WO2004037870A1 - マグネシウムを含む担体成分及びオレフィン重合への応用 - Google Patents
マグネシウムを含む担体成分及びオレフィン重合への応用 Download PDFInfo
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- WO2004037870A1 WO2004037870A1 PCT/JP2003/013361 JP0313361W WO2004037870A1 WO 2004037870 A1 WO2004037870 A1 WO 2004037870A1 JP 0313361 W JP0313361 W JP 0313361W WO 2004037870 A1 WO2004037870 A1 WO 2004037870A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- 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
- C08F4/02—Carriers therefor
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
Definitions
- the present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the olefin polymerization catalyst. More specifically, the present invention relates to an organic aluminum oxy compound or an organic boron compound conventionally used as an olefin polymerization catalyst component. The present invention relates to a catalyst for olefin polymerization containing no compound, a method for producing an olefin polymer using the catalyst for polymerization of olefin, and a polyolefin excellent in powder properties obtained by the production method. Background art
- a method of polymerizing an olefin by using a group having a conjugated C electron, particularly a meta-opencane compound having cyclopentene or its derivative as a ligand, as a catalyst and combining with an organoaluminoxy compound or an organoboron compound is known.
- a group having a conjugated C electron particularly a meta-opencane compound having cyclopentene or its derivative as a ligand
- an organoaluminoxy compound or an organoboron compound is known.
- Japanese Patent Application Laid-Open No. 58-19309 discloses a method for polymerizing olefins using biscyclopentagenenyl zirconium dichloride and methylaluminoxane as catalysts.
- a system in which the olefin polymerization proceeds without combination with an organoaluminoxy compound or an organoboron compound has also been disclosed.
- Japanese Patent Application Laid-Open No. Hei 4- 211405 discloses that a solid support obtained by contacting magnesium chloride and an electron donor containing no active hydrogen with an electron donor containing active hydrogen is combined with a zirconium meta-mouth compound.
- a method for olefin polymerization is disclosed.
- Japanese Patent Application Laid-Open No. 7-330821 discloses a method for polymerizing a solid component obtained by reacting a magnesium compound such as magnesium oxide with an organoaluminum compound in combination with a titanium metamouth compound. I have.
- meta-opencane compounds exhibit high olefin polymerization activity unless used in combination with expensive organoaluminoxy compounds or organoboron compounds.
- the bulk density of the polymer produced after polymerization is low, handling is difficult, and when applied to gas-phase or liquid-phase polymerization, the polymer adheres to the polymerization vessel wall, making it difficult to remove heat due to poor heat transfer.
- the present invention has been made in view of the technical background as described above, and has a high polyolefin polymerization activity even without being used in combination with an expensive organic aluminum compound or an organic boron compound. It is a main object of the present invention to provide a polymerization catalyst capable of maintaining high activity even in polymerization for a long time, and a method for producing an olefin polymer excellent in powder properties using such a catalyst.
- the above-mentioned problems include a magnesium atom, an aluminum atom and an alkoxy group having 1 to 20 carbon atoms, both of which are adjusted by a specific method, and (i) a molar ratio of magnesium atom to aluminum atom (Mg / A l) is within the range of 1.0 ⁇ (M g ZA l) ⁇ 300, and ( ⁇ ) the molar ratio of the alkoxy group to the aluminum atom (OR / A 1) is 0.5 ⁇ (OR / A 1) satisfying 2.0, (iii) having an average particle size of 3 to 80 jm, and a hydrocarbon solvent This is achieved by using an olefin polymerization catalyst containing solid fine particles insoluble in water.
- the present invention relates to 1) a carrier component containing magnesium, 2) a catalyst for polymerization of olefins containing the carrier component, 3) a method for polymerizing olefins using the catalyst for polymerization of olefins, and 4) a polyolefin obtained by the polymerization method.
- a carrier component containing magnesium 2) a catalyst for polymerization of olefins containing the carrier component, 3) a method for polymerizing olefins using the catalyst for polymerization of olefins, and 4) a polyolefin obtained by the polymerization method.
- the carrier component containing magnesium of the present invention (hereinafter may be simply referred to as “carrier”) contains both a magnesium atom, an aluminum atom and an alkoxy group having 1 to 20 carbon atoms, and is insoluble in a hydrocarbon solvent. And the average particle size is 3 to 80 m.
- the molar ratio of magnesium atoms to aluminum atoms (MgZAl) in the carrier component is in the range of 1.0 ⁇ Mg / A 1 ⁇ 300.0, and the molar ratio of alkoxy groups to aluminum atoms (ORZA 1) is 0. .
- insoluble in a hydrocarbon solvent means that at least one solvent selected from hexane, decane, and toluene is used for 1 minute at a temperature ranging from o ° c to the intrinsic boiling point of the solvent under normal pressure.
- the content of dissolved magnesium atoms is 0.5% by weight or less even after stirring for 1 hour and at least one kind of solvent selected from hexane, decane and toluene is added for 1 minute at room temperature under normal pressure. It means that the dissolved amount of aluminum atom and alkoxy group is 1% by weight or less, respectively, even after stirring for up to 1 hour.
- the carrier component of the present invention may contain other metal atoms and other organic groups in addition to magnesium, aluminum, and alkoxy groups, but does not contain group 4 transition metal atoms such as titanium, zirconium, and hafnium. Is preferred.
- the component (A) described below contains a component containing at least two or more atoms selected from a boron atom, a nitrogen atom, an oxygen atom, a phosphorus atom, and an iodine atom.
- Olefin polymer derived from transition metal compounds belonging to Groups 3 to 11 of the periodic table having ligands, and olefin polymer derived from contained titanium atoms are formed together.
- the carrier component of the present invention contains not only a Group 4 transition metal atom, but also the olefin polymerization activity substantially in combination with the component (C) described below, which is optionally used. Preferably do not show
- the total amount of magnesium atoms, aluminum atoms, and alkoxy groups having 1 to 20 carbon atoms in the carrier component of the present invention is usually in the range of 10 to 90% by weight.
- the content is preferably 15 to 60% by weight, particularly preferably 20 to 40% by weight.
- Halogen atoms occupy the largest weight of components other than magnesium atoms, aluminum atoms, and alkoxy groups having 1 to 20 carbon atoms in the carrier components.
- the halogen atoms are chlorine atoms and the amount of chlorine atoms in the carrier component is as low as about 20% by weight, and as much as about 80% by weight.
- the carrier component may contain an alcohol corresponding to an alkoxy group having 1 to 20 carbon atoms, a residual organic solvent used in preparing the carrier component, and the like.
- the alkoxy group having 1 to 20 carbon atoms in the carrier component of the present invention is a group derived from an alcohol having 1 to 20 carbon atoms used as a raw material component when preparing a carrier component described later.
- alkoxy group having 1 to 20 carbon atoms examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy, i -Amyloxy, II-hexoxy, n-heptoxy, 2-ethylhexoxy, n-octoxy, dodecoxy, octadecyloxy, oleoxy, benzyloxy, phenylethoxy, cumyloxy, i- Halogen-containing alkoxy groups such as propylbenzyloxy group, trichloromethoxy group, trichloroethoxy group, trichlorohexoxy group, etc.
- Examples thereof include an alkyl group-containing phenoxy group.
- Molar ratio of magnesium atom to aluminum atom is usually in the range of 1.0 to MgZAl ⁇ 300.0, and is preferably 30.0 and MgNO Al ⁇ 250.0, more preferably, from the viewpoint of the polymerization activity of the olefin and the powder property of the resulting polyolefin. 30.0 ⁇ MgZAl ⁇ 200,0, more preferably 35.0 and MgZA 1 ⁇ 200.0, particularly preferably 40.0 and Mg / A 1 ⁇ 150.0.
- the molar ratio of the alkoxy group to the aluminum atom is usually 0.05 ⁇ ORZA1 ⁇ 2.0, and is preferably 0.8, particularly preferably 0.2, in order to further enhance the polymerization activity of the olefin.
- ⁇ OR / A 1 ⁇ 1.0.
- the average particle size of the carrier component of the present invention is from 3 to 80 zm, preferably from 3 to 50, the polymerization activity is improved when used as a below-described catalyst for olefin polymerization, and at the same time, the bulk density of the generated polyolefin is increased.
- one important parameter along with the average particle size is the crystallite size obtained by X-ray diffraction analysis of the magnesium halide constituting the carrier component. There is a high correlation between the microcrystal size and the polymerization activity, and it is considered that a carrier component with a small crystallite size is necessary to obtain high polymerization activity.
- the crystallite size of the present invention is usually 3 to 80 (A), preferably 10 to 75 (person), more preferably 12 to 70 (A), still more preferably 15 to 60 (person), particularly It is preferably in the range of 20 to 55 (A).
- the carrier component of the present invention is obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms (hereinafter, this contact may be referred to as “first contact”). (Hereinafter, this contact may be referred to as “second contact”), but the method for preparing the carrier component of the present invention is not limited to this method. is not.
- Magnesium bromide is preferably used as magnesium chloride or magnesium bromide.
- Such a magnesium halide may be a commercially available product as it is, may be separately prepared from an alkyl magnesium, and in the latter case, the magnesium halide can be used without isolation.
- the aforementioned alkoxy group having 1 to 20 carbon atoms examples are: methanol, ethanol, n- propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-butanol, i-butanol.
- methanol, ethanol, propanol, butanol, pentanol, i-amyl alcohol, hexanol, heptanol, 2-ethylhexanol, octanol and dodecanol are preferred.
- the contact may be carried out in the presence of a solvent.
- the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatics such as benzene, toluene and xylene Group hydrocarbons; halogenated hydrocarbons such as ethylene dichloride, chlorobenzene, and dichloromethane; and mixtures thereof.
- the contact is usually performed under heating.
- the temperature can be arbitrarily selected up to the boiling point of the solvent used.
- the contact time depends on the contact temperature, for example, n-decane is used as a solvent, and under the condition of a heating temperature of 130 ° C, the contact takes about 4 hours to produce a uniform content, and this is the contact. It is a measure of completion.
- it is usually carried out using a device that promotes contact by stirring or the like. At the start of contact, the system is usually heterogeneous, but as contact progresses, the contents gradually become homogeneous and eventually liquefy.
- the carrier component of the present invention is useful as a component of an olefin polymerization catalyst regardless of the degree of liquefaction, but the preparation method via complete liquefaction is more effective in improving the olefin polymerization activity and the powder property of the resulting polyolefin. Preferred from a viewpoint.
- first contact product The thus prepared contact product of magnesium halide and an alcohol having 1 to 20 carbon atoms (hereinafter sometimes referred to as “first contact product”) is used at the time of contact.
- the solvent may be used after removing it, or may be used without distilling off the solvent. Usually, it is used in the next step without distilling off the solvent.
- R represents a hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. be able to.
- X represents a halogen atom such as a chlorine atom or a bromine atom or a hydrogen atom.
- n represents a real number of 1 to 3, and is preferably 2 or 3.
- each R may be the same or different, and when there are a plurality of X, each X may be the same or different.
- the following compounds are specifically used as the organoaluminum compound.
- organoaluminum compound satisfying such requirements include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum, and isoprenylaluminum.
- the contact method in the second contact is not particularly limited, it is usually carried out by a method in which the organoaluminum compound represented by the general formula (z) is added to the first contact compound with stirring.
- the first contact product may be diluted with a solvent, and such a solvent may be used without any particular limitation as long as it is a hydrocarbon having no active hydrogen, but usually, the solvent used at the time of the first contact is used. It is efficient to use the solvent as it is during the second contact without distilling it off.
- the organic aluminum compound to be added to the first contact product may be used after being diluted with a solvent or may be added without being diluted with the solvent, but is usually a fat such as n-decane or n-hexane.
- the organic aluminum compound is added, it is usually added to the first contacted compound over 5 minutes to 5 hours. If the gradual heating capacity in the contact system is sufficient, the addition can be completed in a short time. If the capacity is insufficient, the addition is preferably performed over a long time.
- the organoaluminum compound may be added all at once or may be added in several portions. When divided addition is performed, the organoaluminum compound in each addition may be the same or different, and the temperature of the first contact compound in each addition may be the same or different.
- the amount of the organoaluminum compound represented by the general formula (Z) is usually 0.1 to 50 times mol, preferably 0.1 times mol of the magnesium atom in the first contact compound. 0.5 to 30 times, more preferably 1.0 to 20 times, more preferably 1.5 to 15 times, and particularly preferably 2.0 to 10 times the mole of aluminum atom.
- An organoaluminum compound is used.
- a hydrocarbon dilute solution of a magnesium compound is contacted with an organoaluminum compound diluted in a hydrocarbon solvent
- a means based on the reaction between the two liquids It is preferable to use a means based on the reaction between the two liquids.
- the amount of the organoaluminum compound used at that time varies depending on the type and contact conditions, but is usually 2 to 10 mol per 1 mol of the magnesium compound. Is preferred. Solid products vary in shape and size depending on their formation conditions.
- a magnesium compound and an organoaluminum compound are contacted and mixed in a liquid state with each other to form a solid product by mutual reaction.
- it is easy to control the particle size of the solid product and it is easy to obtain a granular or spherical solid product having a narrow particle size distribution.
- the obtained polymer is granular or spherical, and the particle size distribution is narrow. Large bulk density and good fluidity.
- the carrier component described above can be used not only as a constituent component of the below-described catalyst for olefin polymerization, but also as a catalyst for many organic synthesis reactions by utilizing the Lewis acid function contained in the carrier component.
- the catalyst for polymerization of olefins of the present invention contains the above-mentioned carrier component.
- Such polymerization catalysts include:
- the Group 3 to 11 transition metal compound (A) having a ligand containing at least two or more atoms selected from the above-mentioned boron, nitrogen, oxygen, phosphorus and iodide atoms May be supported on the carrier component (B), and is more preferable from the viewpoint of powder properties of the resulting olefin polymer.
- Group 3 to Group 1 transition metal compound having a ligand containing at least two or more atoms selected from a boron atom, a nitrogen atom, an oxygen atom, a phosphorus atom and a zeo atom used in the present invention.
- Examples thereof include the following compounds (a-1) to (a-27). These transition metal compounds may be used alone or in combination of two or more. It can be used in combination.
- the compound (a-1) represented by the following general formulas (I) and (III) can be used as the component (A).
- M in the formula (I) M 2 in the formula (II) and M 3 in the formula (II) may be the same or different from each other, and may be a transition metal atom selected from Groups 3 to 11 of the periodic table (the Group 3 also includes a lanthanide node), preferably a transition metal atom of Groups 3 to 6 and Groups 8 to 10, and more preferably a transition metal atom of Group 4, 5 or 6 A transition metal atom, particularly preferably a Group 4 or Group 5 metal atom.
- it is scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, nickel, palladium, etc., preferably. Scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladium, etc., and more preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, etc. Yes, particularly preferably titanium, zirconium, hafdium, vanadium, niobium, and tantalum.
- M in the formula (I), m 'in the formula (II) and m' in the formula (in) may be the same or different and are integers of 1 to 6, preferably 1 to 4 And more preferably an integer of 1-3, particularly preferably an integer of 1-2.
- K in equation (I), 'in equation (II) and k''in equation (ill) are the same May be different, and are integers of 1 to 6, preferably integers of 1 to 4, more preferably integers of 1 to 3, and particularly preferably integers of 1 to 2.
- a in the formula (I) represents an oxygen atom, a zeo atom or a nitrogen atom having a substituent—R 6 (one N (R 6 ) —), and is preferably an oxygen atom or a nitrogen atom.
- D in the formula (I) represents a nitrogen atom, a phosphorus atom, or a carbon atom having a substituent—R 7 (one N (R 7 ) —), and is preferably a carbon atom having a substituent—R 7 .
- ⁇ To 7 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an i-containing group, a phosphorus-containing group, and a heterocyclic compound residue.
- G is an oxygen atom in Formula (II), Iou atom or a nitrogen atom having a substituent Kiichi R 12 (- N (R 12 ) -) indicates, preferably oxygen atom.
- R 8 to R 16 in the formula (II) may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeolite-containing group, and a phosphorus-containing group.
- Group, a heterocyclic compound residue, a gayne-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
- T in the formula (III) represents a nitrogen atom or a phosphorus atom, and is preferably a nitrogen atom.
- L is a nitrogen atom
- R 17 to R 21 in the formula (III) may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeolite-containing group, and phosphorus. And a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
- R 1 s , R 2 s , R 3 s , R 4 s , R 5 s , R 6 s , and R 7 s are the same or different. Is also good. If m is 2 or more! Two of the groups represented by ⁇ to 7 may be linked.
- R 8 , R 9 , R 1Q , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 And may be the same or different.
- p is 2 or more, two groups may be connected among the groups represented by R 8 to R 16.
- R 17 , R 18 , R 19 , R 2 °, and R 21 may be the same or different.
- r is 2 or more, two of the groups represented by R 17 to R 21 may be linked.
- hydrocarbon group represented by ⁇ to shaku 7 , R 8 to R 16 in the formula (II), and R 17 to R 21 in the formula (ill) include methyl, ethyl, n-propyl, isopropyl, n Linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as -butyl, isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl;
- Ethynyl, propargyl and the like having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms.
- alkyl-substituted aryl groups such as methylphenyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, diisopropylphenyl, di-t-butylphenyl, trimethylphenyl, triisopropylphenyl, and tri-t-butylphenyl.
- a hydrogen atom may be substituted with octogen, and examples thereof include halogens having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl, penfluorofluorophenyl, and chlorophenyl. Hydrocarbon group.
- the hydrocarbon group may be substituted with another hydrocarbon group, such as an aryl-substituted alkyl group such as benzyl and cumyl.
- the hydrocarbon group may be a heterocyclic compound residue such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, or a carboxylic anhydride group.
- Oxygen-containing group amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group Nitrogen-containing groups such as those which have become ammonium salts; boron-containing groups such as porandil, poranthryl, and diboranyl; mercapto, thioester, dithioester, alkylthio, arylthio, thioacyl, thioether, and thiocyan Acid ester group, isothiocyanate Group, a sulfonic ester group, a sulfonamido group, Chiokarupokishiru group, Jichiokarupoki sill group, a sulfo group, a sulfonyl group, a sulfinyl group, I O ⁇ containing
- the hydrocarbon group may be substituted with an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zirconium-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like.
- the substituent such as an oxygen-containing group is such that the atomic group characterizing the group is a carbon atom in N or D in the formula (I), a carbon atom in E in the formula (II), a carbon atom in the formula (III) ) Is not directly bonded to a carbon atom in J, L, Q, T or R.
- phenyl, naphthyl, biphenyl, biphenyl, phenanthryl, anthryl, etc. having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms
- a substituted aryl group substituted with 1 to 5% of a substituent such as an aryloxy group is preferable.
- R 1 to R 7 may be two or more of these groups, preferably adjacent groups may be linked to each other to form a ring; R 8 to R 16 may be two or more of these; And preferably, adjacent groups may be linked to each other to form a ring, and R 17 to R 21 may be two or more of these groups, preferably, the adjacent groups may be linked to each other. Rings can also be formed.
- Examples of such a ring include a condensed group such as a benzene ring, a naphthalene ring, an acenaphthene ring, and an indene ring, and a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl, and butyl. Groups.
- R 8 ⁇ R 16 in Formula (II) the oxygen-containing group represented by R 17 to R 21 in formula (III), the oxygen raw horse in group 1
- the group contains up to 5 heterocyclic ring compound residues described below. Also contains a nitrogen atom, a y atom, a phosphorus atom, an halogen atom or a silicon atom, and these atoms are directly bonded to oxygen atoms. Groups are not included in the oxygen-containing groups.
- the oxygen-containing group examples include an alkoxy group, an aryloxy group, an ester group, a ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid anhydride group.
- Preferred are an alkoxy group, an aryloxy group, an acetyloxy group, a carbonyl group, a hydroxy group and the like.
- the oxygen-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.
- R 8 ⁇ R 16 in Formula (II) the nitrogen-containing group represented by R 17 to R 21 in the formula (ill) in formula (I), 1 to the nitrogen atom in the radical
- This group contains 5 and does not include the following heterocyclic compound residue.
- Specific examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, and a diazo group. And the like, wherein the amino group and the amino group are in the form of an ammonium salt.
- an amino group, an imino group, an amide group, an imide group, a nitro group and a cyano group are preferred.
- the nitrogen-containing group contains a carbon atom
- the number of carbon atoms is desirably 1 to 30, preferably 1 to 20.
- R 8 to R 16 in the formula (II) and R 17 to R 21 in the formula (ill) represent a group containing 1 to 5 boron atoms in the group, The following heterocyclic compound residues are not included.
- the boron-containing group include a boron-containing group such as a pollandyl group, a pollanthryl group, and a dipolar group.
- the hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms is 1 group.
- a substituted or unsubstituted poly group or a substituted or unsubstituted poly group is preferred. When two or more hydrocarbon groups are substituted, each hydrocarbon may be the same or different.
- R 8 to R 16 in the formula (II), and R 17 to R 21 in the formula (III) are groups containing 1 to 5 Y atoms.
- the following does not include the aromatic ring compound residue.
- Specific examples of the thio-containing group include, for example, mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group, isothiocyanate ester group, sulfone ester group, and sulfonamide group.
- the i-containing group contains a carbon atom
- the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.
- R 8 to R 16 in the formula (II) and R 17 to R 21 in the formula (ill) represent a group containing 1 to 5 phosphorus atoms in the group, The following heterocyclic compound residues are not included.
- Specific examples of the phosphorus-containing group include a phosphino group, a phosphoryl group, a phosphothioyl group, and a phosphono group.
- the heterocyclic compound residue represented by a ring containing 1 to 5 heteroatoms in the group Heteroatoms include ⁇ , N, S, P, B and the like.
- the ring include a 4- to 7-membered monocyclic and polycyclic ring, preferably a 5- to 6-membered monocyclic and polycyclic ring.
- residues of a nitrogen-containing compound such as pyrrole, pyridine, pyrimidine, quinoline, and triazine
- residues of an oxygen-containing compound such as furan and pyran
- residues of an io-containing compound such as thiophene
- a substituent such as an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
- Bi-containing group represented by R 17 to R 21 in formula (II I) is 1 to 5 in the base And a silyl group such as a hydrocarbon-substituted silyl group and a siloxy group such as a hydrocarbon-substituted siloxy group.
- methylsilyl dimethylsilyl, trimethylsilyl, ethylsilyl, getylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl (pentafluorophenyl) silyl.
- methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, getylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferred, and trimethylsilyl, triethylsilyl, triphenylsilyl and ditylphenylsilyl are particularly preferred.
- the hydrocarbon-substituted siloxy group Trimethylsiloxy and the like.
- the silicon-containing group contains a carbon atom
- the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.
- alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc., and lipoxy groups such as phenoxy, 2,6-dimethylphenyl Enoxy, 2,4,6-trimethylphenoxy, etc.
- asyl groups include formyl, acetyl, benzoyl, P-chlorobenzoyl, P-methoxybenzyl, etc., and as ester groups, acetyloxy, benzoyloxy. , Methoxycarbonyl, phenoxyl-ponyl, P-chlorophenoxyl-ponyl, and the like.
- the amino group includes alkylamino groups such as methylamino, dimethylamino, methylamino, dipropylamino, dibutylamino, dicyclohexylamino, and arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. Or an alkylarylamino group and the like; imino groups such as methylimino, ethylimino, propylimino, butylimino and phenylimino; and amide groups such as acetamido, N-methylacetoamide and N-methylbenzamide.
- the imide group include acetoimide and benzimide.
- the alkylthio groups include methylthio and ethylthio
- the arylthio groups include phenylthio, methylphenylthio, and nartylthio
- the thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthio.
- sulfonate groups such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate
- sulfonamide groups such as phenylsulfonamide, N-methylsulfonamide and N-methyl-P-toluenesulfonamide And the like.
- sulfonate group examples include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, P-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, and P-chlorobenzene sulfonate.
- sulfonate fluorobenzene sulphonate examples include methylsulfinate, phenylsulfinate, benzylsulfinate, P-toluenesulfinate and trimer.
- examples of the phosphino group include dimethylphosphino and diphenylphosphino
- examples of the phosphoryl group include methylphosphoryl, isopropylpropyl, and phenylphosphoryl.
- examples of the phosphothioyl group include: Examples include methyl phosphothioyl, isopropyl phosphothioyl, and phenyl phosphothioyl.
- examples of the phosphono group include phosphate groups such as dimethyl phosphate, diisopropyl phosphite, and diphenyl phosphate, and phosphate groups. It is.
- n in is a number satisfying the valence of M 1, specifically 0-5, rather preferably has 0-4, and more preferably an integer of 0 to 3.
- Formula (II) Q in is a number satisfying the valence of M 2, specifically 0 to 5, rather preferably has 0-4, and more preferably an integer of 0-3.
- Formula (III) r in is a number satisfying the valence of M 3, in particular 0-5, rather preferably has 0-4, and more preferably an integer of 0-3.
- n in the formula (I) is an atom or a group other than an oxygen atom
- n is preferably an integer of 1 to 4, more preferably 1 to 3.
- Q is preferably an integer of 1-4, more preferably 1-3.
- r is preferably an integer of 1 to 4, more preferably 1 to 3.
- X 1 is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a boron-containing group, a phosphorus-containing group, an octogen Containing group, heterocyclic compound residue, silicon-containing group, aluminum-containing group, germanium-containing group or tin-containing group;
- X 2 is a hydrogen atom, an octogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, an octogen-containing group, An atom or group arbitrarily selected from a cyclic compound residue, a silicon-containing group, an aluminum-containing group, a germanium-containing group or a tin-containing group,
- X 3 represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a boron-containing group, a phosphorus-containing group, an octogen-containing group, or a heterocyclic ring. It represents an atom or group arbitrarily selected from a formula compound residue, a silicon-containing group, an aluminum-containing group, a germanium-containing group, or a tin-containing group.
- a plurality of groups represented by X 1 may be the same or different from each other, and when ⁇ is 2 or more in the formula (II), And a plurality of groups represented by X 2 may be the same or different from each other.
- ⁇ is 2 or more in the formula (II I)
- the plurality of groups represented by X 3 are the same as each other. Or different.
- a plurality of groups represented by X 1 may be bonded to each other to form a ring, and when ⁇ is 2 or more in the formula (II), a plurality of groups represented by X 2 may form a ring together, when Oite the formula (ill) eta is 2 or more, plural groups represented by X 3 are each They may combine to form a ring.
- X 1 in formula (I), X 2 in Formula (II), is a halogen atom represented by X 3 in the In the formula (III), the fluorine, chlorine, bromine, and iodine.
- X 1 in formula (I), X 2 in Formula (II), is a hydrocarbon group represented by X 3 in the In the formula (III), the ones exemplified for the 1 ⁇ ! ⁇ In the formula (I) And the same.
- alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; and those having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl.
- Cycloalkyl groups alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl and dimethyl. Examples include aryl groups such as tylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.
- the hydrocarbon group also includes a halogenated hydrocarbon, specifically, a group in which at least one hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms has been replaced with octalogen. Of these, those having 1 to 20 carbon atoms are preferred.
- X 1 in formula (I), X 2 in Formula (II), is an oxygen-containing group represented by X 3 in the In the formula (III), the include the same ones as exemplified above Ri R 21 Specifically, a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryl group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; and a phenyloxy group such as phenylmethoxy and phenylethoxy. Aryloxy group; acetoxy group; carbonyl group and the like.
- i-containing groups represented by X 1 in the formula (I), X 2 in the formula (II), and X 3 in the formula (I II) are the same as those exemplified in 1 to! ⁇ 1 above.
- Specific examples include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, P-toluene sulfonate, trimethylbenzene sulfonate, and trimethyl sulfonate.
- Sulfonate groups such as isobutylbenzenesulfonate, P-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, P-toluenesulfinate, trimethyl Benzenesulfite, Pentafluo Sulfinate groups such as benzenesulfinate; alkylthio groups; arylthio groups and the like.
- the heterocyclic compound residue represented by X 1 in the formula (I), X 2 in the formula (II), and X 3 in the formula (III) is as described above! ⁇ To those similar to those exemplified in Shaku 21 .
- Hydrocarbon-substituted silyl groups such as tolylsilyl and trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.
- transition metal compound represented by the general formula (1), (II) or (III) will be described. A specific example will be described.
- M is a transition metal atom, for example, Sc (111), T i (III), T i (iv), Z r (III), Z r (iv), H f (iv), V (III), V (iv), V (V), Nb (V), Ta (V), Fe (II), Fe (III), Co (11), Co (III), Rh ( II), Rh (III), Rh (iv), Cr (III), Ni ( ⁇ ), and P d (ii).
- T i (iv), Z r (iv), H f (iv), V (i 11), V (iv), V (V), Nb (V), and Ta (V) are preferred.
- T i ( ⁇ ), ⁇ r (iv), and ⁇ f ( ⁇ ) are preferable.
- X represents, for example, a halogen such as Cl or Br, an oxygen atom, or an alkyl group such as methyl.
- Xs may be the same or different.
- transition metal compound represented by the general formula (1), (II) or (III) is described below. Here is a specific example.
- tBu represents a t-butyl group
- OMe represents a methoxy group
- Ph represents a phenyl group
- Me represents a methyl group
- Adm represents an adamantyl group.
- a transition metal compound in which zirconium is replaced with a metal selected from Groups 4 and 5 of the periodic table, such as titanium, hafnium, and vanadium, in the above compounds can also be exemplified.
- a compound (a-2) represented by the following general formula (IVa) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 7 of the periodic table, preferably a transition metal atom selected from Groups 4 and 5.
- Specific examples include titanium, zirconium, hafnium, vanadium, niobium, tantalum, and the like, and preferably titanium, zirconium, and vanadium.
- R 5 and R 6 are preferably a hydrocarbon group, more preferably an alkyl-substituted aryl group.
- Examples of the octogen and hydrocarbon groups represented by to in the formula (IVa) include the same halogen atoms and hydrocarbon groups as those exemplified as 1 to! ⁇ 7 in the above formula (I).
- the hydrocarbon groups represented by 1 to! ⁇ In the formula (IVa) are an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, a gayne-containing group, a germanium-containing group, and a tin-containing group. Although it may be substituted with a group or the like, in this case, it is desirable that the substituent such as an oxygen-containing group does not directly bond to N in the formula (IVa).
- Substituted or aryl substituted with 1 to 5 substituents such as an alkyl or alkoxy group preferably having 1 to 20 carbon atoms, preferably having 6 to 30 carbon atoms, and preferably having 6 to 20 carbon atoms. Groups are preferred.
- ⁇ 6 in the formula (IVa) represents an aromatic ring, an aliphatic ring or a nitrogen atom, an iodine atom, an oxygen atom
- These rings may form a hydrocarbon ring containing a substituent or the like, and these rings may further have a substituent.
- R 3 and R 4 are linked to form an aromatic ring.
- the oxygen-containing group, nitrogen-containing group, boron-containing group, ⁇ -containing group, phosphorus-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group and tin-containing group represented by ⁇ to 6 The same groups as those exemplified as shaku 1 to! ⁇ 7 in the above formula (I) can be mentioned.
- n represents a number that satisfies the valence of M, and specifically 1 to 5, preferably 1 to 4, and more preferably; Is an integer of ⁇ 3.
- X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, Indicates a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group.
- the residue, the gayne-containing group, the germanium-containing group and the tin-containing group include the same atoms or groups as those exemplified as X 1 in the above formula (I). Of these, those having 1 to 20 carbon atoms are preferred as the hydrocarbon group.
- a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- the compound (a-2) represented by the general formula (IVa) is preferably a compound represented by the following general formula (IVa ').
- M represents a transition metal atom selected from Groups 4 and 5 of the periodic table, and specific examples include titanium, zirconium, vanadium, niobium, and tantalum.
- R 7 to R 13 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeolite-containing group, and phosphorus. Group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
- R 12 and R 13 are preferably a hydrocarbon group, more preferably a 0-alkyl-substituted aryl group.
- examples of the halogen atom and the hydrocarbon group represented by R 7 to R 13 include the same atoms or groups as 1 to! ⁇ In the general formula (I).
- the hydrocarbon group may be substituted with an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, etc.
- the substituent such as an oxygen-containing group is preferably such that the atomic group characterizing the group is not directly bonded to N in the formula (IVa ').
- R 7 to R 13 represent an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, and a germanium-containing group.
- Examples of the group and tin-containing groups include the same groups as R ⁇ R 7 in the general formula (I).
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X represents a hydrogen atom, an octogen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic group. Indicates a compound residue, an aluminum-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.
- X in the formula (IVa ') represents a halogen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic group.
- Examples of the compound residue, the gayne-containing group, the germanium-containing group, and the tin-containing group include the same atoms or groups as those exemplified as X 1 in the above formula (I).
- n 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- specific examples of the compound represented by the general formula (IVa) will be shown.
- i Pr is an isopropyl group
- c 8 ⁇ 1 is 1
- p h represents a phenyl group.
- a compound (a-3) represented by the following general formula (IVb) can be used as the component (A).
- M represents a transition metal atom selected from Groups 8 to 11 of the periodic table, preferably a transition metal atom selected from Groups 8 and 9.
- iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, copper and the like can be mentioned, preferably iron, ruthenium, conorelet, rhodium and the like, more preferably iron or cobalt It is.
- ⁇ 1 to! ⁇ 6 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, and a heterocyclic group.
- a compound residue, a gayne-containing group, a germanium-containing group, or a tin-containing group, two or more of which are connected to each other to form an aromatic ring, an aliphatic ring, or a nitrogen atom, an iodine atom, or an oxygen atom May form a ring such as a hydrocarbon ring containing a hetero atom.
- R 5 and R 6 are preferably a hydrocarbon group, more preferably an alkyl-substituted aryl group.
- the hydrocarbon group represented by R 1 ⁇ in the formula (ivb) is an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an io-containing group, a phosphorus-containing group, a gayne-containing group, a germanium-containing group, and a tin-containing group.
- the substituent such as an oxygen-containing group it is desirable that in the substituent such as an oxygen-containing group, the atomic group characterizing the group is not directly bonded to N in the formula (IVb).
- carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isoptyl, sec-butyl, t-butyl, neopentyl, n-hexyl
- ⁇ 6 in the formula (IVb) represents an aromatic ring, an aliphatic ring or a nitrogen atom, an iodine atom, an oxygen atom
- These rings may form a hydrocarbon ring containing a substituent or the like, and these rings may further have a substituent.
- R 3 and R 4 are linked to form an aromatic ring.
- As the containing group and the tin-containing group, 1 to! The same groups as those exemplified as ⁇ 7 can be mentioned.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X in the formula (IVb) represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, Indicates a heterocyclic compound residue, a gayne-containing group, a germanium-containing group or a tin-containing group.
- Examples of the compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms and groups as those exemplified as X 1 in the above formula (I).
- a hydrocarbon group having 1 to 20 carbon atoms is preferable.
- n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- the compound (a-3) represented by the above-mentioned (IVb) is preferably a compound represented by the following general formula (IVb ′).
- M represents a transition metal atom selected from Groups 8 and 9 of the periodic table, and specifically includes iron or cobalt.
- R 7 to R 13 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeolite-containing group, and phosphorus.
- Group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
- R 12 and R 13 are preferably a hydrocarbon group, more preferably an 0-alkyl-substituted aryl group.
- the hydrocarbon group may be substituted with an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, etc.
- an oxygen-containing group it is desirable that the atomic group characterizing the group is not directly bonded to N in the formula (IVb ').
- R 7 to R 13 represent an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeolite-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, and a germanium-containing group.
- Examples of the group and tin-containing groups include the same groups as long 1 ⁇ ! ⁇ 7 in the general formula (I).
- R 7 to R 13 in the formula (IVb ′) include the same groups as those shown as more specific examples of to in the above formula (I).
- n is a number that satisfies the valence of M, and specifically 1 to 5, preferably; To 4, more preferably an integer of 1 to 3.
- X represents a hydrogen atom, an octogen atom, a hydrocarbon group, an oxygen-containing group, an io-containing group, a nitrogen-containing group, a boron-containing group, a phosphorus-containing group, an octogen-containing group, or a heterocyclic group. Indicates a compound residue, an aluminum-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.
- X in the formula (ivb ') represents a halogen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic group.
- Examples of the compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms and groups as those exemplified as X 1 in the above formula (I).
- a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- specific examples of the compound represented by the general formula (iVb) will be shown.
- i Pr represents an isopropyl group
- tBu represents a t-butyl group
- Ph represents a phenyl group
- a transition metal compound in which iron is replaced with a metal selected from Groups 8 to 11 of the periodic table other than iron, such as rhodium and cobalt, in the above-mentioned compounds can also be exemplified.
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom selected from Groups 4 and 5 and Groups 8 and 9.
- titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, copper, etc. are preferable, and titanium, zirconium, vanadium, and the like are preferable.
- m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- ⁇ To 6 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, and a heterocyclic compound residue.
- R 5 and R 6 are preferably a hydrocarbon group, more preferably an alkyl-substituted aryl group.
- halogen atom and the hydrocarbon group represented by ⁇ to 6 include the same halogen atoms and hydrocarbon groups as those exemplified as to 7 in the above formula (I).
- the hydrocarbon groups represented by shaku 1 to! ⁇ 6 in the formula (IVc) are oxygen-containing groups, nitrogen-containing groups, boron-containing groups, io-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, although it may be substituted with a nitrogen-containing group or the like, in this case, it is desirable that an atomic group characterizing the group such as an oxygen-containing group does not directly bond to N in the formula (ivc).
- the number of carbon atoms is 1 to 30, preferably 1 to 30, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl.
- ⁇ To shaku 6 are two or more of these groups, preferably adjacent groups linked to each other to form an aromatic ring, an aliphatic ring or a hydrocarbon ring containing a nitrogen atom, a zeo atom, an oxygen atom, or the like. And these rings may further have a substituent, and it is particularly preferable that R 3 and R 4 are linked to form an aromatic ring.
- Oxygen-containing group represented by scale 1 ⁇ R 6 in the formula (ivc) nitrogen-containing group, a boron-containing group, I O ⁇ -containing group, a phosphorus-containing group, heterocyclic compound residue, Kei-containing group, a germanium-containing organic In the above formula (I), the!
- the same groups as those exemplified as ⁇ to 7 can be mentioned.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X is an oxygen atom
- n is 2 or more, at least one of X is an oxygen atom, and the others are a hydrogen atom, a halogen atom, an oxygen atom, or a hydrocarbon group.
- X in formula (IVc) represents a genogen, a hydrocarbon group, an oxygen-containing group
- the above-mentioned formula (I) can be used as the organic group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, gayne-containing group, germanium-containing group and tin-containing group.
- a hydrocarbon group having 1 to 20 carbon atoms is preferable.
- n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- the compound (a-4) represented by the general formula (IVc) is preferably a compound represented by the following general formula (IVc,).
- M represents a transition metal atom selected from Groups 4 and 5 and Groups 8 and 9 of the periodic table, and specifically includes titanium, zirconium, vanadium, niobium, tantalum, iron or cobalt.
- m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- R 7 to R 13 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeolite-containing group, and phosphorus.
- Group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
- R 12 and R 13 are preferably a hydrocarbon group, more preferably a 0-alkyl-substituted aryl group.
- the octogen atom and the hydrocarbon group represented by R 7 to R 13 include the same atoms or groups as those of L to R 7 in the general formula (I).
- Hydrocarbon groups include oxygen-containing groups, nitrogen-containing groups, boron-containing groups, thio-containing groups, and phosphorus-containing groups. May be substituted with a group containing silicon, a group containing silicon, a group containing germanium, a group containing tin, or the like.
- the substituent such as an oxygen-containing group is represented by the formula (IVC) Desirably, it is not directly bonded to N.
- R 7 to R 13 represent an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zirconium-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, and a germanium-containing group.
- Examples of the group and tin-containing groups include the same groups as long 1 ⁇ ! ⁇ 7 in the general formula (I).
- n is a number that satisfies the valence of M, and specifically 1 to 5, preferably 1 to 4, and more preferably; Is an integer of ⁇ 3.
- X is an oxygen atom
- n is 2 or more, at least one of X is an oxygen atom, and the others are a hydrogen atom, a halogen atom, an oxygen atom, or a hydrocarbon group.
- Oxygen-containing groups, thio-containing groups, nitrogen-containing groups, boron-containing groups, phosphorus-containing groups, halogen-containing groups, residues of heterocyclic compounds, aluminum-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups Represents a group.
- Examples of the compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms and groups as those exemplified as X 1 in the above formula (I).
- a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- a compound ( a -5) represented by the following general formula (V) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 6 of the Periodic Table, and is preferably a Group 4 atom, specifically, titanium, zirconium or hafnium.
- R and R ′ may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, or an organic compound.
- a carbon atom represented by R or R ′ Examples of the hydrocarbon group having 1 to 50 carbon atoms and the halogenated hydrocarbon group having 1 to 50 carbon atoms include, for example,! In the above general formula (I).
- ⁇ Include the hydrocarbon groups and halogenated hydrocarbon groups exemplified as shaku 7 , and the organic silyl groups represented by R and R 'include, for example, ketones exemplified as 1 to! ⁇ 7 in the above general formula (I).
- Examples of a nitrogen-containing group, an oxygen-containing group, a zeo-containing group, and a heterocyclic compound residue exemplified above as ⁇ ! ⁇ 7 include a residue having nitrogen, oxygen, phosphorus, iodide or silicon.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- Xs may be the same or different from each other, and include a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenation having 1 to 20 carbon atoms.
- X represents a hydrocarbon group, an oxygen-containing group, a zirconium-containing group, a silicon-containing group or a nitrogen-containing group, and X may be mutually bonded to form a ring.
- ⁇ 1 in the above general formula (I) The octogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, oxygen-containing groups, zeo-containing groups, silicon-containing groups, and nitrogen-containing groups exemplified as ⁇ to 7 are exemplified.
- n B u is n- butyl group
- M e is methyl
- iP r is an isopropoxy port propyl group
- P h denotes a phenylene Le group.
- a compound (a-6) represented by the following general formula (VI) can be used as the component (A).
- M represents a transition metal atom selected from Groups 4 and 5 of the periodic table, and specifically, is titanium, zirconium, hafnium, vanadium, niobium, and tantalum.
- 1 to! ⁇ 1 May be the same or different from each other, and may include a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a hydrogen halide group having 1 to 50 carbon atoms or an organic silyl group or nitrogen, oxygen, A hydrocarbon group substituted with a substituent containing at least one atom selected from phosphorus, io, and silicon, preferably hydrogen or hydrocarbon.
- the groups represented by may be linked to each other to form a ring.
- the hydrocarbon group having 1 to 50 carbon atoms and the octogenated hydrocarbon group having 1 to 50 carbon atoms represented by 1Q for example, in the above general formula (I)
- the hydrocarbon groups and halogenated hydrocarbon groups exemplified as 1 to! ⁇ 7 are included in! ⁇ ⁇ Shaku 1 .
- the be organic silyl group such illustrated Kei-containing group can be mentioned as a ⁇ ! ⁇ 7 in the general formula (I), the scale 1 ⁇ ! ⁇ .
- hydrocarbon group substituted with a substituent having at least one atom selected from nitrogen, oxygen, phosphorus, zeolite, and silicon represented by A nitrogen-containing group, an oxygen-containing group, a zeo-containing group, or a hydrocarbon group substituted with a residue having nitrogen, oxygen, phosphorus, iodide or gayne among heterocyclic compound residues exemplified as ⁇ to 7 Is mentioned.
- n represents a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, and an io-containing group.
- n is 2 or more, a plurality of groups represented by X may be the same as or different from each other.
- the group and the nitrogen-containing group include, for example,! In the above formula (I).
- Examples of the halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, oxygen-containing groups, zeo-containing groups, silicon-containing groups and nitrogen-containing groups exemplified as ⁇ to shaku 7 are given.
- Y represents an atom selected from Groups 15 and 16 of the periodic table. Specifically, it indicates a nitrogen, phosphorus, arsenic, antimony, oxygen, or zeolite atom, preferably a nitrogen or oxygen atom
- Ph represents a phenyl group.
- a compound (a-7) represented by the following general formula (VII) or (VIII) can be used as the component (A).
- M represents a transition metal atom selected from Groups 4 and 5 of the periodic table, and is specifically titanium, zirconium, hafnium, vanadium, niobium or tantalum.
- R 1 ! ⁇ 6 in the formula (VII) and R 7 to R 10 in the formula (VIII) may be the same or different from each other, and include hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, carbon A halogenated hydrocarbon group or an organic silyl group having from 50 to 50 atoms or nitrogen, oxygen, And represents a hydrocarbon group substituted with a substituent containing at least one atom selected from the group consisting of carbon, silicon, and silicon, and preferably represents hydrogen or a hydrocarbon. At least two groups selected from R 1 to R 6 in the formula (VII) and R 7 to R 1G in the formula (VIII) are linked to each other to form a ring. Is also good.
- the hydrocarbon group includes, for example,! In the above general formula (I).
- Examples of the hydrocarbon groups and halogenated hydrocarbon groups exemplified as ⁇ to shaku 7 include the organic silyl groups represented by 1 ⁇ to 16 in the formula (VII) and R 7 to R 1Q in the formula (VIII). Is, for example, in the above general formula (I)!
- Examples of the silicon-containing group exemplified as ⁇ to 7 include: ⁇ 1 to!
- ⁇ Carbon substituted by a substituent having at least one atom selected from nitrogen, oxygen, phosphorus, iodide and silicon represented by R 7 to R 1 () in formula (VI II)
- the hydrogen group include, for example,! In the above general formula (I). ⁇ ⁇ 7 and to illustrate nitrogen-containing group, an oxygen-containing group, Iou-containing group or a nitrogen of the heterocyclic compound residue, oxygen, phosphorus, hydrocarbon group substituted with a residue having an Iou or Kei containing Is mentioned.
- m represents an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.
- n represents a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and containing oxygen.
- n is 2 or more, a plurality of groups represented by X may be the same as or different from each other.
- Y represents an atom of Group 15 or 16 of the periodic table, preferably an atom of Group 15. Specifically, it represents nitrogen, phosphorus, arsenic, antimony, oxygen, or silicon, and is preferably an oxygen atom.
- Me represents a methyl group.
- a compound (a-8) represented by the following general formula (IX) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 6 of the periodic table, preferably a Group 4 transition metal. Specifically, scandium, ittrium, titanium, It is zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably titanium, zirconium or hafnium.
- R and R ′ may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, or an organic compound. It represents a silyl group or a substituent having at least one atom selected from nitrogen, oxygen, phosphorus, zeolite and silicon, and is preferably a hydrocarbon group. More preferably, the hydrocarbon group is an alkyl-substituted aryl group.
- the hydrocarbon group having 1 to 50 carbon atoms and the halogenated hydrocarbon group having 1 to 50 carbon atoms represented by R and R ′ are, for example, 1 in the above general formula (I)
- Examples of the organic silyl group represented by R and R ′ include the hydrocarbon groups and halogenated hydrocarbon groups exemplified as R to R 7, for example, the silicon groups exemplified as 1 to! ⁇ 7 in the general formula (I).
- R and R ′ examples include, for example, R in the above general formula (I) ⁇ exemplified nitrogen-containing groups as R 7, the oxygen-containing group, I O ⁇ -containing groups and the heterocyclic nitrogen of compound residue, oxygen, phosphorus, residue having Iou or Kei element.
- m is an integer of 0 to 2, and preferably 2.
- n is an integer of 1 to 5, preferably an integer of 1 to 3.
- A represents an atom selected from Groups 13 to 16 of the periodic table, and preferably represents an atom of Group 14 of the periodic table. Specific examples include boron, carbon, nitrogen, oxygen, silicon, phosphorus, zeolite, germanium, tin and the like, and preferably carbon or gayne. When n is 2 or more, a plurality of A may be the same or different from each other.
- E is a substituent having at least one atom selected from carbon, hydrogen, oxygen, halogen, nitrogen, zeolite, phosphorus, boron and silicon, preferably hydrogen or carbon Is an atom.
- the plurality of groups represented by E may be the same or different from each other, and two or more groups represented by E are linked to each other to form a ring. You may.
- Examples of the substituent represented by E in the formula (IX) having at least one atom selected from the group consisting of carbon, hydrogen, oxygen, halogen, nitrogen, zeolite, phosphorus, hydrogen and silicon include, for example, the above general formula ( illustrated as!
- p is an integer of 0 to 4, and is preferably 2.
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, Indicates a zeo-containing group, a silicon-containing group or a nitrogen-containing machine.
- p is 2 or more, a plurality of groups represented by X may be the same or different from each other.
- the group and the nitrogen-containing group include, for example,! In the above formula (I).
- the octogen atoms, hydrocarbon groups, octogenated hydrocarbon groups, oxygen-containing groups, zeo-containing groups, silicon-containing groups and nitrogen-containing groups exemplified as ⁇ 1 to! ⁇ 7 are exemplified.
- a compound ( a- ) represented by the following general formula (X) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom selected from Groups 3 to 6 of the periodic table, and more preferably a periodic metal atom. It is a transition metal atom of Table 4 group. Specifically, it is scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, and more preferably titanium, zirconium or hafnium.
- A represents an atom selected from Groups 14 to 16 of the periodic table, and preferably represents an atom selected from Groups 15 and 16. Specifically, NR 9 , PR 10 , 0, and S are preferable.
- n is an integer of 0 or 1
- p is an integer of 1 to 3
- Q is a number satisfying the valence of M
- m is When 0, n is preferably 0 and p is preferably 2.
- ⁇ 1 to; ⁇ 1 May be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, and an i-containing group.
- the group, the silicon-containing group and the nitrogen-containing group include, for example,!
- Examples of the halogen atom, the hydrocarbon group, the octogenated hydrocarbon group, the oxygen-containing group, the y-containing group, the silicon-containing group, and the nitrogen-containing group exemplified as ⁇ to shaku 7 are given.
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, Indicates a zeo-containing group, a silicon-containing group or a nitrogen-containing machine.
- Q is 2 or more, a plurality of groups represented by X may be the same or different from each other.
- the containing group and the nitrogen-containing group include, for example, an octogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, an io-containing group, which are exemplified as 1 to! ⁇ 7 in the general formula (I).
- Gay-containing groups and nitrogen-containing groups are included.
- Y is a group bridging A with the borane overnight benzene ring, and represents carbon, silicon or germanium.
- ipr represents an isopropyl group
- tBu represents a tert-butyl group
- Ph represents a phenyl group
- a compound (a-10) represented by the following general formula (Xla) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom of Groups 3 to 6 of the periodic table, and more preferably a transition metal atom of Group 4 to 6 of the periodic table.
- a and A ′ may be the same or different from each other, and represent a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon having 1 to 50 carbon atoms or an oxygen-containing group, A hydrocarbon group having an iodine-containing group or a silicon-containing group, or an octogenated hydrocarbon group having an oxygen-containing group, an iodine-containing group or a gayne-containing group, preferably a hydrocarbon, and more preferably an alkyl group. It is a substituted aryl group.
- Examples of the hydrocarbon group having 1 to 50 carbon atoms and the halogenated hydrocarbon group having 1 to 50 carbon atoms represented by A and A ′ in the formula (Xla) include, for example, R in the above general formula (I)
- the hydrocarbon groups and halogenated hydrocarbon groups exemplified as 1 ′ to R 7 are exemplified.
- Examples of the hydrocarbon group having an oxygen-containing group, a zeo-containing group or a silicon-containing group represented by A and A ′ are, for example, those described above.
- the octogenated hydrocarbon group having a silicon-containing group include a halogenated hydrocarbon group having an oxygen-containing group, an i-containing group or a silicon-containing group exemplified as 1 to! ⁇ 7 in the general formula (I). Are mentioned.
- D may or may not be present, and when present, indicates a linking group that bridges A and A ′, and when not present, A and A ′ are — It is linked only through O—M—O—.
- D in the formula (Xla) include a single bond, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms, an oxygen atom, an iodine atom or R 1 It is a group represented by R 2 Z.
- R 1 and R 2 may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom, They may combine with each other to form a ring, and Z represents a carbon atom, a nitrogen atom, an io atom, a phosphorus atom or a silicon atom.
- n represents a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an i-containing group, and a silicon atom.
- n 2 or more, the groups represented by X may be the same or different, and the groups represented by X are bonded to each other to form a ring May be.
- the group and the nitrogen-containing group include a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, an oxygen-containing group, and a silicon-containing group exemplified as R 1 ⁇ 7 in the general formula (I). And nitrogen-containing groups.
- tBu is a tert- heptyl group
- Me represents a methyl group
- a compound (a-11) represented by the following general formula (Xlb) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom of Groups 3 to 6 of the periodic table, and more preferably. Is a transition metal atom of Groups 4 and 5 of the periodic table, particularly preferably a transition metal atom of Group 4 of the periodic table.
- it is scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, more preferably titanium, zirconium or hafnium.
- m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- a and A ′ may be the same or different from each other, and represent a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon having 1 to 50 carbon atoms or an oxygen-containing group, A hydrocarbon group having an iodine-containing group or a silicon-containing group, or a halogenated hydrocarbon group having an oxygen-containing group, an iodine-containing group or a silicon-containing group, preferably a hydrocarbon group, more preferably an alkyl group. It is a substituted aryl group.
- Examples of the hydrocarbon group having 1 to 50 carbon atoms and the halogenated hydrocarbon group having 1 to 50 carbon atoms represented by A and A ′ in the formula (Xlb) include, for example, R in the above general formula (I) exemplified hydrocarbon groups as 1 to R 7, include a halogenated hydrocarbon group, the hydrocarbon group having an oxygen-containing group, Iou-containing group or a gay-containing group represented by a and a ', for example, the general formula (I) an oxygen-containing groups exemplified as R ⁇ R 7 in, there are mentioned hydrocarbon groups having I O ⁇ -containing group or a gay-containing group, an oxygen-containing group represented by a and a ', Iou-containing group or Gay
- the halogenated hydrocarbon group having a silicon-containing group for example, the halogenated hydrocarbon group having an oxygen-containing group, an io-containing group or a silicon-containing group exemplified as R i to R 7 in the above general formula
- D may or may not be present, and when present, indicates a linking group that bridges A and A ′. O— M—O It is linked through only one.
- Specific examples of D include a single bond, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms, an oxygen atom, an iodine atom or It is a group represented by Z.
- R 1 and R 2 may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including at least one or more heteroatoms, They may combine with each other to form a ring, and Z represents a carbon atom, a nitrogen atom, an io atom, a phosphorus atom, or a silicon atom.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X is an oxygen atom
- n is 2 or more, at least one of X is an oxygen atom, and the others are a hydrogen atom, a halogen atom
- O represents an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an iodine-containing group, a gayne-containing group or a nitrogen-containing group.
- the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.
- the containing group and the nitrogen-containing group include, for example, the octogen atom exemplified as 1 to! ⁇ 7 in the above general formula (I), a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, an io-containing group, Silicon-containing groups and nitrogen-containing groups are included.
- a compound (a-12) represented by the following general formula (XII) can be used as the component (A).
- M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, preferably a transition metal atom belonging to Groups 3 to 6 of the periodic table, and more preferably a transition metal atom belonging to Group 4 of the periodic table. It is a metal atom. Specifically, it is scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, and more preferably titanium, zirconium, or hafnium.
- Y may be the same as or different from each other, and represents an atom belonging to groups 13 to 15 of the periodic table, and specifically represents carbon, silicon, germanium, nitrogen, phosphorus, oxygen, or io. At least one of Y is an atom other than carbon.
- m is an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3.
- Ri R 5 is present when Y to be bonded is an atom selected from Group 14 of the periodic table, and may be the same or different from each other, and may represent a hydrogen atom, a halogen atom, A hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, or a hydrocarbon group substituted with a substituent containing at least one atom selected from nitrogen, oxygen, phosphorus, zeolite, and silicon; Two or more of them may be connected to each other to form a ring.
- hydrocarbon group represented by the shaku 1 to R 5 in the formula (XII) and the octogenated hydrocarbon group include, for example, the hydrocarbon groups exemplified as 1 to! ⁇ 7 in the general formula (I), and halogenated carbon.
- hydrocarbon group can be mentioned, 1 ⁇ ! ⁇ the organosilyl group represented, for example, illustrated Gay-containing group can be mentioned as a 1 ⁇ ! ⁇ 7 in the general formula (I), Shaku 1 ⁇ ! ⁇ 5
- substituent having at least one atom selected from nitrogen, oxygen, phosphorus, zeolite and silicon represented by the following include, for example, nitrogen-containing groups exemplified as 1 to! ⁇ 7 in the above general formula (I).
- n is a number that satisfies the valence of M, and specifically, is an integer of 1 to 5, preferably 1 to, and more preferably 1 to 3.
- X is a hydrogen atom, an octogen, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, an octogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, N-containing group, silicon-containing group or nitrogen-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X The groups may be linked together to form a ring.
- a halogen atom represented by X in the formula (XII), a hydrocarbon group having 1 to 20 carbon atoms, an octogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an oxygen-containing group, and a silicon-containing group And the nitrogen-containing group include, for example,! In the above general formula (I).
- Examples of ⁇ to 6 include the halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, oxygen-containing groups, thio-containing groups, silicon-containing groups and nitrogen-containing groups exemplified above.
- tBu represents a tert-butyl group
- Me represents a methyl group
- a compound (a-13) represented by the following general formula (XIII) can be used as the component (A).
- ⁇ represents a transition metal compound of Groups 3 to 11 of the periodic table, and is preferably a transition metal atom of Groups 4 to 5.
- Specific examples include titanium, zirconium, vanadium, niob, and tantalum.
- m is an integer of 1 to 6, and preferably 1 to 3.
- R may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. And two or more of them may be connected to each other to form a ring.
- n represents a number that satisfies the valence of M, and specifically 1 to 5, preferably:! To 4, more preferably an integer of 1 to 3.
- X is an oxygen atom when n is 1, and when n is 2 or more, at least one of X is an oxygen atom, and the others are a hydrogen atom, a halogen atom, or an oxygen atom.
- Atom a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an iodine-containing group, a gayne-containing group or a nitrogen-containing group.
- the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X are bonded to each other to form a ring. Is also good.
- the group and the nitrogen-containing group include, for example,! In the above formula (I).
- Examples of ⁇ to shaku 7 include /, a logene atom, a hydrocarbon group, an octahydrogenated hydrocarbon group, an oxygen-containing group, a zeo-containing group, a gayne-containing group and a nitrogen-containing group.
- Y may or may not be present, and if present, is an atom of Groups 15 and 16 of the periodic table, specifically 0, S, Se, and NR .
- a compound (a-14) represented by the following general formula (XlVa) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 7 and 11 of the periodic table, and preferably a transition metal atom selected from Groups 4 and 5.
- 1 to! ⁇ 4 may be the same or different from each other, and may be a hydrocarbon group having 1 to 50 carbon atoms, an octogenated hydrocarbon group having 1 to 50 carbon atoms, or organic silyl. And a hydrocarbon group substituted by a group or a substituent containing at least one atom selected from nitrogen, oxygen, phosphorus, zeolite and silicon. Groups represented by 1 ⁇ to 1 4, two or more of these, preferably may form a ring adjacent groups together.
- Examples of the 1 to 50 perogenated hydrocarbon group include, for example,! In the above general formula (I).
- Examples of the organic silyl groups represented by 1 to! ⁇ 4 include the hydrocarbon groups and halogenated hydrocarbon groups exemplified as ⁇ to 7, and for example,! ⁇ 1 to! ⁇ 7 include the silicon-containing groups exemplified as!
- Examples of the substituent having at least one atom selected from nitrogen, oxygen, phosphorus, zeolite and silicon represented by ⁇ to 4 include, for example, the nitrogen-containing groups exemplified as the scale 1 to! ⁇ In the above general formula (I).
- n is a number satisfying the valence of M, and specifically represents an integer of 0 to 4.
- X is a hydrogen atom, an octogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an oxygen-containing group.
- the group and the nitrogen-containing group include, for example, halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, oxygen-containing groups, io-containing groups, and cations exemplified as the lengths 1 to! ⁇ 7 in the general formula (I). And nitrogen-containing groups.
- a compound (a-15) represented by the following general formula (XlVb) can be used as the component (A).
- M represents a transition metal atom selected from Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum.
- ⁇ To 4 may be the same or different from each other, and may be a hydrocarbon group having 1 to 50 carbon atoms, a hydrogenated hydrocarbon group having 1 to 50 carbon atoms, an organic silyl group, or nitrogen or oxygen. And a hydrocarbon group substituted with a substituent containing at least one atom selected from the group consisting of phosphorus, phosphorus, silicon and silicon. Two or more of these groups represented by shaku 1 to ⁇ are preferably connected to each other to form a ring.
- ⁇ 1 to! ⁇ 4 are examples of the hydrocarbon group having 1 to 50 carbon atoms and the octogenated hydrocarbon group having 1 to 50 carbon atoms, which are represented by the above formula (I).
- the hydrocarbon groups and halogenated hydrocarbon groups exemplified as ⁇ to 7 are exemplified.
- the organic silyl groups represented by 1 to! ⁇ Are exemplified as the scales 1 to! ⁇ 7 in the general formula (I). And silicon-containing groups.
- the substituent having at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, zeo and silicon represented by ⁇ to shaku 4 is, for example, a nitrogen-containing group exemplified as R ⁇ R 7 in the above general formula (I).
- the oxygen-containing group, the zeo-containing group, and the residue of the heterocyclic compound having a nitrogen, oxygen, phosphorus', zeo or gayne is, for example, a nitrogen-containing group exemplified as R ⁇ R 7 in the above general formula (I).
- n is a number that satisfies the valence of M, and specifically represents an integer of 0 to 4.
- XlVb represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an iodine-containing group, A n-containing group or a nitrogen-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same as or different from each other.
- the nitrogen-containing group and the nitrogen-containing group include, for example,!
- Examples of ⁇ to 7 include an octogen atom, a hydrocarbon group, an octogenated hydrocarbon group, an oxygen-containing group, an io-containing group, a silicon-containing group, and a nitrogen-containing group.
- a compound (a-16) represented by the following general formula (XIVc) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 10 of the periodic table, and is preferably nickel, palladium or platinum.
- m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- 1 to! ⁇ 4 may be the same or different, and may be a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, or an organic silyl group. And a hydrocarbon group substituted with a substituent containing at least one atom selected from nitrogen, oxygen, phosphorus, zeolite, and silicon. Two or more of these groups represented by 1 to! ⁇ 4 , preferably adjacent groups, may be connected to each other to form a ring.
- Examples of the hydrocarbon group having 1 to 50 carbon atoms and the halogenated hydrocarbon group having 1 to 50 carbon atoms represented by Ri R 4 in the formula (XIVc) include I ⁇ in the above general formula (I).
- To R 7 include the hydrocarbon groups and halogenated hydrocarbon groups.
- Examples of the organic silyl group represented by Shaku 1 to! ⁇ Include, for example, Shaku 1 to! ⁇ 7 in the general formula (I).
- Examples of the substituent having at least one atom selected from nitrogen, oxygen, phosphorus, iodide and silicon represented by 1 to! ⁇ Include, for example, the above-mentioned general formula (I): !
- Examples of the nitrogen-containing group, the oxygen-containing group, the zeo-containing group, and the heterocyclic compound residues exemplified as ⁇ to 7 include residues having nitrogen, oxygen, phosphorus, zeo or silicon.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X is an oxygen atom when n is 1, and when n is 2 or more, at least one of X is an oxygen atom, and the others are a hydrogen atom, an octogen atom, and an acid.
- the plurality of groups represented by X may be the same as or different from each other.
- the nitrogen-containing group and the nitrogen-containing group include, for example,! ⁇ ⁇ 6 and to exemplified ⁇ androgenic atom, a hydrocarbon group, eight halogenated hydrocarbon group, an oxygen-containing group, I O-containing groups, silicon-containing groups and nitrogen-containing groups.
- a compound (a-17) represented by the following general formula (XV) can be used as the component (A).
- Y 1 and Y 3 may be the same or different and represent an atom selected from Group 15 of the periodic table.
- ⁇ 2 represents an atom selected from the first group 6 of the periodic table.
- 1 ⁇ to 18 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenation having 1 to 20 carbon atoms.
- a hydrocarbon group, an oxygen-containing group, a zeo-containing group or a silicon-containing group is shown, and two or more of these may be connected to each other to form a ring.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by 1 to R 8 in the formula (XV) include, for example, 1 in the above general formula (I) To! ⁇ Include the hydrocarbon groups and octogenated hydrocarbon groups.
- Examples of the halogen atom, oxygen-containing group, io-containing group and silicon-containing group represented by 1 to! ⁇ Are, for example, those represented by the above general formula (I In the above, there may be mentioned halogen atoms, oxygen-containing groups, thio-containing groups, and silicon-containing groups exemplified as to in. .
- a compound (a-18) represented by the following general formula (XVI) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom of Groups 3 to 6 and 8 to 10, and more preferably It is a Group 4 group, 5 group or 6 group transition metal atom, particularly preferably a 4th group or 5 group metal atom.
- m represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- A represents an oxygen atom, a zeo atom, or a nitrogen atom having a bonding group R 5 (—N (R 5 ) —).
- D is one C (R 6 ) (R 7 ) —, S i (R 8 ) (R 9 ) —, one P (0) (R 10 ) —, one P (RU) — Indicates one SO—or—S—.
- 1 to! ⁇ 16 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a boron-containing group, and a phosphorus-containing group.
- n is a number that satisfies the valency of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, and a halogen-containing group.
- Examples of the residue, silicon-containing group, germanium-containing group, and tin-containing group include the same atoms or groups as those exemplified as X 1 in the above general formula (I).
- a compound (a-19) represented by the following general formula (XVII) or (XVIII) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom of Groups 3 to 6 and 8 to 10; More preferably, it is a Group 4, 5 or 6 transition metal atom, particularly preferably a Group 4 or 5 metal atom.
- n represents an integer of 1 to 3.
- m ′ represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- G represents an oxygen atom, a zeo atom, or a nitrogen atom having one R 6 substituent (one N (R 6 ) —).
- ⁇ 6 may be the same or different from each other, and may be a hydrogen atom, an octogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, Represents a zirconium-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, even if two or more of these are linked to each other to form a ring
- m is 2 or more in the formula (XVII)
- group, silicon-containing group, germanium-containing group, and tin-containing group include the same atoms or groups as those exemplified as the lengths 1 to! ⁇ 7 in the above general formula (I).
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, more preferably 1 to 3.
- X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, an iodide-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, Group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group.
- n is 2 or more
- X represents A plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the! In the above general formula (I).
- the same atoms or groups as those exemplified as ⁇ to 7 can be mentioned.
- a compound (a-20) represented by the following general formula (XIX) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom of Groups 3 to 6 and 8 to 10, and more preferably Is a Group 4, 5 or 6 transition metal atom, particularly preferably a Group 4 or 5 metal atom.
- m represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- A represents an oxygen atom, a zeolite atom, or a nitrogen atom having a substituent —R 5 (—N (R 5 ) —).
- Expression (XIX) ⁇ ⁇ Shaku 1 May be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a zeo-containing group, a phosphorus-containing group, a heterocyclic compound residue, -Containing group, germanium-containing group or tin-containing group, two or more of these may be linked to each other to form a ring, and when m is 2 or more, one coordination The child contains a shaku 1 ⁇ ! ⁇ 1 .
- R 1 s , R 2 s , R 3 s , R 4 together, R 5 each other, R 6 together, R 7 together, R 8 together, each other R 9, R 1Q each other may be the same or different from each other.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, and a halogen-containing group.
- Examples of the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms or groups as those exemplified as X 1 in the general formula (I).
- a compound (a-21) represented by the following general formula (XXa) or (XXla) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 and 4 of the periodic table.
- a 1 represents an oxygen atom, a zeolite atom or a hydrocarbon-substituted nitrogen atom.
- a 2 represents a hydrocarbon-substituted oxygen atom, a hydrocarbon-substituted zeo atom or a hydrocarbon-substituted nitrogen atom.
- E represents an oxygen atom or an io atom.
- the lengths 1 to! ⁇ 5 may be the same or different and represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group.
- n is a number that satisfies the valence of M, and specifically, 0 To 5, preferably 0 to 4, more preferably 0 to 3.
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, Represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group.
- n is 2 or more, a plurality of groups represented by X may be the same or different. And a plurality of groups represented by X may be bonded to each other to form a ring.
- X represents a halogen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic ring.
- Examples of the formula compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms or groups as those exemplified as X 1 in the general formula (I).
- a compound (a-22) represented by the following general formula (XXb) or (XXIb) can be used as the component (A).
- M represents a transition metal atom selected from Groups 5 to 11 of the periodic table, and is preferably a transition metal atom belonging to Groups 8 to 10 of the periodic table.
- a 1 represents an oxygen atom, a zeolite atom or a hydrocarbon-substituted nitrogen atom.
- a 2 represents a hydrocarbon-substituted oxygen atom or a hydrocarbon-substituted iodine atom or a hydrocarbon-substituted nitrogen atom;
- E represents an oxygen atom or an io atom.
- m is :! Shows an integer of ⁇ 2.
- ⁇ To 5 may be the same or different, and represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group.
- n is a number that satisfies the valency of M, and is specifically an integer of 1 to '5, preferably 1 to 4, and more preferably 1 to 3.
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, and a halogen.
- a hydrocarbon group an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a hetero group
- the cyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms or groups as those exemplified as X 1 in the general formula (I).
- a compound (a-23) represented by the following general formula (XXI I), (XXI II), (XXIV) or (XXV) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the Periodic Table, preferably Groups 3 to 6 and Groups 8 to 1 0 It is a transition metal atom, more preferably a Group 4, 5 or 6 transition metal atom, and particularly preferably a Group 4 or 5 metal atom.
- A represents an oxygen atom, a zeo atom, or a nitrogen atom.
- A may also have a substituent R 6 depending on the mode of bonding to the metal M.
- D is one C (R 7 ) (R 8 ) —, one Si (R 9 ) (R 10 ) —, one CO— One S ⁇ 2 —, one SO— or one PiOHOR 11 )
- m represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, It is preferably an integer of 1-2.
- Ri R 11 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, Nitrogen-containing group, boron-containing group, zeo-containing group, phosphorus-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, two or more of which are linked to each other To form a ring.
- R 1 each other, R 2 together, R 3 together, R 4 together, R 5 each other, R 6 to each other, each other R 7, R 8 together, R 9 together, R 1 together, R 11 may be the same or different from each other, and at least one of the groups represented by 1 to R 11 included in any one of the ligands and one included in the other ligands At least one of the groups represented by 1 may be linked.
- nitrogen-containing group, the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include, for example,! The same atoms or groups as those exemplified as ⁇ to scale 7 can be mentioned.
- n is a number satisfying the valency of M, and specifically 1 to 5, preferably 1 to 4, more preferably 1 to 3. Is an integer.
- X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, Aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and when n is 2 or more, a plurality of groups represented by X May be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.
- a halogen atom represented by X, a hydrocarbon group, an oxygen-containing group, a bio-containing group, a nitrogen-containing group, a boron-containing group, and an aluminum
- the containing group, the phosphorus-containing group, the porogen-containing group, the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include those exemplified as X 1 in the above general formula (I). Similar atoms or groups are mentioned.
- a compound (a-24) represented by the following general formula (XXVI), (XXVI I), (XXVIII) or (XXVIX) can be used as the component (A).
- m represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- A represents an oxygen atom, a zeolite atom, or a nitrogen atom.
- the A can also have a substituent R 5 in accordance with the mode of binding to the metal M.
- Two or more of them may be connected to each other to form a ring. If m is 2 or more, 1 ⁇ ! ⁇ 1 . Two of the groups represented by may be linked, and each R may be the same or different.
- Examples of the group, the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include, for example, the same atoms or groups as those exemplified as 1 to! ⁇ 7 in the above general formula (I). No.
- n is a number satisfying the valency of M, and specifically 1 to 5, preferably 1 to 4, more preferably 1 to 3. Is an integer of
- X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, an iodine-containing group, a nitrogen-containing group, and a boron-containing atom.
- X represents a halogen atom, a hydrocarbon group, an oxygen-containing group, an iodide-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group
- phosphorus-containing group, the halogen-containing group, the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include the same atoms or the same as those exemplified as X 1 in the above general formula (I). Groups.
- a compound (a-25) represented by the following general formula (XXX) can also be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal atom of Groups 3 to 6 and 8 to 10, and more preferably Is a Group 4, 5 or 6 transition metal atom, particularly preferably a Group 4 or 5 metal atom.
- a 1 and A 2 may be the same or different and represent a nitrogen atom or a phosphorus atom.
- R 1 and R 2 may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, and a boron-containing group.
- a group, an ⁇ -containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of these may be connected to each other to form ⁇ .
- the containing group, the boron-containing group, the zeo-containing group, the phosphorus-containing group, the heterocyclic compound residue, the silicon-containing group, the germanium-containing group, and the tin-containing group include, for example, 1 ⁇ to 1 in the above general formula (I). Examples include the same atoms or groups as those exemplified as 17 .
- m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.
- m is 2 or more, with any of the RR 2 contained in one ligand may be bonded with either a free Murrell R to other ligands, also R 1 together, R 2 Each may be the same or different.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X is a hydrogen atom, an octogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a zeo-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, an octogen -Containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group.
- n is 2 or more, a plurality of groups represented by X may be the same or different from each other. And a plurality of groups represented by X may be bonded to each other to form a ring.
- XXX a heterocyclic compound represented by X in the formula (XXX)
- Examples of the residue, silicon-containing group, germanium-containing group, and tin-containing group include the same atoms or groups as those exemplified as X 1 in the above general formula (I).
- a compound (a-26) represented by the following general formula (XXXIa) or (XXXlIa) can be used as the component (A).
- M represents a transition metal atom selected from Groups 3 to 6 of the periodic table, preferably a transition metal atom selected from Groups 4 and 5.
- 1 to! ⁇ 6 may be the same or different, and each represents a hydrogen atom or a hydrocarbon group, an octogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. , ⁇ -containing group, silicon-containing group, nitrogen-containing group or phosphorus-containing group, two or more of which may be linked to each other to form a ring.
- hydrocarbon groups represented by 1 to! ⁇ 6 hydrocarbon groups represented by 1 to! ⁇ 6 , octogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, io-containing groups, gayne-containing groups, and nitrogen
- the containing group and the phosphorus-containing group include, for example, the hydrocarbon groups exemplified as 1 to! ⁇ 7 in the above general formula (I), octogenated hydrocarbon groups, oxygen-containing groups, y-containing groups, and silicon-containing groups.
- examples include a nitrogen-containing group and a phosphorus-containing group.
- n is a number that satisfies the valence of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X may be the same or different from each other, and may be a hydrogen atom, an halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 2 carbon atoms.
- 0 represents a halogenated hydrocarbon group, an oxygen-containing group, or an iodine-containing group.
- a compound (a-27) represented by the following general formula (XXXIb) or (XXXIIb) can be used as the component (A).
- M represents a transition metal atom selected from Groups 8 to 11 of the periodic table, and preferably represents a transition metal atom selected from Groups 8 and 9.
- Ri R 6 may be the same or different from each other, and includes a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, and a y-containing group. Group, a nitrogen-containing group, a nitrogen-containing group or a phosphorus-containing group, and two or more of these may be connected to each other to form a ring.
- hydrocarbon group represented by ⁇ to 6 a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a zeo-containing group, a silicon-containing group, a nitrogen-containing group, and a phosphorus-containing group are, for example, those represented by the above general formula exemplified hydrocarbon groups as Ri ⁇ R 7 in (I), a halogenated hydrocarbon group, an oxygen-containing group, Iou-containing group, Kei-containing group, a nitrogen-containing group and a phosphorus-containing group.
- n is a number that satisfies the valency of M, and is specifically an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
- X may be the same or different, and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an oxygen-containing group or an i-containing group.
- a hydrocarbon group having 1 to 20 carbon atoms an octogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, and an io-containing group
- a halogen atom represented by X in the formulas (XXXIb) and (XXXIIb
- a hydrocarbon group having 1 to 20 carbon atoms an octogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group
- an io-containing group examples thereof include a halogen atom, a hydrocarbon group, an octogenated hydrocarbon group, an oxygen-containing group, and a zeo-containing group exemplified as 1
- a 3rd to 1st group 1 transition metal compound having a ligand containing at least two or more atoms selected from a boron atom, a nitrogen atom, an oxygen atom and an iodine atom
- the transition metal compound (A) may be supported on the carrier component (B).
- the transition metal compound (A) is obtained by stirring and mixing the carrier component (B) with the carrier component (B) for a predetermined time in an inert solvent, followed by filtration. At this time, a heating operation may be performed.
- the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic saturated hydrocarbons such as hexane, heptane and decane; alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; and ethylene chloride.
- halogenated hydrocarbons such as chlorobenzene and dichloromethane, or mixtures thereof.
- the heating temperature depends on the solvent used, but is usually from a temperature not lower than the freezing point of the solvent to 200, preferably up to 150 ° C.
- the mixing time is usually 30 seconds to 24 hours, preferably 10 minutes to 10 hours, depending on the temperature.
- a filtration method used in ordinary organic production chemistry can be employed.
- the cake component after filtration may be washed with an aromatic hydrocarbon or an aliphatic hydrocarbon exemplified above as necessary.
- the molar ratio of magnesium atoms to aluminum atoms (Mg / A 1) and the molar ratio of alkoxy groups to aluminum atoms, which are characteristics of the carrier component of the present invention, are also described.
- the ratio (O RZA 1) satisfies the range of l ⁇ MgZAl ⁇ 300.0.0, 0.05 and ORZAl ⁇ 2.0.
- organometallic compound (C) (optionally referred to as “organometallic compound” in the following description) which is used as necessary, is specifically as follows.
- Organometallic compounds of Groups 1 and 2 and Groups 12 and 13 can be used arbitrarily.
- R a and R b may be the same or different from each other, and represent a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms.
- X is a halogen atom
- Specific examples of such compounds include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, and diisobutyl aluminum hydride.
- M a is i, indicates N a or K, R a is. Showing a is 1 to 15, the good Mashiku 1-4 hydrocarbon group carbon atoms) the periodic table represented by Complex alkylated product of Group 1 metal and aluminum. Such compounds, L i Al (C 2 H 5) 4, L i A 1 (C 7 H 15) 4 and the like can be exemplified.
- C-lc General formula R ab M b
- R a and R b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M b is Mg, Zn or C d
- organoaluminum compounds are preferred, and the organoaluminum compound (C-la) is particularly preferred. Further, such an organometallic compound (C-1) may be used alone or in combination of two or more.
- One of the points of the present invention is that by using the carrier component of the present invention, it is not necessary to use a conventionally used organoaluminoxy compound or organoboron compound together with a transition metal compound. . Therefore, at least one compound selected from (C-la), (C-lb) and (C-lc) is sufficient as an optional component in the olefin polymerization catalyst.
- the organometallic compound (C-2) or (C-3) as shown below may be contained as the organometallic compound (C) in the catalyst for polymerization of the present invention.
- the organoaluminoxy compound (C-2) used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminoxy compound as exemplified in JP-A-2-78687. It may be a compound.
- a conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
- an organoaluminum compound such as a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
- an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.
- the aluminoxane may contain a small amount of an organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for aluminoxane.
- organoaluminum compound used for preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-la).
- trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.
- organoaluminum compounds are used alone or in combination of two or more.
- the A1 component soluble in benzene 6 is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of A1 atom. That is, those which are insoluble or hardly soluble in benzene are preferred.
- These organic aluminum oxy compounds (B-2) are used alone or in combination of two or more.
- the compound (C-3) (hereinafter referred to as “ionized ionic compound”) which forms an ion pair by reacting with the transition metal compound (A) according to the present invention is disclosed in JP-A-1-501950, Lewis acids and ions described in Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Compounds, polan compounds, and porphyrin compounds. Further, heteropoly compounds and isopoly compounds can also be mentioned. Such an ionized ionic compound (C-3) is used alone or in combination of two or more.
- the catalyst for polymerization of olefins of the present invention comprises: (B) a carrier component; Group compound, in addition to (C) a specific organometallic compound, further S I_ ⁇ 2, A 1 2 0 3, Mg ⁇ , Z rO, T i 0 2 , B 2 0 3, C A_ ⁇ , Zn_ ⁇ , B A_ ⁇ , polyethylene Th_ ⁇ 2
- such inorganic carriers and particle sizes of granular or fine particulate organic polymer is in the range of 10 to 300 im, polypropylene, it may be used in combination Poriputen
- Polyolefin of the present invention in the presence of said Orefin polymerization catalyst, obtainable by homopolymerization or copolymerization with Orefu fin high activity, KasamiHisoka degree is 0.20 (g / cm 3) or more It is a polyolefin.
- the olefin used for the polymerization reaction is at least one monomer selected from ethylene and Q! -Olefin, and at least one of the monomers is ethylene or propylene.
- olefins include linear or branched ⁇ -olefins having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, 1-butene, 2-butene, 1-pentene, 3 -Methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicose, etc.
- a cyclic olefin having 3 to 30, preferably 3 to 20 carbon atoms for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norporene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; a polar monomer such as allylic alcohol, acrylic acid, methacrylic acid, fumaric acid, 3-unsaturated carboxylic acids such as maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, and their sodium salts; Metal salts such as potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso
- the polymerization may be carried out in the presence of a functional group-containing styrene derivative of the formula; 3-phenylpropylene, 4-phenyl
- an olefin polymer is obtained by polymerizing or copolymerizing the olefin in the presence of the above-described catalyst for olefin polymerization.
- the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods.
- the inert hydrocarbon medium used in the solution polymerization or suspension polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as pentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; octacyclic hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like; A mixture and the like can be mentioned, and olefin itself can be used as a solvent.
- the component (A) per liter of the reaction volume usually 1 0- 8-1 0- 2 moles, rather preferably 1 0 used in one 7 to 1 0 amounts such that one 3 moles.
- Component (B) is a magnesium atom, and the molar ratio [Mg / M] to all transition metal atoms (M) in component (B) is usually from 1.0 to 100, preferably from 10 to 8 It is used in such an amount that it becomes 0 0.
- the component (C) is composed of the metal atom ( ⁇ ') in the component (C), It is used in an amount such that the molar ratio [M'ZM] to the total transition metal (M) in the component (A) is usually 5 to 5000, preferably 100 to 3000.
- the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of ⁇ 50 to + 200 ° C., preferably 0 to 170 ° C.
- the polymerization pressure is usually from normal pressure to 1 OMPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. it can. Further, the polymerization can be performed in two or more stages under different reaction conditions.
- the molecular weight of the resulting olefin polymer can also be controlled by the presence of hydrogen, organosilane compounds or other known molecular weight regulators in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by the amount of the component (A) used.
- the polymer obtained by the polymerization method of the present invention described above has a feature that the bulk density is 0.20 (g / cm 3 ) or more, preferably 0.22 (g / cm 3 ) or more.
- the metal content in the carrier component was determined by plasma emission mass spectrometry.
- the halogen content was measured by a potentiometric titration method, and the alkoxy group content was measured by gas chromatography.
- the average particle diameter was determined as a number average by the light transmission sedimentation method using the known Stokes equation (Equation 1).
- the crystallite size was measured by measuring the half width (FWHM) of the (110) plane of magnesium chloride with an X-ray diffractometer (RU-300, manufactured by Rigaku Denki), and using the well-known Scherrer equation (where , 0.9 is reduced to a constant K). All samples used for the measurement of crystallite size were handled under a nitrogen atmosphere. The method of measuring the crystallite size using Scherrer's equation is detailed in “Carity X-Ray Diffraction Theory (Translated by Gentaro Matsumura), Agnesha”.
- Mobile phase ⁇ -Dichlorobenzene (Wako Pure Chemical Industries). Mobile phase flow rate: 1ml / min.
- Detection method Detected by refractometer integrated with chromatograph
- ASTM D Value measured under a load of 190 ⁇ 2.16 kg by the standard method of 1238.
- the structure of the compound obtained in the synthesis example was determined using 27 OMHz iH-NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A) and the like.
- component (b 1-1) Into a flask with an internal volume of 200 ml, which had been sufficiently purged with nitrogen, 25 ml of the component (bl) (25 mmol in terms of magnesium atoms) and 10 Oml of purified decane were charged, and the mixture was purified while maintaining the liquid temperature at 15 with stirring. 26 mmol of triethylaluminum diluted with decane were charged dropwise over 30 minutes. Thereafter, the liquid temperature was raised to 80 ° C. over a period of 120 minutes, and the reaction was further carried out for 60 minutes.
- the polymerization activity was 167.2 kg / mmol-zr-hr, and the polymerization activity per 1 g of the component (bl-1-a2-172) was 5.1 kg / g-cat'hr. 7?] was 16.3 d 1 /, and the bulk density was 0.24 g / ml.
- the Mw of the polyethylene measured by GPC measurement was 1.9 ⁇ 10 6 , and the MwZMn ratio was 4.1. (Example 2)
- Example 2 In the same manner as in Example 1 except that the component (bl-l-a2-140) prepared above was used in place of the component (bl-l-a2-172) in [Polymerization] of Example 1 Polymerization was performed. As a result, 50.9 g of polyethylene was obtained.
- Polymerization activity is 127.3 kg / mmol-Zr-r, component (b1-1-a2-140)
- the polymerization activity per lg is 4.2 kg Zg-cat'hr.
- [77] was 18.3 dl / g, and the bulk density was 0.33 gZm1.
- the Mw of the polyethylene measured by GPC was 2.4 ⁇ 10 6 , and the MwZMn ratio was 5.9.
- a part of the component (b1-1-a2-204) prepared by the above operation was dried and the composition was examined.
- magnesium was 17.0% by weight and aluminum was 2.7% by weight.
- the content of 2,2-ethylhexoxy groups was 24.0% by weight, the content of chlorine was 50.0% by weight, and the content of zirconium was 0.31% by weight. Therefore, the molar ratio of magnesium to aluminum (MgZAl) was 7.0, and the molar ratio of 2-ethylhexoxy group to aluminum (ORZA1) was 1.8.
- Example 2 Same as Example 1 except that the component (bl-1-a2-204) prepared above was used in place of the component (b1-1-a2-172) in [Polymerization] of Example 1 And the polymerization was carried out. As a result, 40.3 g of polyethylene was obtained.
- the polymerization activity is 100.8 kg / mmol-zr-hr, and the polymerization activity per 1 g of the component (bl-l-a2-204) is 3.4 kg / g-cat'hr.
- a part of the component (b1-1-a2-126) prepared by the above operation was dried and the composition was examined.
- magnesium was 17.0% by weight and aluminum was 2.8% by weight.
- the content of 2,2-ethylhexoxy groups was 25.8% by weight, chlorine was 51.0% by weight, and zirconium was 0.31% by weight. Therefore, the molar ratio of magnesium to aluminum (Mg / A 1) was 6.7, and the molar ratio of 21-ethylhexoxy group to aluminum (ORZA 1) was 1.9.
- Example 1 instead of the component (b 1-1-1 a2-172), Polymerization was carried out in the same manner as in Example 1 except that the component (b1-1-a2-126) (0.001 mmol in terms of zirconium atom) prepared above was used. As a result, 20.5 g of polyethylene was obtained.
- the polymerization activity is 20.5 kg / mmol-Zr-hr, and the polymerization activity per 1 g of the component (b1-1-1a2-126) is 0.7 kg / g-cat'hr. ⁇ ?] was 0.5 d l // g, and the bulk density was 0.20 g / ml.
- a part of the component (b1-1-a2-116) prepared by the above operation was dried and the composition was examined.
- magnesium was 17.0% by weight and aluminum was 2.8% by weight.
- 2,2-ethylhexoxy group was 26.6% by weight, chlorine was 49.0% by weight, and zirconium was 0.30% by weight. Therefore, the molar ratio of magnesium to aluminum (Mg / Al) was 6.7, and the molar ratio of 2-ethylhexoxy group to aluminum (ORZA1) was 2.0.
- Example 1 In the [Polymerization] of Example 1, in place of the component (bl-1—a2—172), the component (b1-1—a2—116) prepared above (0.011 mmol in terms of zirconium atom) Polymerization was carried out in the same manner as in Example 1 except that was used. As a result, 17.5 g of polyethylene was obtained.
- the polymerization activity was 17.5 kg / mmol-Zr-hr, and the polymerization activity per 1 g of the component (b1-1-a2-116) was 0.6 kg / g-cat'hr. [77] had a volume density of 20.0 dlZg and a bulk density of 0.31 gZml.
- a part of the component (bl-l2-a2-228) prepared by the above operation was dried, and the composition was examined.
- magnesium was 18.0% by weight
- aluminum was 2.6% by weight.
- 2-ethylhexoxy group was 20.0% by weight
- chlorine was 54.0% by weight
- zirconium was 0.35% by weight. Therefore, the molar ratio between magnesium and aluminum (MgZAl) was 7.7, and the molar ratio between 2-ethylhexoxy group and aluminum (OR / A1) was 1.6.
- Example 1 In the [polymerization] of Example 1, in place of the component (bl-l-a2-172), the component (bl-l-a2-228) prepared above (0.001 mmol in terms of zirconium atom) was used. Polymerization was carried out in the same manner as in Example 1 except that the polymer was used. As a result, 8.8 g of polyethylene was obtained.
- the polymerization activity is 8.8 kg of ethanol-Zr'hr, and the polymerization activity per 1 g of the component (b1-1-a2-228) is 1.2 kg / g-cat'hr. of [? ?] Was 0.24 d lZg.
- the Mw of the polyethylene measured by GPC was 3.0 ⁇ 10 3 , and the MwZMn ratio was 1.9.
- magnesium was 18.0% by weight
- aluminum was 2.5%.
- Example 1 In the [polymerization] of Example 1, in place of the component (b 1-1-a2-172), the component (bl-1-1 a 2-138) prepared above (0.001 mmol in terms of zirconium atom) Polymerization was carried out in the same manner as in Example 1 except that was used. As a result, 55.5 g of polyethylene was obtained.
- the polymerization activity was 55.5 kg mmol-Zr'hr, and the polymerization activity per 1 g of the component (b1-1-a2-138) was 2.0 kgZg-cat'hr. ?] was 13.7 dlZg, and the bulk density was 0.21 gm 1.
- the Mw of the polyethylene measured by GPC measurement was 166.8 ⁇ 10 4 , and the MwZMn ratio was 12.3.
- a part of the component (b1-1-a2-24, 1) prepared by the above operation was dried, and the composition was examined.
- magnesium was 18.0% by weight and aluminum was 2.5% by weight.
- the 2-ethylhexoxy group was 22.8% by weight, chlorine was 52.0% by weight, and zirconium was 0.28% by weight. Therefore, the molar ratio of magnesium to aluminum (Mg / Al) was 8.0, and the molar ratio of 2-ethylhexoxy group to aluminum (OR / A1) was 1.9. (a 2-241) Polymerization
- Example 1 In the [Polymerization] of Example 1, in place of the component (bl-1—a2—172), the component (b1-1—a2—241) prepared above (0.001 mmol in terms of zirconium atom) Polymerization was carried out in the same manner as in Example 1 except that was used. As a result, 22.6 g of polyethylene was obtained.
- the polymerization activity is 22.6 kg / mmol-Zr-hr>
- the polymerization activity per 1 g of the component (bl-1-a2-241) is 0.7 kg Zg-cat'hr. ?] was 9.7 dlZg, and the bulk density was 0.20 g ml.
- component (b1-1) in terms of magnesium atoms and 100 ml of purified toluene were charged, and the following components were added while stirring and maintaining at room temperature. 18.8 ml of a toluene solution of (a 2-172) (0.00 106 mmo 1 / m 1) was charged dropwise over 20 minutes. After stirring for 1 hour, a solid portion was collected by filtration, sufficiently washed with toluene, and 5 Oml of purified decane was added to obtain a decane slurry of the component (bl-a2-134).
- Example 1 In the [Polymerization] of Example 1, in place of the component (b1-1-a2-172), the component (b1-1-a2-134) prepared above (0.001 mmol in terms of zirconium atom) was used. Polymerization was carried out in the same manner as in Example 1 except that) was used. As a result, 15.0 g of polyethylene was obtained.
- the polymerization activity was 15.0 kg / mmol-Zr-hr, and the polymerization activity per 1 g of the component (bl-1—a2-241) was 0.5 kg Zg-cat'hr. ?] was 2.8 dl / g and the bulk density was 0.23 gZml.
- the polymerization activity is 160.6 kg / nunol-Zr-hr, and the polymerization activity per lg of the component (bl-1 a 2-195) is 3.9 kg gg-cat'hr. Was 17.2 dl / g, and the bulk density was 0.28 g_ml.
- magnesium was 18.0% by weight
- aluminum was 26.0% by weight
- 2-ethyl Hexoxy groups were 21.4% by weight and chlorine was 52.0% by weight.
- the molar ratio of magnesium to aluminum (MgZAl) was 7.7
- the molar ratio of 2-ethylhexoxy group to aluminum (ORZA 1) was 1.7.
- the zirconium atom content in 1 g of the component (b1-2-a2-172) was calculated to be 4.5 mg / g.
- Example 12 Same as Example 12 except that in the [polymerization] of Example 12, the component (bl-2-a2-172) prepared above was used instead of the component (bl-1-a2-195). And the polymerization was carried out. As a result, 57.2 g of polyethylene was obtained.
- the polymerization activity is 163.3 kg gZ ol-Zr'hr, and the polymerization activity per component (b 2-l-a 2-172) lg is 8.1 kg gZg-cat'hr. 17.4 dl // g, bulk density was 0.27 gZml.
- component (b 2) 95.2 g (1.0 mol) of anhydrous magnesium chloride, 55 lml of decane and 325.5 g (2.5 mol) of 2-ethylhexyl alcohol were reacted with 13 for 2 hours to obtain a homogeneous solution (component (b2 )) was obtained.
- a part of the component (b2-1) prepared by the above operation was dried, and the composition was examined.
- magnesium was 18.0% by weight
- aluminum was 2.3% by weight
- the ethylhexoxy group was 19.0% by weight and the chlorine was 54.0% by weight. Therefore, the molar ratio between magnesium and aluminum (Mg / Al) was 8.7, and the molar ratio between 2-ethylhexoxy group and aluminum (ORZA 1) was 1.6.
- Example 12 [Polymerization] of Example 12 In the same manner as in Example 12, except that the component (b2-1-a2-172) prepared above was used instead of the component (bl-11-a2-195), Polymerization was performed. As a result, 55.9 g of polyethylene was obtained.
- the polymerization activity was 159.7 kg / mmol-Zr-hr, and the polymerization activity per 1 g of component (b2-1-a2-172) was 7.2 kg Zg-cat'hr.
- [5] was 17.2 dlZg and the bulk density was 0.29 gZml.
- magnesium was 25.0% by weight and aluminum was 0. 6% by weight, 2.6% by weight of 2-ethylhexoxy group, and 71.0% by weight of chlorine. Therefore, the molar ratio of magnesium to aluminum (Mg / Al) was 46.3, and the molar ratio of 2-ethylhexoxy group to aluminum (OR / A1) was 0.9.
- component (b 1— 3— a2— 172) Purified toluene and the component (bl-3) were charged in an amount of 35.3 mol in terms of magnesium atoms in a 20-mL flask with an internal volume of 20 OmL, which had been sufficiently purged with nitrogen, so that the total volume became 85.3 mL. While maintaining this at 25, 14.7 mL of a toluene solution (0.00102 lmmo 1 / mL) of the following component (a2-172) was added dropwise over 20 minutes with stirring. After stirring for 1 hour, a solid portion was collected by filtration, washed sufficiently with toluene, and decane was added to obtain a decane slurry of the component (b 1-3-a 2-172).
- the zirconium content in 1 g of the component (b 1-3 -a2-172) was calculated to be 5.72 mg g.
- Example 12 In the same manner as in Example 12 except that the component (bl-3-a2-172) prepared above was used instead of the component (bl-1-a2-195) in [Polymerization] of Example 12, Polymerization was performed. As a result, 37.8 g of polyethylene was obtained.
- the polymerization activity is 108. I kg / mmol-Zr-r component (bl-3-3-a2-172) The polymerization activity per lg is 6.8 kgZg-cat'hr, and [?)] Of this polyethylene is 16.6 dl / g and bulk density was 0.40 g / ml.
- magnesium was 24.0% by weight
- aluminum was 0.6% by weight
- 2-ethylhexoxy was obtained.
- the group was 4.8% by weight and chlorine was 68.0% by weight. Therefore, the molar ratio of magnesium to aluminum (MgZAl) was 44.4, and the molar ratio of 2-ethylhexoxy group to aluminum (ORZA 1) was 1.66.
- Purified toluene and the component (b1-4) were charged into a flask having an internal volume of 20 OmL, which had been sufficiently purged with nitrogen, to have a total volume of 85.2 mL, in an amount of 3 mmol in terms of magnesium atoms. While maintaining the temperature at 25, 14.8 mL of a toluene solution (0.00001014 mmo 1 ZmL) of the component (a 2-172) used in Example 1 was added dropwise with stirring over 20 minutes. After stirring for 1 hour, a solid portion was collected by filtration, sufficiently washed with toluene, and decane was added to obtain a decane slurry of the component (bl-4-a2-172).
- Example 12 In the same manner as in Example 12, except that the component (bl-4-1a2-172) prepared above was used in place of the component (bl-1-a2-195) in [Polymerization] of Example 12, To carry out the polymerization. As a result, 70.3 g of polyethylene was obtained.
- the polymerization activity is 20.8 kg ZZol-Zr'hr
- the polymerization activity per lg of the component (b1-2-a2-172) lg is 13.2 kgZg-cat'hr.
- the [77] of the styrene was 16.2 dlZg
- the bulk density was 0.34 gZml.
- component (b 1-5) To a flask with an inner volume of 40 OmL, which was sufficiently purged with nitrogen, 25 mL (25 mmol in terms of magnesium atom) of the component (b1) prepared in Example 1 and 10 OmL of purified toluene were charged, and the temperature of the solution was stirred. While keeping at 0, 13 mmol of triethylaluminum diluted with toluene were charged dropwise over 15 minutes. Thereafter, the liquid temperature was raised to 105 ° C over 110 minutes, and the reaction was performed for 2 hours.
- reaction solution was cooled to 120 ° C, and while stirring, the solution temperature was maintained at 120 ° C, and 13 mmol of triethylaluminum diluted with toluene was dropped in over 15 minutes. did. Thereafter, the liquid temperature was raised to 105 ° C over 200 minutes, and the reaction was carried out for 1 hour. Thereafter, the mixture was cooled to 120 ° C. again, charged with 13 mmol of triethylaluminum in the same manner as above, and heated to 105T. After reacting at 105 ° 0 for 1 hour, 162 mmol of triethylaluminum diluted with toluene was charged dropwise over 30 minutes, and then heated and reacted for 1 hour.
- Purified toluene and the component (bl-5) were charged into a flask with an internal volume of 20 OmL, which had been sufficiently purged with nitrogen, to have a total volume of 85.5 mL. While keeping the temperature at 25, 14.5 mL of a toluene solution (0.00001032 mmol / mL) of the component (a 2-172) used in Example 1 was added dropwise with stirring over 20 minutes. After stirring for 1 hour, the solid portion was collected by filtration, washed sufficiently with toluene, and decane was added to obtain a decane slurry of the component (bl-5-a2-172).
- Example 10 component instead of (BL- 1 one a2-195), component prepared above (b 1 - 5-a 2 - 172) except for using Example 10 and same as And the polymerization was carried out. As a result, 53.lg of polyethylene was obtained.
- the polymerization activity is 151.6 kgZmmol-Zr'lu:
- the polymerization activity per lg of the component (bl-5-a2-172) lg is 9.4 kgZg-cat'hr. [??] was 16.4 dlZg and the bulk density was 0.37 gZml.
- the average particle size of the obtained component (bl-6) was as follows.
- Purified toluene and the component (bl-6) were charged in an amount of 35.3 mol in terms of magnesium atoms in a 20-mL flask with an internal volume of 20 OmL, which had been sufficiently purged with nitrogen, so that the total volume became 85.3 mL. While maintaining the temperature at 25 ° C., 14.7 mL of a toluene solution (0.001018 mmo 1 ZmL) of the component (a2-172) used in Example 1 was added dropwise with stirring over 20 minutes. After stirring for 1 hour, the solid portion was collected by filtration, sufficiently washed with toluene, and decane was added to obtain a decane slurry of the component (bl-6-a2-l72).
- Example 10 [Polymerization] of Example 10 was repeated except that the component (b1-6-a2-l72) prepared above was used instead of the component (b1-1-1a2-195). Polymerization was carried out in the same manner. As a result, 60.5 g of polyethylene was obtained.
- the polymerization activity was 173.0 kg gZol-Zr.'hr, and the polymerization activity per lg of the component (bl-6-a2-172) lg was 9.8 kg / g-cat'hr.
- Polyethylene [7]] was 17.2 dl / s, and bulk density was 0.22 g / 1.
- Example 19 Preparation of component (bl-6)
- the component (b1) was prepared in the same manner as in Example 19 except that anhydrous benzene was used in place of anhydrous 1,2-dichlorobenzene. — 7) was prepared.
- the average particle size of the prepared component (bl-7) was 5 m, a part was dried, and the composition was examined.
- magnesium was 18.0% by weight and aluminum was 2.6% by weight.
- the content of 2-ethylhexoxy groups was 20.4% by weight, and the content of chlorine was 52.0% by weight. Therefore, the molar ratio between magnesium and aluminum (MgZAl) is 7.7, and the molar ratio between 2-ethylhexoxy group and aluminum (ORZA 1) is 1.6.
- Example 1 Purified toluene and the component (bl-7) were charged in an amount of 35.7 mol in terms of magnesium atoms in a 20-mL flask with an internal volume of 20 OmL, which had been sufficiently purged with nitrogen, so that the total volume became 85.7 mL. While keeping this at 25 ° C, the components used in Example 1 were stirred and stirred.
- the zirconium atom content in 1 g of the component (b 1-7 -a2-172) was calculated to be 5.67 mg / g.
- Example 10 [Polymerization] was performed in the same manner as in Example 10 except that the component (b 1-7 -a2-172) prepared above was used instead of the component (b 1-1 -8,2-195). Polymerization was carried out in the same manner. As a result, 58.6 g of polyethylene was obtained.
- the polymerization activity is 167.5 kg / mmol-Zr-hr
- the polymerization activity per lg of the component (bl-7-a2-172) lg is 8.4 kg / g-cat'hr. [??] was 18. ld lZg and bulk density was 0.23 gZml.
- the ethylhexoxy group was 4.8% by weight, and chlorine was 68.0% by weight. Therefore, the molar ratio of magnesium to aluminum (MgZAl) was 72.2, and the molar ratio of 2-ethylhexoxy group to aluminum (OR / A1) was 0.3.
- Purified toluene and component (b3-1) were charged into a flask having a content of 20 OmL, which had been sufficiently purged with nitrogen, in an amount of 85.4 mL, to be 3 mmol in terms of magnesium atoms. While maintaining the mixture at 25, 14.5 mL of a toluene solution (0.00001022 mmol 1 ZmL) of the component (a 2-172) used in Example 1 was added dropwise over 20 minutes with stirring. After stirring for 1 hour, the solid portion was collected by filtration, sufficiently washed with toluene, and 5 Oml of decane was added to obtain a decane slurry of the component (b3-l-a2-172).
- Example 10 Same as Example 10 except that the component (b3-1-a2-172) prepared above was used instead of the component (b1-1-a2-195) in [Polymerization] of Example 10. And the polymerization was carried out. As a result, polyethylene, 108. Og was obtained. Therefore, the polymerization activity is 308.4 kg / mmol-Zr-hr, and the polymerization activity per lg of the component (b3-1-a2-172) lg is 21.0 kg Zg-cat'hr. [7?] Was 17.9 dlZg and the bulk density was 0.1 S SgZml.
- magnesium was 26.0% by weight
- aluminum was 0.4% by weight
- the ethylhexoxy group was 0.7% by weight and chlorine was 19.% by weight. Therefore, the molar ratio of magnesium to aluminum (MgZAl) was 72.2, and the molar ratio of 2-ethylhexoxy group to aluminum (ORZA1) was 0.4.
- Example 10 Same as Example 10 except that the component (b3-1-E2-195) was replaced by the component (b3-2-a2-172) prepared above in [Polymerization] of Example 10 And the polymerization was carried out. As a result, 82.9 g of polyethylene was obtained.
- the polymerization activity is 236.7 kg / mmol-Zr-hr.
- the polymerization activity per lg of the component (b3-2-a2-172) lg is 15.8 kg Zg-cat'hr. Its [77] was 17.4dl_g and its bulk density was 0.23gZml.
- component (b3-3) prepared by the above operation was dried, and the composition was examined.
- magnesium was 24.0% by weight
- aluminum was 0.4% by weight
- the ethylhexoxy group was 0.8% by weight
- chlorine was 69.0% by weight. Therefore, the molar ratio of magnesium to aluminum (MgZAl) was 66.6, and the molar ratio of 2-ethylhexoxy group to aluminum (ORZA1) was 0.4.
- Purified toluene and the component (b3-3) were charged in an amount of 35.7 mol in terms of magnesium atoms into a 20-mL flask with an internal volume of 20 OmL, which had been sufficiently purged with nitrogen, so that the total volume became 85.7 mL. While maintaining the temperature at 25 ° C., 14.3 mL of a toluene solution (0.00001052 mmol / mL) of the component (a 2-172) used in Example 1 was added dropwise with stirring over 20 minutes. After stirring for 1 hour, a solid portion was collected by filtration, sufficiently washed with toluene, and decane was added to obtain a decane slurry of the component (b3-3-a2-172).
- Example 10 [Polymerization] was the same as Example 10 except that the component (b3-3-a2-172) prepared above was used instead of the component (b1-1-a2-195). Polymerization was carried out as described above. As a result, 99.5 g of polyethylene was obtained.
- the average particle size of the obtained component (bl-8) was 20 m.
- a part of the component (component (bl-8)) prepared by the above operation was dried and the composition was examined.
- 6.5% by weight of magnesium, 3.5% by weight of aluminum, and 2% The methylhexoxy group was 78.0% by weight, the chlorine was 18.0% by weight, and the molar ratio of magnesium to aluminum (Mg / A1) was 2.0, 2-ethylhexoxy group and aluminum.
- the molar ratio (OR / A 1) was 4.6.
- the polymerization activity per molecule of the component (a 2 -116) is as high as 266,000 g / mmol-Zr-hr
- the activity per 1 g of the raw material used for preparing the carrier component (B) is 0.2 kg /
- the g-cat'hr was very low, and the bulk density was as low as 0.09 g / ml.
- the molar ratio between magnesium and aluminum (MgZAl) in the system was calculated as 0.26, and the molar ratio between 2-ethylhexoxy group and aluminum (OR / A1) was calculated as 0.79.
- a carrier component (B) was separately prepared in the same manner as described above, and the particle size was measured.
- an olefin polymer having excellent powder properties can be obtained with extremely high polymerization activity without using it in combination with expensive organoaluminum oxy compound or organoboron compound, which is industrially useful. is there.
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AU2003301539A AU2003301539A1 (en) | 2002-10-23 | 2003-10-20 | Magnesium-containing carrier components and application thereof to olefin polymerization |
KR1020057004356A KR100662836B1 (ko) | 2002-10-23 | 2003-10-20 | 마그네슘을 함유하는 담체 성분 및 올레핀 중합에의 응용 |
US10/526,906 US7253132B2 (en) | 2002-10-23 | 2003-10-20 | Magnesium-containing carrier components and application thereof to olefin polymerization |
JP2005501569A JP5221848B2 (ja) | 2002-10-23 | 2003-10-20 | マグネシウムを含む担体成分及びオレフィン重合への応用 |
CNB2003801019147A CN1331896C (zh) | 2002-10-23 | 2003-10-20 | 含镁的载体成分以及在烯烃聚合中的应用 |
EP03756697A EP1555272B1 (en) | 2002-10-23 | 2003-10-20 | Supported olefin polymerisation catalyst |
DE60335281T DE60335281D1 (de) | 2002-10-23 | 2003-10-20 | Geträgerter olefin-polymerisationskatalysator |
US11/822,012 US7528091B2 (en) | 2002-10-23 | 2007-06-29 | Magnesium-containing carrier component and application to olefin polymerization |
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WO2006016101A1 (en) * | 2004-08-12 | 2006-02-16 | Ineos Europe Limited | Polymerisation and oligomerisation catalysts |
US8067328B2 (en) | 2004-08-12 | 2011-11-29 | Ineos Europe Limited | Polymerisation and oligomerisation catalysts |
WO2006030199A1 (en) * | 2004-09-15 | 2006-03-23 | Ineos Europe Limited | Polymerisation catalysts |
JP2006206769A (ja) * | 2005-01-28 | 2006-08-10 | Mitsui Chemicals Inc | 非凝集・球状のエチレン系重合体微粒子からの無機物除去方法 |
JP2006206768A (ja) * | 2005-01-28 | 2006-08-10 | Mitsui Chemicals Inc | 非凝集・球状のエチレン系重合体粒子の製造方法 |
EP1767549A1 (en) | 2005-09-20 | 2007-03-28 | Ineos Europe Limited | Polymerisation catalysts |
WO2007034149A2 (en) | 2005-09-20 | 2007-03-29 | Ineos Europe Limited | Polymerisation catalysts |
US7902308B2 (en) * | 2005-09-20 | 2011-03-08 | Ineos Europe Limited | Polymerisation catalysts |
JP2014181278A (ja) * | 2013-03-19 | 2014-09-29 | Mitsui Chemicals Inc | オレフィン重合用触媒、それを用いたオレフィン系重合体の製造方法 |
CN109400778A (zh) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | 用于烯烃聚合的催化剂组分及其制备方法和用于烯烃聚合的催化剂以及烯烃聚合方法 |
CN109400778B (zh) * | 2017-08-18 | 2021-02-05 | 中国石油化工股份有限公司 | 用于烯烃聚合的催化剂组分及其制备方法和用于烯烃聚合的催化剂以及烯烃聚合方法 |
Also Published As
Publication number | Publication date |
---|---|
JP5221848B2 (ja) | 2013-06-26 |
DE60335281D1 (de) | 2011-01-20 |
JPWO2004037870A1 (ja) | 2006-02-23 |
AU2003301539A1 (en) | 2004-05-13 |
CN1705685A (zh) | 2005-12-07 |
EP1555272A1 (en) | 2005-07-20 |
US7528091B2 (en) | 2009-05-05 |
US7253132B2 (en) | 2007-08-07 |
US20080015401A1 (en) | 2008-01-17 |
EP1555272B1 (en) | 2010-12-08 |
CN1331896C (zh) | 2007-08-15 |
KR20050053661A (ko) | 2005-06-08 |
US20060155083A1 (en) | 2006-07-13 |
KR100662836B1 (ko) | 2006-12-28 |
EP1555272A4 (en) | 2006-08-02 |
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