルチジンのピークと区別することができる。
酢酸やアクリル酸などのプロトン酸は、重合モノマーである極性基含有オレフィン中に不純物として存在している。参考例1の結果は、本発明の金属錯体がその不純物に対して非常に安定であり、重合反応中でもそれによる分解が起こりにくいことを示している。
窒素雰囲気下、120mLオートクレーブ中に、金属錯体触媒2(0.50mmol)のトルエン溶液(75mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、15分撹拌した。室温に冷却後、反応液をメタノール(400mL)に加えた。生じた重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体1を得た。収量は0.24g、数平均分子量は19,000、重量平均分子量は42,000、Mw/Mnは2.2であった。
窒素雰囲気下、酢酸アリル(37.5mL,34.9g,350mmol)を含む120mLオートクレーブ中に、金属錯体触媒2(0.10mmol)のトルエン溶液(37.5mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、5時間撹拌した。室温に冷却後、反応液をメタノール(400mL)に加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体2を得た。収量は2.7g、数平均分子量は12,000、重量平均分子量は25,000、Mw/Mnは2.1であった。重合体2中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C-NMRにより、モル分率で3.1%と決定した。
窒素雰囲気下、酢酸アリル(37.5mL,34.9g,350mmol)を含む120mLオートクレーブ中に、金属錯体触媒2(0.010mmol)のトルエン溶液(37.5mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、25時間撹拌した。室温に冷却後、反応液をメタノール(400mL)に加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体3を得た。収量は2.2g、数平均分子量は12,000、重量平均分子量は28,000、Mw/Mnは2.3であった。共重合体中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C-NMRにより、モル分率で3.4%と決定した。
アルゴン雰囲気下、化合物2b(0.12mmol)とPd2(DBA)3・CHCl3(DBA=ジベンジリデンアセトン,0.10mmol)を含む50mLオートクレーブ中に、塩化メチレン(3.75mL)を加え、10分間撹拌した。このとき、触媒種として、Pd-ヒドリド錯体が形成していると考えられる(参考文献:J. Am. Chem. Soc., 131, 14605 (2009))。その後、触媒液にトルエン(3.75mL)及び酢酸アリル(7.5mL,7.0g,70mmol)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、15時間撹拌した。室温に冷却後、オートクレーブ中にメタノール(約20mL)を加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥して、重合体を得た。収量は1.7g、数平均分子量は4,000、重量平均分子量は9,000、Mw/Mnは2.7であった。共重合体中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C-NMRにより、モル分率で2.7%と決定した。
窒素雰囲気下、酢酸アリル(188mL,174g,1740mmol)を含む500mLオートクレーブ中に、金属錯体触媒2(0.050mmol)のトルエン溶液(188mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、50時間撹拌した。室温に冷却後、反応液をメタノール(1000mL)に加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体4を得た。収量は23g、数平均分子量は12,000、重量平均分子量は28,000、Mw/Mnは2.3であった。共重合体中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C-NMRにより、モル分率で3.4%と決定した。
31P-NMR(162MHz,CD2Cl2):δ 16.6 (s)。
窒素雰囲気下、金属錯体触媒3(0.050mmol)を含む50mLオートクレーブ中に、トルエン(6mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、7時間撹拌した。室温に冷却後、オートクレーブ中にメタノール(20mL)を加えた。生じた重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体5を得た。収量は0.12g、数平均分子量は2,800、重量平均分子量は9,800、Mw/Mnは3.5であった。
Claims (11)
- 一般式(C1)
で示されるカルボキシラート金属錯体。 - 一般式(C2)中のMが、NiまたはPdである請求項2に記載のカルボキシラート金属錯体。
- 一般式(C2)中のR1が、ハロゲン原子で置換されていてもよい炭素原子数1~30の炭化水素基である請求項2または3に記載のカルボキシラート金属錯体。
- 一般式(C2)中のR1がメチル基またはトリフルオロメチル基である請求項4に記載のカルボキシラート金属錯体。
- 一般式(C2)中のR1がメチル基である請求項5に記載のカルボキシラート金属錯体。
- 一般式(C2)中のR2及びR3がともにイソプロピル基またはシクロヘキシル基である請求項2~6のいずれかに記載のカルボキシラート金属錯体。
- 一般式(C2)中のR4がすべて水素原子である請求項2~7のいずれかに記載のカルボキシラート金属錯体。
- 一般式(C2)中のLが2,6-ジメチルピリジンであり、nが1である請求項2~8のいずれかに記載のカルボキシラート金属錯体。
- 請求項1~9のいずれかに記載のカルボキシラート金属錯体を主成分とするオレフィン重合用触媒。
- 請求項1~9のいずれかに記載のカルボキシラート金属錯体を触媒として使用し、一般式(1)
で示されるオレフィンを単独であるいは2種以上を組み合わせて重合するか、または前記一般式(1)で示されるオレフィンと一般式(2)
で示される極性基含有オレフィンとを共重合することを特徴とする重合体の製造方法。
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