WO2013099626A1 - α-オレフィンの製造方法 - Google Patents
α-オレフィンの製造方法 Download PDFInfo
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- WO2013099626A1 WO2013099626A1 PCT/JP2012/082359 JP2012082359W WO2013099626A1 WO 2013099626 A1 WO2013099626 A1 WO 2013099626A1 JP 2012082359 W JP2012082359 W JP 2012082359W WO 2013099626 A1 WO2013099626 A1 WO 2013099626A1
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
- C07C2/34—Metal-hydrocarbon complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/007—Promoter-type Additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of chromium, molybdenum or tungsten
Definitions
- the present invention relates to a method for producing an ⁇ -olefin, which is widely used industrially as a raw material for polyethylene comonomer, synthetic lubricating oil, surfactant and the like.
- ⁇ -olefins especially 1-hexene, 1-octene and the like are synthesized as comonomers of linear low density polyethylene (L-LDPE), and ⁇ -olefins containing up to 14 carbon atoms containing 1-tetradecene are synthesized.
- L-LDPE linear low density polyethylene
- ⁇ -olefins containing up to 14 carbon atoms containing 1-tetradecene are synthesized.
- these ⁇ -olefins are obtained by polymerizing from ethylene.
- the polymerization degree distribution of the obtained ⁇ -olefins follows the Schulz-Flory distribution, and in the normal distribution, the dimer is the most, and the tetramer Satisfy the relationship that there are more trimers than n + 1 and more n-mers than n + 1-mers.
- ⁇ -olefins conforming to such a Schulz-Flory distribution are obtained in many industrially produced processes.
- a method using a triethylaluminum catalyst is also known, but ⁇ -olefins are known to have a Schultz-Flory distribution and to be used under high temperature and high pressure conditions.
- the amount and price of ⁇ -olefin varies depending on the number of carbon atoms, and the needs fluctuate. Therefore, in the conventional method in which ⁇ -olefin is produced according to the Schulz-Flory distribution, ⁇ -olefin more than 1-octene is produced. -There was a problem that the yield of olefins was low.
- the ⁇ -olefin As a countermeasure against this, by performing two-stage polymerization using a triethylaluminum catalyst, the ⁇ -olefin has the advantage of obtaining many products of 1-octene or more in accordance with the Poisson distribution. It is necessary to use a large amount (stoichiometrically), and there are disadvantages such as the catalyst recovery being indispensable and the apparatus becoming complicated and the ⁇ -olefin purity being low.
- Patent Documents 1 to 4 disclose methods for producing 1-hexene and 1-octene using a chromium compound. However, the ⁇ -olefin obtained thereby is one in which 1-hexene is the main component and 1-octene is low.
- Patent Document 5 discloses a transition metal compound having aminophosphine as a ligand, which is intended for production of a polymer.
- a catalyst system that improves the yield of ⁇ -olefins from 1-hexene to 1-tetradecene having 6 to 14 carbon atoms, particularly 1-octene.
- the present invention has been made in view of the above circumstances, and does not follow the Schulz-Flory distribution, and yields of ⁇ -olefins having 1 to 6 carbon atoms from 1 to hexene to 1 to tetradecene, particularly 1 to octene yields. It is an object of the present invention to provide a method for producing an ⁇ -olefin excellent in the above.
- the present invention relates to the following ⁇ -olefin production method.
- A a chromium compound
- B a ligand compound represented by the following general formula (1)
- C an ethylene-polymerizing method using a promoter
- L 1 to L 3 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 ring carbon atoms.
- chromium compound (A) is represented by the following general formula (2): CrX n D m (2)
- X represents a ⁇ -binding ligand, and when there are a plurality of X, a plurality of X may be the same or different
- D represents a Lewis base, and when there are a plurality of D, a plurality of D May be the same or different
- n is an integer of 2 to 3 and represents the valence of Cr
- m represents an integer of 0 to 6.
- L 1 to L 3 in the general formula (1) are each independently a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexyl group, and the substituent is an alkyl having 1 to 4 carbon atoms.
- the yield of ⁇ -olefins from 1 to hexene to 1-tetradecene having 6 to 14 carbon atoms, particularly the yield of 1-octene, which does not follow the Schulz-Flory distribution, is excellent.
- a manufacturing method is provided.
- the method for producing an ⁇ -olefin according to the present invention comprises polymerizing ethylene using (A) a chromium compound, (B) a ligand compound represented by the following general formula (1), and (C) a promoter. It is characterized by.
- L 1 to L 3 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 ring carbon atoms. Group, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
- carbon number ab in the expression “substituted or unsubstituted X group having carbon number ab” represents the number of carbons when X group is unsubstituted. The carbon number of the substituent when the X group is substituted is not included.
- the (A) chromium compound used in the present invention is not particularly limited as long as the chromium atom can form a complex with the ligand compound (B) described later, but is represented by the following general formula (2). Those are preferably used. CrX n D m (2) (In the formula, X represents a ⁇ -binding ligand, and when there are a plurality of X, a plurality of X may be the same or different, D represents a Lewis base, and when there are a plurality of D, a plurality of D May be the same or different, n is an integer of 2 to 3 and represents the valence of Cr, and m is an integer of 0 to 6, preferably 0 to 3.)
- X represents a ⁇ -bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and may be cross-linked with other X or D.
- this ⁇ -bonding ligand include halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and 1 to 20 amide groups, silicon-containing groups having 1 to 20 carbon atoms, phosphide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, acyl groups having 1 to 20 carbon atoms, substituted or unsubstituted acetylacetonate Substituted or unsubstituted carboxylate, and the like.
- halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
- hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group; vinyl group, propenyl group, cyclohexenyl group, etc.
- An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthrenyl group, and the like.
- alkyl groups such as methyl group, ethyl group, and propyl group
- aryl groups such as phenyl group are preferable.
- Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
- Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, methylphenoxy group, and dimethylphenoxy group.
- Examples of the amide group having 1 to 20 carbon atoms include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, methylethylamide group, and other alkylamide groups, divinylamide group, and dipropenylamide group.
- Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
- Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group Examples thereof include substituted silyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl group; silicon-substituted aryl groups such as trimethylsilylpheny
- Examples of the phosphide group having 1 to 20 carbon atoms include dimethyl phosphide group, diethyl phosphide group, dipropyl phosphide group, dibutyl phosphide group, dicyclohexyl phosphide group, and dioctyl phosphide group; An alkenyl phosphide group such as a fido group, a dipropenyl phosphide group and a dicyclohexenyl phosphide group; an arylalkyl phosphide group such as a dibenzyl phosphide group and a bis (phenylethylphenyl) phosphide group; a diphenyl phosphide group and a di Examples thereof include aryl phosphide groups such as a tolyl phosphide group and a dinaphthyl phosphide group.
- Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, E
- acyl group having 1 to 20 carbon atoms examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, stearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.
- D represents a Lewis base, and when there are a plurality of D, the plurality of D may be the same or different, and may be cross-linked with other D or X.
- Specific examples of the Lewis base of D include amines, ethers, phosphines, thioethers and the like.
- amines having 1 to 20 carbon atoms examples include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and dicyclohexylamine.
- Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, and dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, and phenylpropylamine; And arylamines such as naphthylamine.
- ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethy
- phosphines include phosphines having 1 to 20 carbon atoms. Specifically, monohydrocarbon substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkylphosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphin
- the chromium compound (A) include tris (acetylacetonato) chromium (III), tris (ethylhexanato) chromium (III), tri-t-butoxychromium (III), chromium trichloride, tribromide. Chromium, chromium dichloride, trichlorotris (THF) chromium, etc., tris (acetylacetonate) chromium (III), chromium trichloride, chromium dichloride, trichlorotris (THF) chromium, dichlorobis (THF) chromium, etc. Preferably used.
- the (B) ligand compound used in the present invention is represented by the following general formula (1).
- L 1 to L 3 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 ring carbon atoms. Group, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
- L 1 to L 3 are preferably a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 ring carbon atoms.
- alicyclic hydrocarbon group represented by L 1 to L 3 examples include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like, and a cyclopentyl group or a cyclohexyl group is preferable.
- the aromatic hydrocarbon group represented by L 1 to L 3 include a phenyl group, a naphthyl group, a phenanthryl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a fluoranthenyl group, a triphenylenyl group, and a fluorenyl group.
- Benzo [c] phenanthrenyl group benzo [a] triphenylenyl group, naphtho [1,2-c] phenanthrenyl group, naphtho [1,2-a] triphenylenyl group, dibenzo [a, c] triphenylenyl group, benzo [b] Fluoranthenyl group and the like, preferably phenyl group, 4-biphenylyl group, 3-biphenylyl group, 5′-m-terphenylyl group, 1-naphthyl group, fluoren-2-yl group, 2-naphthyl group, 9-phenanthrenyl group.
- Examples of substituted aromatic hydrocarbon groups represented by L 1 to L 3 include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5- Dimethylphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-6-methoxyphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-n-butylphenyl Group, 4-t-butylphenyl group and the like.
- aromatic heterocyclic group represented by L 1 to L 3 those containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
- Specific examples thereof include a pyrrolyl group. , Furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, indolyl Group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothiophenyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazinyl group, quina
- L 1 to L 3 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms. It is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and particularly preferably a substituted or unsubstituted phenyl group.
- the substituted phenyl group used as L 1 to L 3 is particularly preferably one having an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms as a substituent.
- the optional substituent in the case of “substituted or unsubstituted” described above and below is a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5), and 3 to 20 carbon atoms (preferably 5 carbon atoms).
- a cycloalkyl group an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 5), a haloalkyl group having 1 to 20 carbon atoms (preferably 1 to 5), a 1 to 20 carbon atoms (preferably 1 to 5) a haloalkoxy group, an alkylsilyl group having 1 to 10 carbon atoms (preferably 1 to 5), an aryl group having 6 to 30 ring carbon atoms (preferably 6 to 18 carbon atoms), a ring carbon atom number 6 to 30 ( Preferably 6-18) aryloxy group, 6-30 carbon atoms (preferably 6-18) arylsilyl group, 7-30 carbon atoms (preferably 7-20) aralkyl group, and 5 ring atoms.
- ⁇ 30 (good) Properly it may include 5 to 18) heteroaryl group.
- the use ratio of the component (A) to the component (B) is preferably in the range of 0.1 to 10 and in the range of 0.2 to 5 in terms of the molar ratio of the component (B) / the component (A). More preferably, it is particularly preferably in the range of 0.5 to 3.0. Moreover, 1 type, or 2 or more types can be used as (B) component.
- (C) Cocatalyst Specific examples of the (C) promoter used in the present invention include (C-1) aluminoxane and (C-2) a boron compound.
- R 1 represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization.
- R 1 represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom
- w represents an average degree of polymerization.
- aluminoxane examples include methylaluminoxane (MAO), methylisobutylaluminoxane (MMAO), ethylaluminoxane (EMAO), isobutylaluminoxane (IBAO) and the like, and methylaluminoxane (MAO) or methylisobutylaluminoxane (MMAO) is preferably used.
- Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method.
- a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) Crystal water contained in metal salts, etc., a method of reacting water adsorbed on inorganic or organic materials with an organoaluminum compound, (4) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water is there.
- the aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.
- the use ratio of the component (A) and the component (C) is preferably in the range of 1 to 10,000 as the molar ratio of the component (C) / the component (A), and in the range of 10 to 1,000. More preferably.
- the component (C) one or more selected from the components (C-1) and (C-2) can be used.
- (C-2) Boron compound Specific examples of the (C-2) boron compound include tris (pentafluorophenyl) boron, dimethylanilinium tetrakis (pentafluorophenyl) borate, and trityl tetrakis (pentafluorophenyl) borate.
- an organoaluminum compound in the method for producing an ⁇ -olefin of the present invention, can be used as the component (D) in addition to the components (A) to (C).
- the organoaluminum compound of the component (D) the general formula (III) R 2 v AlJ 3-v (III) [Wherein R 2 represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. Which is an integer].
- Specific examples of the compound represented by the general formula (III) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
- an organoaluminum compound to which a hydrocarbon group having 4 or more carbon atoms is bonded is preferable from the viewpoint of excellent high-temperature stability, and a compound having a hydrocarbon group having 4 to 8 carbon atoms is more preferable from this viewpoint. More preferably, when the reaction temperature is 100 ° C. or higher, a hydrocarbon group having 6 to 8 carbon atoms is more preferable.
- the (D) organoaluminum compound may be used singly or in combination of two or more.
- the use ratio of the component (A) to the component (D) is preferably 1: 1 to 1: 10,000, more preferably 1: 5 to 1: 2,000, and still more preferably 1:10 in molar ratio. A range of ⁇ 1: 1,000 is desirable.
- the component (D) the polymerization activity per chromium can be improved. However, when the amount is too large, the organoaluminum compound is wasted and a large load is applied to the post-treatment step. Absent.
- ethylene is polymerized in the presence of the above components (A) to (C).
- the components (A) to (C) may be added to the polymerization solvent after contacting any two or more of them in advance, or the components (A) to (C) may be mixed simultaneously.
- the polymerization temperature is preferably 0 to 150 ° C, more preferably 20 to 80 ° C.
- the polymerization pressure is preferably from normal pressure to 10 MPa, more preferably from 0.2 to 8.0 MPa, and particularly preferably from 0.5 to 5.0 MPa.
- polymerization solvent examples include benzene, toluene, xylene, pentane, heptane, cyclohexane, and methylcyclohexane. Toluene and cyclohexane are preferably used.
- the ratio of 1-octene in the ⁇ -olefin to be obtained is preferably not less than the ratio of 1-hexene. Further, the ratio of 1-octene is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. .
- Example 1 [Preparation of chromium complex solution] Add 20 ml (40 ⁇ mol) of tris (acetylacetonato) chromium toluene solution and 6 ml (120 ⁇ mol) of ligand compound A solution represented by the following formula to a 50 ml Schlenk tube substituted with nitrogen with a stirrer at room temperature. And stirred for about 2 hours. The solution was a light purple uniform solution.
- Example 2 A chromium complex solution was prepared and ethylene polymerization was carried out in the same manner as in Example 1 except that the amount of the ligand compound A solution used was changed from 6 ml (120 ⁇ mol) to 2 ml (40 ⁇ mol). The results are shown in Table 1.
- Example 3 To a THF (15 mL) solution of the ligand compound A (0.54 g, 1.96 mmol), an n-BuLi hexane solution (2.05 mmol, 0.82 mL) was added at ⁇ 10 ° C. The reaction mixture was stirred at room temperature overnight and this solution was added to a suspension of CrCl 2 (THF) 2 (0.27 g, 1.01 mmol) in THF (5 mL). After stirring for 18 hours, the solvent was distilled off under reduced pressure, and the solid residue was redissolved in toluene.
- THF CrCl 2
- Example 4 Ethylene polymerization was carried out in the same manner as in Example 2 except that the solvent was changed from toluene to cyclohexane. The results are shown in Table 1.
- Example 5 Ethylene polymerization was carried out in the same manner as in Example 1 except that the following ligand compound B solution was used instead of the ligand compound A solution. The results are shown in Table 1.
- Example 6 Ethylene polymerization was carried out in the same manner as in Example 1 except that the following ligand compound C solution was used instead of the ligand compound A solution. The results are shown in Table 1.
- Example 7 Ethylene polymerization was carried out in the same manner as in Example 1 except that the following ligand compound D solution was used instead of the ligand compound A solution. The results are shown in Table 1.
- Example 8 A chromium complex solution was prepared and ethylene polymerization was carried out in the same manner as in Example 7, except that the amount of the ligand compound D solution was changed from 6 ml (120 ⁇ mol) to 2 ml (40 ⁇ mol). The results are shown in Table 1.
- the yield of 1-octene (C8) is lower than the yield of 1-hexene (C6).
- the composition distribution of ⁇ -olefin obtained by the production method of the present invention does not follow the Schulz-Flory distribution.
- the 1-hexene (C6) yield is 1-octene. It has a feature that the yield of (C8) is higher, and it can be confirmed that the yield of 1-octene is excellent.
- the yield of 1-butene (C4) is low in any of Examples 1 to 8 and Comparative Examples 1 and 2, but this is volatilized because 1-butene is light. It is understood that it comes from.
- the ⁇ -olefin obtained by the production method of the present invention is useful for LLDPE comonomer, synthetic lubricating oil use and surfactant use.
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Abstract
Description
以上のような背景により、炭素数6から14までの1-ヘキセンから1-テトラデセンまでのα-オレフィンの得率、特に1-オクテンの得率を向上させる触媒系の開発が望まれている。
すなわち本発明は、以下のα-オレフィンの製造方法に関するものである。
1.(A)クロム化合物、(B)下記一般式(1)で表される配位子化合物、及び(C)助触媒を用いてエチレンを重合することを特徴とするα-オレフィンの製造方法、
2.前記(A)クロム化合物と、(B)配位子化合物とを接触させる工程と、その反応生成物と前記(C)助触媒とを反応させる工程とを有する上記1に記載のα-オレフィンの製造方法、
3.前記(A)クロム化合物が、下記一般式(2)で表される上記1又は2に記載のα-オレフィンの製造方法、
CrXnDm ・・・(2)
(式中、Xはσ結合性の配位子を示し、Xが複数ある場合、複数のXは同じでも異なっていてもよく、Dはルイス塩基を示し、Dが複数ある場合、複数のDは同じでも異なっていてもよく、nは2~3の整数であってCrの原子価を示し、mは0~6の整数を示す。)
4.前記一般式(1)におけるL1~L3が、それぞれ独立に、置換もしくは無置換のフェニル基、又は置換もしくは無置換のシクロヘキシル基であり、かつ、該置換基が炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、又は環形成炭素数5~6のシクロアルキル基である上記1~3のいずれかに記載のα-オレフィンの製造方法、及び
5.前記(C)助触媒がアルミノキサンである上記1~4のいずれかに記載のα-オレフィンの製造方法、
尚、本明細書において、「置換もしくは無置換の炭素数a~bのX基」という表現における「炭素数a~b」は、X基が無置換である場合の炭素数を表すものであり、X基が置換されている場合の置換基の炭素数は含めない。
本発明において用いられる(A)クロム化合物は、そのクロム原子が後述の(B)配位子化合物と錯体を形成し得るものであれば特に限定されないが、下記一般式(2)で表されるものが好ましく用いられる。
CrXnDm ・・・(2)
(式中、Xはσ結合性の配位子を示し、Xが複数ある場合、複数のXは同じでも異なっていてもよく、Dはルイス塩基を示し、Dが複数ある場合、複数のDは同じでも異なっていてもよく、nは2~3の整数であってCrの原子価を示し、mは0~6、好ましくは0~3の整数を示す。)
炭素数1~20の炭化水素基として具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基、オクチル基などのアルキル基;ビニル基、プロペニル基、シクロヘキセニル基などのアルケニル基;ベンジル基、フェニルエチル基、フェニルプロピル基などのアリールアルキル基;フェニル基、トリル基、ジメチルフェニル基、トリメチルフェニル基、エチルフェニル基、プロピルフェニル基、ビフェニル基、ナフチル基、メチルナフチル基、アントラセニル基、フェナントレニル基などのアリール基などが挙げられる。なかでもメチル基、エチル基、プロピル基などのアルキル基やフェニル基などのアリール基が好ましい。
炭素数1~20のアミド基としては、ジメチルアミド基、ジエチルアミド基、ジプロピルアミド基、ジブチルアミド基、ジシクロヘキシルアミド基、メチルエチルアミド基等のアルキルアミド基や、ジビニルアミド基、ジプロペニルアミド基、ジシクロヘキセニルアミド基などのアルケニルアミド基;ジベンジルアミド基、フェニルエチルアミド基、フェニルプロピルアミド基などのアリールアルキルアミド基;ジフェニルアミド基、ジナフチルアミド基などのアリールアミド基が挙げられる。
炭素数1~20の珪素含有基としては、メチルシリル基、フェニルシリル基などのモノ炭化水素置換シリル基;ジメチルシリル基、ジフェニルシリル基などのジ炭化水素置換シリル基;トリメチルシリル基、トリエチルシリル基、トリプロピルシリル基、トリシクロヘキシルシリル基、トリフェニルシリル基、ジメチルフェニルシリル基、メチルジフェニルシリル基、トリトリルシリル基、トリナフチルシリル基などのトリ炭化水素置換シリル基;トリメチルシリルエーテル基などの炭化水素置換シリルエーテル基;トリメチルシリルメチル基などの珪素置換アルキル基;トリメチルシリルフェニル基などの珪素置換アリール基などが挙げられる。なかでもトリメチルシリルメチル基、フェニルジメチルシリルエチル基などが好ましい。
炭素数1~20のアシル基としては、ホルミル基、アセチル基、プロピオニル基、ブチリル基、バレリル基、パルミトイル基、ステアロイル基、オレオイル基等のアルキルアシル基、ベンゾイル基、トルオイル基、サリチロイル基、シンナモイル基、ナフトイル基、フタロイル基等のアリールアシル基、シュウ酸、マロン酸、コハク酸などのジカルボン酸からそれぞれ誘導されるオキサリル基、マロニル基、スクシニル基などが挙げられる。
エーテル類としては、メチルエーテル、エチルエーテル、プロピルエーテル、イソプロピルエーテル、ブチルエーテル、イソブチルエーテル、n-アミルエーテル、イソアミルエーテル等の脂肪族単一エーテル化合物;メチルエチルエーテル、メチルプロピルエーテル、メチルイソプロピルエーテル、メチル-n-アミルエーテル、メチルイソアミルエーテル、エチルプロピルエーテル、エチルイソプロピルエーテル、エチルブチルエーテル、エチルイソブチルエーテル、エチル-n-アミルエーテル、エチルイソアミルエーテル等の脂肪族混成エーテル化合物;ビニルエーテル、アリルエーテル、メチルビニルエーテル、メチルアリルエーテル、エチルビニルエーテル、エチルアリルエーテル等の脂肪族不飽和エーテル化合物;アニソール、フェネトール、フェニルエーテル、ベンジルエーテル、フェニルベンジルエーテル、α-ナフチルエーテル、β-ナフチルエーテルなどの芳香族エーテル化合物、酸化エチレン、酸化プロピレン、酸化トリメチレン、テトラヒドロフラン、テトラヒドロピラン、ジオキサン等の環式エーテル化合物が挙げられる。
本発明において用いられる(B)配位子化合物は、下記一般式(1)で表される。
上記L1~L3は、好ましくは、置換もしくは無置換の炭素数5~14の脂環式炭化水素基、又は置換もしくは無置換の環形成炭素数6~14の芳香族炭化水素基である。
前記L1~L3で表される芳香族炭化水素基の例としては、フェニル基、ナフチル基、フェナントリル基、ビフェニリル基、ターフェニリル基、クォーターフェニリル基、フルオランテニル基、トリフェニレニル基、フルオレニル基、ベンゾ[c]フェナントレニル基、ベンゾ[a]トリフェニレニル基、ナフト[1,2-c]フェナントレニル基、ナフト[1,2-a]トリフェニレニル基、ジベンゾ[a,c]トリフェニレニル基、ベンゾ[b]フルオランテニル基などが挙げられ、好ましくは、フェニル基、4-ビフェニリル基、3-ビフェニリル基、5’-m-ターフェニリル基、1-ナフチル基、フルオレン-2-イル基、2-ナフチル基、9-フェナントレニル基である。
L1~L3で表される置換芳香族炭化水素基の例としては、2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、2-エチルフェニル基、3-エチルフェニル基、4-エチルフェニル基、2,3-ジメチルフェニル基、2,4-ジメチルフェニル基、2,5-ジメチルフェニル基、2,6-ジメチルフェニル基、3,4-ジメチルフェニル基、3,5-ジメチルフェニル基、2-メチル-4-メトキシフェニル基、2-メチル-6-メトキシフェニル基、2,4,5-トリメチルフェニル基、2,4,6-トリメチルフェニル基、4-n-ブチルフェニル基、4-t-ブチルフェニル基などが挙げられる。
前記L1~L3で表される芳香族複素環基としては、窒素原子、酸素原子、及び硫黄原子から選ばれる少なくとも1個のヘテロ原子を含むものが好ましく、その具体例としては、ピロリル基、フリル基、チエニル基、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、イミダゾリル基、オキサゾリル基、チアゾリル基、ピラゾリル基、イソオキサゾリル基、イソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、インドリル基、イソインドリル基、ベンゾフラニル基、イソベンゾフラニル基、ベンゾチオフェニル基、インドリジニル基、キノリジニル基、キノリル基、イソキノリル基、シンノリル基、フタラジニル基、キナゾリニル基、キノキサリニル基、ベンズイミダゾリル基、ベンズオキサゾリル基、ベンズチアゾリル基、インダゾリル基、ベンズイソキサゾリル基、ベンズイソチアゾリル基、カルバゾリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、フェナントリジニル基、アクリジニル基、フェナントロリニル基、フェナジニル基、フェノチアジニル基、フェノキサジニル基、及びキサンテニル基が挙げられ、好ましくはフリル基、チエニル基、ベンゾフラニル基、ベンゾチオフェニル基、ジベンゾフラニル基、ジベンゾチオフェニル基である。
前記L1~L3として用いられる置換フェニル基としては、置換基として炭素数1~20のアルキル基又は炭素数1~20のアルコキシ基を有するものが特に好ましい。
また、(B)成分としては一種又は二種以上を用いることができる。
本発明において用いられる(C)助触媒の具体例としては、(C-1)アルミノキサンと、(C-2)硼素化合物とが挙げられる。
(C-1)成分のアルミノキサンとしては、一般式(I)
(C-1)アルミノキサンの具体例としては、メチルアルミノキサン(MAO)、メチルイソブチルアルミノキサン(MMAO)、エチルアルミノキサン(EMAO)、イソブチルアルミノキサン(IBAO)等が挙げられ、メチルアルミノキサン(MAO)又はメチルイソブチルアルミノキサン(MMAO)が好ましく用いられる。
例えば、(1)有機アルミニウム化合物を有機溶剤に溶解しておき、これを水と接触させる方法、(2)重合時に当初有機アルミニウム化合物を加えておき、後で水を添加する方法、(3)金属塩などに含有されている結晶水、無機物や有機物への吸着水を有機アルミニウム化合物と反応させる方法、(4)テトラアルキルジアルミノキサンにトリアルキルアルミニウムを反応させ、更に水を反応させる方法などがある。尚、アルミノキサンとしては、トルエン不溶性のものであってもよい。これらのアルミノキサンは一種用いてもよく、二種以上を組み合わせて用いてもよい。
また、(C)成分としては(C-1)成分及び(C-2)成分から選択される一種又は二種以上を用いることができる。
(C-2)硼素化合物の具体例としては、トリス(ペンタフルオロフェニル)硼素、テトラキス(ペンタフルオロフェニル)硼酸ジメチルアニリニウム,テトラキス(ペンタフルオロフェニル)硼酸トリチルなどを挙げることができる。
また、本発明のα-オレフィンの製造方法においては、上記(A)~(C)成分に加えて、(D)成分として有機アルミニウム化合物を用いることができる。ここで、(D)成分の有機アルミニウム化合物としては、一般式(III)
R2 vAlJ3-v・・・(III)
〔式中、R2は炭素数1~10のアルキル基、Jは水素原子、炭素数1~20のアルコキシ基、炭素数6~20のアリール基又はハロゲン原子を示し、vは1~3の整数である〕で示される化合物が用いられる。
重合温度は、0~150℃が好ましく、20~80℃がより好ましい。
重合圧力は、常圧~10MPaが好ましく、0.2~8.0MPaがより好ましく、0.5~5.0MPaが特に好ましい。
重合溶媒としては、ベンゼン、トルエン、キシレン、ペンタン、ヘプタン、シクロヘキサン、メチルシクロヘキサンなどが挙げられ、トルエンやシクロヘキサンが好ましく用いられる。
反応液に内部標準液として、ウンデカン(C11)を一定量加え、以下の条件でガスクロマトグラフィー(GC)測定を行い、各α-オレフィン成分(C4~C18)の質量比を、内部標準液C11を基準に求めた。
GC測定条件
カラム:Ultra2(25m×0.2mm×0.33μm)
注入口温度:270℃
検出器温度:270℃
カラム温度:40~200℃(1.5℃/min)、200~270℃(8℃/min)
〔クロム錯体溶液の調製〕
攪拌子入りの窒素置換した50mlシュレンク管にトリス(アセチルアセトナート)クロムトルエン溶液を20ml(40μmol)と、下記式で表される配位子化合物A溶液6ml(120μmol)とを添加し、室温下で約2時間攪拌して調製した。溶液は淡紫色の均一な液であった。
十分に脱水・窒素置換した1Lの攪拌機付きオートクレーブに、乾燥溶媒トルエン300mlを張り込み、次いで上記クロム錯体溶液17.88ml(27.5μmol)と、メチルアルミノキサンのトルエン溶液2.75ml(8250μmol)とを張り込み、攪拌を開始した。反応温度を40℃まで昇温し、40℃になった時点で、エチレンを4MPa張り込み、反応を開始した。1時間反応後、加圧下でエタノール30mlを添加し、触媒を失活させた。室温まで冷却後脱圧し、オートクレーブを開放し、反応液中にGC分析用の内部標準液であるウンデカンを3.5g添加し、よく攪拌した。反応液はGC分析を行い、各α-オレフィン成分の分布・純度を求めた。ポリマーが副生する場合は、生成液を吸引ろ過し、ろ過物を1日風乾後、重量を測定した。結果を第1表に示す。
配位子化合物A溶液の使用量を、6ml(120μmol)から2ml(40μmol)に変更した以外は、実施例1と同様にしてクロム錯体溶液の調製及びエチレン重合を行った。結果を第1表に示す。
配位子化合物A(0.54g,1.96mmol)のTHF(15mL)溶液にn-BuLiヘキサン溶液(2.05mmol,0.82mL)を-10℃で添加した。反応混合物を室温で終夜攪拌し、この溶液をCrCl2(THF)2(0.27g,1.01mmol)のTHF(5mL)懸濁液に添加した。18時間攪拌後、減圧下溶媒を留去し、固体残渣をトルエンに再溶解した。少量の無色不溶物をろ別し得られた褐色溶液の溶媒を減圧下留去し、得られた緑褐色固体を触媒として使用し、実施例1と同様にしてエチレン重合を行った。結果を第1表に示す。
溶媒をトルエンからシクロヘキサンに変更した以外は、実施例2と同様にしてエチレン重合を行った。結果を第1表に示す。
配位子化合物D溶液の使用量を、6ml(120μmol)から2ml(40μmol)に変更した以外は、実施例7と同様にしてクロム錯体溶液の調製及びエチレン重合を行った。結果を第1表に示す。
配位子化合物A溶液を添加しなかったこと以外は、実施例1と同様にしてエチレン重合を行った。結果を第1表に示す。
尚、第1表中、実施例1~8及び比較例1~2のいずれにおいても1-ブテン(C4)の得率が低いが、これは1-ブテンが軽質であるため、揮発していることに由来するものと解される。
Claims (5)
- 前記(A)クロム化合物と、(B)配位子化合物とを接触させる工程と、その反応生成物と前記(C)助触媒とを反応させる工程とを有する請求項1に記載のα-オレフィンの製造方法。
- 前記(A)クロム化合物が、下記一般式(2)で表される請求項1又は2に記載のα-オレフィンの製造方法。
CrXnDm ・・・(2)
(式中、Xはσ結合性の配位子を示し、Xが複数ある場合、複数のXは同じでも異なっていてもよく、Dはルイス塩基を示し、Dが複数ある場合、複数のDは同じでも異なっていてもよく、nは2~3の整数であってCrの原子価を示し、mは0~6の整数を示す。) - 前記一般式(1)におけるL1~L3が、それぞれ独立に、置換もしくは無置換のフェニル基、又は置換もしくは無置換のシクロヘキシル基であり、かつ、該置換基が炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、又は環形成炭素数5~6のシクロアルキル基である請求項1~3のいずれかに記載のα-オレフィンの製造方法。
- 前記(C)助触媒がアルミノキサンである請求項1~4のいずれかに記載のα-オレフィンの製造方法。
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US14/369,509 US9394213B2 (en) | 2011-12-27 | 2012-12-13 | Method for producing α-olefin |
BR112014015969A BR112014015969A8 (pt) | 2011-12-27 | 2012-12-13 | processo de produção para alfa-olefina |
KR20147019291A KR20150000868A (ko) | 2011-12-27 | 2012-12-13 | α-올레핀의 제조 방법 |
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JP2003261588A (ja) * | 2002-03-08 | 2003-09-19 | Japan Science & Technology Corp | オレフィン重合などに用いられる遷移金属錯体 |
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JPH08183746A (ja) | 1994-12-28 | 1996-07-16 | Idemitsu Kosan Co Ltd | α−オレフィンオリゴマーの製造方法 |
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BR0317510A (pt) | 2002-12-20 | 2005-11-16 | Sasol Tech Pty Ltd | Tetramerização de olefinas |
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JP2003261588A (ja) * | 2002-03-08 | 2003-09-19 | Japan Science & Technology Corp | オレフィン重合などに用いられる遷移金属錯体 |
JP2004067511A (ja) * | 2002-06-10 | 2004-03-04 | Japan Science & Technology Corp | ヘテロ原子配位子と2つの金属を含む金属錯体 |
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CN104011089B (zh) | 2016-08-24 |
US20140364669A1 (en) | 2014-12-11 |
CN104011089A (zh) | 2014-08-27 |
BR112014015969A8 (pt) | 2017-07-04 |
BR112014015969A2 (pt) | 2017-06-13 |
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