Classifications

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  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
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  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/14—Fractional distillation or use of a fractionation or rectification column
  • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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  • 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
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  • 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
  • B01J31/1805—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 nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
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  • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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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
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  • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
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  • 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
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  • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
  • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
  • C07C5/25—Migration of carbon-to-carbon double bonds
  • C07C5/2506—Catalytic processes
  • C07C5/2562—Catalytic processes with hydrides or organic compounds
  • C07C5/2575—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
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  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
  • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
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  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
  • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
  • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
  • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
  • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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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  • B01J2531/48—Zirconium
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  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
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  • 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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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Definitions

• the present invention relates to a method for producing an ⁇ -olefin oligomer composition.
• lubricating oils are required to have long drain properties. In order to improve the long drain property, stability against heat and oxidation reaction is required.
• Various synthetic lubricating oils have been developed as such lubricating oils with excellent stability.
• poly ⁇ -olefins, polybutenes, alkylbenzenes, polyol esters, dibasic acid esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, silicones, etc. are used as base oils for synthetic lubricating oils. .
• poly- ⁇ -olefins are widely used due to their high chemical stability and excellent viscosity index. Olefins are produced and used. Under these circumstances, production methods have been investigated in order to efficiently obtain poly- ⁇ -olefins with controlled molecular weights and structures.
• Patent Document 1 describes a process of reacting an ⁇ -olefin in the presence of hydrogen using a specific catalyst and co-catalyst for the purpose of reducing the amount of catalyst and obtaining an oligomer with a specific degree of polymerization with high selectivity.
• a method of making an ⁇ -olefin oligomer composition comprising:
• Patent Document 2 as a method for obtaining a component of a lubricating oil composition excellent in oxidation stability, thermal stability and low temperature stability, ⁇ -olefin is dimerized in the presence of a metallocene complex catalyst to produce vinylidene olefin.
• Patent Document 3 also discloses that 1-decene is oligomerized in the presence of hydrogen, a metallocene catalyst and an activator compound to obtain a low-viscosity oil containing 9-methyl-11,13-dioctyltricosane. Also disclosed is the catalytic hydrogenation of the oligomerization product in the presence of a hydrogenation catalyst and the separation of the resulting tetramer fraction by vacuum distillation.
• Patent Document 1 The use of a metallocene catalyst as in Patent Document 1 can selectively obtain an oligomer with a specific degree of polymerization, and is therefore an excellent method depending on the use of the oligomer.
• a metallocene catalyst as in Patent Document 1 can selectively obtain an oligomer with a specific degree of polymerization, and is therefore an excellent method depending on the use of the oligomer.
• the degree of polymerization distribution widens, resulting in poor selectivity, leading to a decrease in yield and performance. It will happen. Therefore, there has been a demand for a method of obtaining an ⁇ -olefin oligomer that is excellent in selectivity and performance when used as a lubricating oil regardless of the degree of polymerization.
• An object of the present invention is to selectively obtain an ⁇ -olefin oligomer having a desired degree of polymerization, and to obtain an ⁇ -olefin oligomer composition having excellent performance when used as a lubricating oil.
• the object is to provide a method for producing the composition.
• the present inventors combined a polymerization process using a metallocene catalyst, a distillation separation process, and a polymerization process using a low molecular weight fraction obtained in the distillation separation process. Furthermore, the inventors have found that the above problems can be solved by a production method having a mixing step of mixing each polymer and the like.
• the present invention relates to the following ⁇ 1> to ⁇ 16>.
• a method for producing an ⁇ -olefin oligomer composition comprising a mixing step C of mixing part or a hydrogenated product thereof with part or all of the polymer (b), an isomer thereof, or a hydrogenated isomer thereof.
• ⁇ 2> The method for producing an ⁇ -olefin oligomer composition according to ⁇ 1> above, further comprising a distillation separation step D in which the mixture obtained in the mixing step C is separated into a plurality of fractions by distillation.
• ⁇ 3> The above ⁇ 1, further comprising a hydrogenation step A3 to obtain a hydrogenated polymer (a11) by hydrogenating the high molecular weight fraction (a1), and subjecting the hydrogenated polymer (a11) to the mixing step C > or the method for producing the ⁇ -olefin oligomer composition according to ⁇ 2>.
• ⁇ 4> The method for producing an ⁇ -olefin oligomer composition according to any one of ⁇ 1> to ⁇ 3> above, wherein the ⁇ -olefin to be subjected to the polymerization step A1 is 1-decene.
• ⁇ 5> Any of the above ⁇ 1> to ⁇ 4>, wherein the high-molecular-weight fraction (a1) is a fraction having more than 20 carbon atoms, and the low-molecular-weight fraction (a2) is a fraction having 20 or less carbon atoms.
• ⁇ 6> The method for producing an ⁇ -olefin oligomer composition according to any one of ⁇ 1> to ⁇ 5> above, wherein the metallocene catalyst contains a transition metal compound represented by the following general formula (1).
• M is zirconium or hafnium
• R 1 is an alkyl group having 1 to 10 carbon atoms or an alkyl group-substituted silyl group having 1 to 10 carbon atoms
• R 2 is a phenyl group or an alkyl group-substituted phenyl group having 1 to 10 carbon atoms.
• R 3 is a hydrogen atom or a methyl group
• X is a halogen atom or an alkyl group having 1 to 10 carbon atoms, provided that two R 1s and five R 3s may be the same or different.
• R 4 , R 5 and R 6 each independently represent a hydrocarbon group having 1 to 10 carbon atoms, and two or more groups may be bonded to each other to form a ring.
• A is represents the elements of Group 14.
• ⁇ 8> The ⁇ -olefin oligomer composition according to any one of ⁇ 1> to ⁇ 5> or ⁇ 7> above, wherein the metallocene catalyst contains a transition metal compound represented by the following formula (3): Production method.
• ⁇ 11> Further having a distillation separation step B4 for obtaining a high molecular weight fraction (b11) and a low molecular weight fraction (b21) by distilling and separating the hydrogenated isomers obtained in the hydrogenation step B3, The method for producing an ⁇ -olefin oligomer composition according to ⁇ 10> above, wherein the molecular weight fraction (b11) is subjected to the mixing step C.
• ⁇ 12> The ⁇ -olefin according to ⁇ 11> above, wherein the high-molecular-weight fraction (b11) is a fraction having more than 20 carbon atoms, and the low-molecular-weight fraction (b21) is a fraction having 20 or less carbon atoms.
• a method for producing an oligomeric composition ⁇ 13> The method for producing an ⁇ -olefin oligomer composition according to any one of ⁇ 1> to ⁇ 12> above, wherein the acid catalyst used in the polymerization step B1 is a Friedel-Crafts catalyst. ⁇ 14> Production of the ⁇ -olefin oligomer composition according to any one of ⁇ 10> to ⁇ 13> above, wherein the isomerization step B2 is isomerization in the presence of a Friedel-Crafts catalyst. Method.
• ⁇ 15> The method for producing an ⁇ -olefin oligomer composition according to ⁇ 13> or ⁇ 14> above, wherein the Friedel-Crafts catalyst contains an organoaluminum compound.
• ⁇ 16> The method for producing an ⁇ -olefin oligomer composition according to any one of ⁇ 2> to ⁇ 15> above, wherein the distillation separation step D is short-path distillation.
• the present invention it is possible to selectively obtain an ⁇ -olefin oligomer having a desired degree of polymerization, and to obtain an ⁇ -olefin oligomer composition having excellent performance when used as a lubricating oil.
• a method of making the composition can be provided.
• the present invention comprises a polymerization step A1 in which an ⁇ -olefin is polymerized using a metallocene catalyst to obtain a polymer (a), and the polymer (a) is separated by distillation to obtain a high molecular weight fraction (a1) and a low molecular weight fraction.
• a method for producing an ⁇ -olefin oligomer composition comprising a mixing step C of mixing a portion or a hydrogenated product thereof with a portion, the whole portion, an isomer thereof, or a hydrogenated isomer thereof of the polymer (b).
• the polymerization step A1 is a polymerization step of polymerizing an ⁇ -olefin using a metallocene catalyst to obtain a polymer (a).
• the metallocene catalyst used in the polymerization step A1 includes (i) a transition metal compound (metallocene complex) having a ligand having a conjugated five-membered carbon ring and containing zirconium or hafnium, and (ii) a catalyst containing an aluminum compound. is preferably used.
• a transition metal compound (metallocene complex) having a ligand having a conjugated five-membered carbon ring and containing zirconium or hafnium, which constitutes the catalyst, from the viewpoint of activity as a catalyst, the following general formula (1) It preferably contains at least one selected from the group consisting of a transition metal compound represented by the following general formula (2) and a transition metal compound represented by the following general formula (2): It is more preferable to include Further, at least one selected from the group consisting of a transition metal compound represented by the following general formula (1) and a transition metal compound represented by the following general formula (2) is preferable, and is represented by the following general formula (2). transition metal compounds are more preferred.
• transition metal compounds represented by the following general formula (2) transition metal compounds represented by the following formula (3) are more preferable.
• the transition metal compound represented by the following formula (3) is bis(t-butylcyclopentadienyl)zirconium dichloride.
• the transition metal compound (metallocene complex) is preferably used as a solution dissolved in a solvent.
• the solvent used include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, preferably toluene. . ⁇ C5H4 ( AR4R5R6 ) ⁇ 2ZrCl2 ( 2 ) ⁇ C5H4 ( CMe3 ) ⁇ 2ZrCl2 ( 3)
• M is zirconium or hafnium
• R 1 is an alkyl group having 1 to 10 carbon atoms or an alkyl group-substituted silyl group having 1 to 10 carbon atoms
• R 2 is a phenyl group or an alkyl group having 1 to 10 carbon atoms.
• a substituted phenyl group, R 3 is a hydrogen atom or a methyl group
• X is a halogen atom or an alkyl group having 1 to 10 carbon atoms.
• two R 1 and five R 3 may be the same or different.
• R 4 , R 5 and R 6 each independently represent a hydrocarbon group having 1 to 10 carbon atoms, and two or more groups may combine with each other to form a ring.
• A represents an element of group 14 of the periodic table.
• Me represents a methyl group (CH 3 ).
• the alkyl group having 1 to 10 carbon atoms for R 1 and X includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, t-butyl group, various pentyl groups, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
• Examples of the alkyl group-substituted silyl group having 1 to 10 carbon atoms for R 1 include trialkyl group-substituted silyl groups substituted with the above alkyl groups.
• Specific examples include a trimethylsilyl group, a methyldiphenylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and a triethylsilyl group, preferably a trimethylsilyl group.
• Examples of the alkyl group-substituted phenyl group having 1 to 10 carbon atoms for R 2 include 1 to 5 substituted phenyl groups substituted with the above alkyl groups.
• Specific examples include 4-methylphenyl group, 1,3,5-trimethylphenyl group, 2,5-dimethylphenyl group, 2,5-diisopropylphenyl group and 1,3,5-triisopropylphenyl group.
• Halogen atoms for X include fluorine, chlorine, bromine and iodine atoms.
• transition metal compound represented by the general formula (1) in which M is hafnium include pentamethylcyclopentadienyl [N,N'-bis(trimethylsilyl)benzamidinato]hafnium dichloride, pentamethylcyclo Pentadienyl [N,N'-bis (trimethylsilyl) benzamidinato] hafnium dibromide, cyclopentadienyl [N,N'-bis (trimethylsilyl) benzamidinato] hafnium dichloride, cyclopentadienyl [N , N′-bis(trimethylsilyl)benzamidinato]hafnium dibromide, pentamethylcyclopentadienyl (dimethylbenzamidinato) hafnium dichloride, pentamethylcyclopentadienyl (dimethylbenzamidinato) hafnium dibromide, cyclopentadienyl (di
• transition metal compound represented by the general formula (1) in which M is zirconium examples include pentamethylcyclopentadienyl[N,N'-bis(trimethylsilyl)benzamidinato]zirconium dichloride, pentamethylcyclo Pentadienyl [N,N'-bis(trimethylsilyl)benzamidinato] zirconium dibromide, pentamethylcyclopentadienyl (dimethylbenzamidinato) zirconium dichloride, pentamethylcyclopentadienyl (dimethylbenzamidinato) ) zirconium dibromide, cyclopentadienyl[N,N'-bis(trimethylsilyl)benzamidinato]zirconium dichloride, cyclopentadienyl[N,N'-bis(trimethylsilyl)benzamidinato]zirconium dichloride, cyclopentadienyl[N,N'-bis
• Examples of bis(monosubstituted cyclopentadienyl)zirconocene include bis(t-butylcyclopentadienyl)zirconium dichloride, bis(t-pentylcyclopentadienyl)zirconium dichloride, bis((2-methylpentan-2-yl ) cyclopentadienyl)zirconium dichloride, bis((2,4-dimethylpentan-2-yl)cyclopentadienyl)zirconium dichloride, bis((2,3-dimethylbutan-2-yl)cyclopentadienyl) Zirconium dichloride, bis((2,3,3-trimethylbutan-2-yl)cyclopentadienyl)zirconium dichloride, bis((3-methylpentan-3-yl)cyclopentadienyl)zirconium dichloride,
• Bis(disubstituted cyclopentadienyl)zirconocene includes bis(1-methyl-3-t-butylcyclopentadienyl)zirconium dichloride and bis(1-methyl-3-t-pentylcyclopentadienyl)zirconium dichloride.
• Bis(trisubstituted cyclopentadienyl)zirconocene includes bis(1,2-dimethyl-3-t-butylcyclopentadienyl)zirconium dichloride, bis(1,2-dimethyl-3-t-pentylcyclopentadie enyl)zirconium dichloride, bis(1,2-dimethyl-3-(2-methylpentan-2-yl)cyclopentadienyl)zirconium dichloride, bis(1,2-dimethyl-3-(2,4-dimethylpentane) -2-yl)cyclopentadienyl)zirconium dichloride, bis(1,2-dimethyl-3-(2,3-dimethylbutan-2-yl)cyclopentadienyl)zirconium dichloride, bis(1,2-dimethyl) -3-(2,3,4-trimethylbutan-2-yl)cyclopentadienyl)zirconium dichloride, bis(
• the (ii) aluminum compound that constitutes the catalyst includes an organoaluminum oxo compound and an organoaluminum compound, and the organoaluminum compound is preferably used in combination with an organoboron compound. That is, the metallocene catalyst preferably further contains an organoaluminum oxo compound, or an organoaluminum compound and an organoboron compound.
• Organic aluminum oxo compounds include chain aluminoxanes represented by general formula (4) and cyclic aluminoxanes represented by general formula (5).
• each R 7 independently represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, or a halogen atom having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and may be the same or different.
• n indicates the degree of polymerization and is an integer of usually 3 to 50, preferably 7 to 40.
• methylaluminoxane (MAO) in which R 7 is a methyl group is preferred.
• Methylaluminoxane (MAO) is preferably used as a solution dissolved in a solvent, and the solvent used includes aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, preferably toluene.
• organic aluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum (TIBA), dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, and diethylaluminum. hydride, ethylaluminum sesquichloride, etc., and triisobutylaluminum (TIBA) is preferred.
• organic boron compounds include triphenylboron, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, tris[(4-fluoromethyl)phenyl]boron, trimethylboron, triethyl boron, tri-n-butylboron, tris(fluoromethyl)boron, tris(pentafluoroethyl)boron, tris(nonafluorobutyl)boron, tris(2,4,6-trifluorophenyl)boron, tris(3, 5-difluoro)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, bis(pentafluorophenyl)fluoroboron, diphenylfluoroboron, bis(pentafluorophenyl)chloroboron, dimethylfluoroboron, diethylfluoro boron
• the ratio of the organoaluminum oxo compound used to the transition metal compound (metallocene complex) [organoaluminum oxo compound/transition metal compound] is preferably a molar ratio of 20:1 to 400:1, more preferably. is between 50:1 and 200:1.
• the ratio of the organoaluminum compound used to the transition metal compound (metallocene complex) [organoaluminum compound/transition metal compound] is preferably 1:1 in molar ratio. It is 1 to 10000:1, more preferably 5:1 to 2000:1, still more preferably 10:1 to 1000:1.
• the molar ratio of the organoboron compound to the transition metal compound (metallocene complex) [organoboron compound/transition metal compound] is preferably 1:10 to 100:1, more preferably 1:2 to 10. :1.
• the proportion of the aluminum compound used is within the above range, the degree of polymerization can be easily controlled, and the selectivity can be improved.
• ⁇ -Olefin is an alkene in which the carbon-carbon double bond is in the ⁇ -position (terminal).
• the ⁇ -olefin used in the polymerization step A1 is preferably an ⁇ -olefin having 6 to 12 carbon atoms, more preferably an ⁇ -olefin having 8 to 10 carbon atoms.
• linear ⁇ -olefins represented by the following general formula are preferred, linear ⁇ -olefins having 6 to 12 carbon atoms are more preferred, and linear ⁇ -olefins having 8 to 10 carbon atoms are even more preferred.
• H2C CH-( CH2 ) n - CH3 (In the formula, n represents an integer from 3 to 9.)
• ⁇ -olefins include 1-octene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene and the like.
• -octene, 1-decene, 1-dodecene and 1-tetradecene are preferred, 1-octene and 1-decene are more preferred, and 1-decene is even more preferred. That is, it is more preferable that the ⁇ -olefin supplied to the polymerization step A1 is 1-decene.
• These ⁇ -olefins may be used singly or in combination of two or more.
• Polymerization conditions in the polymerization step A1 are as follows.
• the polymerization temperature is preferably 0 to 200°C, more preferably 40 to 140°C, even more preferably 40 to 100°C, still more preferably 40 to 60°C.
• the pressure during polymerization is preferably atmospheric pressure to 1 MPaG, more preferably atmospheric pressure to 0.2 MPaG.
• MPaG represents "MPa (gauge pressure)".
• the polymerization time is preferably 0.5 to 50 hours.
• a solvent may be used in the polymerization step A1, and examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, with toluene being preferred.
• the polymerization reaction is preferably terminated by mixing a base with the reaction solution after polymerization.
• the base that can be used is preferably at least one selected from the group consisting of alkali metal hydroxides, ammonia and amines, more preferably alkali metal hydroxides.
• Alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and the like, and are preferably mixed with the reaction solution in the form of an aqueous solution.
• reaction solution in order to decompose and remove the catalyst and the catalyst after neutralization with the base, it is preferable to wash the reaction solution with an aqueous solvent such as water. In addition, it is preferable to heat the reaction liquid as necessary, reduce the pressure, and remove the solvent and unreacted ⁇ -olefin before the distillation separation step in the next step.
• the distillation separation step A2 is a step of distilling and separating the polymer (a) obtained in the polymerization step A1 to obtain a high molecular weight fraction (a1) and a low molecular weight fraction (a2).
• this step is performed before the polymerization step B1 and the mixing step C, and among the obtained fractions, a part or all of the low-molecular-weight fraction (a2) is subjected to the polymerization step B1.
• the fraction obtained in this step including the low-molecular-weight fraction (a2) and the high-molecular-weight fraction (a1) that were not used in the polymerization step B1, may be subjected to the mixing step C.
• the high molecular weight fraction (a1) it is preferable to subject the high molecular weight fraction (a1) to the mixing step C.
• the distillation conditions may be determined so that each fraction obtained has the desired degree of polymerization (molecular weight).
• Preferred conditions are as follows.
• the distillation temperature is preferably 200-300°C, preferably 220-280°C, more preferably 230-270°C.
• the pressure is preferably 0.1-15 Pa, more preferably 0.4-7 Pa, still more preferably 0.6-4 Pa.
• the high-molecular-weight fraction (a1) obtained in the distillation separation step A2 is a fraction having more than 20 carbon atoms
• the low-molecular-weight fraction (a2) is a fraction having 20 or less carbon atoms.
• the hydrogenation step A3 is an optional step, and is a step of hydrogenating the high molecular weight fraction (a1) obtained in the distillation separation step A2 to obtain a hydrogenated polymer (a11). It is preferable to subject the obtained hydrogenated polymer (a11) to the mixing step C described later.
• the high-molecular-weight fraction (a1) By hydrogenating the high-molecular-weight fraction (a1), the resulting hydrogenated polymer becomes a saturated hydrocarbon, and when used as a lubricating oil, it has improved stability from external stimuli and can withstand long-term use. become a thing.
• the reaction conditions of the hydrogenation step A3 may be general hydrogenation reaction conditions, but preferred conditions are as follows.
• this hydrogenation step it is preferable to obtain a hydrogenated polymer (a11) by gas phase hydrogenation of the high molecular weight fraction (a1) using a hydrogenation catalyst.
• a generally used vapor-phase hydrogenation method can be used.
• a noble metal catalyst such as palladium or platinum
• a nickel-based catalyst it is preferable to set the reaction temperature to 150 to 250° C. and the hydrogen pressure to 1 to 20 MPa.
• the catalyst amount is preferably 0.05 to 50% by mass relative to the high molecular weight fraction (a1) in any system, and the reaction time is preferably 2 to 48 hours.
• the hydrogenation reaction proceeds rapidly by using the above-mentioned hydrogenation catalyst. Additional operations, such as boosting, may be performed.
• the polymerization step B1 is a polymerization step in which the ⁇ -olefin oligomer containing the low molecular weight fraction (a2) is polymerized using an acid catalyst to obtain the polymer (b).
• the low-molecular-weight fraction (a2) is obtained by distilling and separating the polymer (a) obtained in the above polymerization step A1 in the distillation separation step A2.
• Examples of the acid catalyst used in the polymerization step B1 include Friedel-Crafts catalysts, solid acid catalysts, Lewis acid catalysts and Bronsted acid catalysts, with Friedel-Crafts catalysts being more preferred.
• the Friedel-Crafts catalyst preferably comprises an organoaluminum compound, more preferably consisting of an organoaluminum compound and an organohalide.
• the organoaluminum compound includes trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide and the like, and dialkylaluminum halide is preferred.
• Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. Among them, diethylaluminum chloride is preferred.
• organic halides examples include alkyl halides and allyl halides, with alkyl halides being preferred.
• alkyl halides include t-butyl chloride, sec-butyl chloride, cyclohexyl chloride and 2,5-dimethyl-2-chlorohexane, with t-butyl chloride being preferred.
• the molar ratio of the organoaluminum compound to the organic halide (organoaluminum compound/organic halide) used in this step is preferably 1/10 to 1/0.5, more preferably 1/5 to 1/1. 1/4 to 1/2 is more preferable.
• the ratio is 1/10 or more, the halogen content in the obtained oligomer can be reduced and the removal is facilitated. Further, when the ratio is 1/0.5 or less, the reaction can be carried out with good reproducibility.
• the concentration of the Friedel-Crafts catalyst used in this step is preferably 0.5 to 50 mmol/L, more preferably 0.6 to 20 mmol/L, as the molar amount of aluminum relative to the volume of the substrate (olefin) at 25 ° C.
• 0.8 to 10 mmol/L is more preferable, and 1 to 5 mmol/L is even more preferable.
• the catalyst concentration is 0.5 mmol/L or more, the reaction can be carried out with good reproducibility, and when the catalyst concentration is 50 mmol/L or less, the halogen content in the resulting polymer can be reduced. , making it easier to remove.
• the ⁇ -olefin oligomer used in the polymerization step B1 contains the low molecular weight fraction (a2).
• the low-molecular-weight fraction (a2) is the low-molecular-weight fraction obtained in the distillation separation step A2.
• the low molecular weight fraction (a2) is obtained by further distilling the polymer obtained by polymerizing the ⁇ -olefin using a metallocene catalyst in the polymerization step A1, so the ⁇ -olefin oligomer preferably used in this step. as the main component.
• the ⁇ -olefin oligomer composition is the purpose It is easy to obtain a degree of polymerization of 1, and the performance when used as a lubricating oil is also excellent. Furthermore, by using the low-molecular-weight fraction (a2) as the raw material in this step, it is possible to effectively utilize the low-molecular-weight component that is not suitable as a lubricating oil in the polymer (a) obtained in the polymerization step A1. .
• an ⁇ -olefin oligomer having a relatively low degree of polymerization may be used in the low molecular weight fraction (a2).
• a dimer obtained by dimerizing an ⁇ -olefin is preferable, and a vinylidene olefin having a vinylidene structure is more preferable.
• the vinylidene olefin is preferably one or more selected from compounds represented by the following general formula (6).
• R 8 and R 9 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms.
• R 8 and R 9 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms.
• a linear alkyl group is preferred.
• Examples of the linear alkyl group having 8 to 16 carbon atoms include n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl and n-hexadecyl groups are included.
• ⁇ Polymerization conditions for polymerization step B1> it is preferable to perform a treatment for removing moisture, oxides, etc. in the raw materials before starting the reaction.
• the method for removing water and the like include a method in which an adsorbent is added to the raw material to remove by adsorption, and a method in which an inert gas or dry gas is bubbled to remove with an air current, and these methods are preferably used in combination.
• Preferred adsorbents are activated alumina and molecular sieves. Nitrogen is preferable as the bubbling gas.
• a polymerization reaction is allowed to proceed by contacting a catalyst with an olefin oligomer.
• the reaction temperature during the polymerization reaction is preferably 0 to 100°C, more preferably 25 to 90°C, even more preferably 30 to 80°C.
• the reaction temperature is 0° C. or higher, the time required to start the reaction can be shortened, and the reproducibility of the reaction can be improved.
• the reaction temperature is 100° C. or lower, the desired polymer can be obtained in a high yield without causing deactivation of the catalyst or side reactions. Since this reaction is an exothermic reaction, the temperature rises during the reaction, but it is preferable to adjust the upper limit to the above range.
• the end point of the reaction can be determined by the disappearance of heat generation.
• the isomerization step B2 is an optional step, and is a step of isomerizing the polymer (b) obtained in the polymerization step B1 to obtain an isomer.
• the isomerization step B2 of isomerizing the polymer (b) to obtain an isomer, and hydrogenation of the isomer to obtain a hydrogenated isomer It is preferable to further have an addition step B3 and subject the obtained hydrogenated isomers to the mixing step C.
• the isomerization step B2 is preferably isomerization in the presence of an acid catalyst.
• acid catalysts include Friedel-Crafts catalysts, solid acid catalysts, Lewis acid catalysts and Bronsted acid catalysts, with Friedel-Crafts catalysts being more preferred. That is, the isomerization step B2 is more preferably isomerization in the presence of a Friedel-Crafts catalyst.
• the Friedel-Crafts catalyst preferably comprises an organoaluminum compound, more preferably consisting of an organoaluminum compound and an organohalide.
• the organoaluminum compound includes trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide and the like, and dialkylaluminum halide is preferred.
• Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. Among them, diethylaluminum chloride is preferred.
• organic halides examples include alkyl halides and allyl halides, with alkyl halides being preferred.
• alkyl halides include t-butyl chloride, sec-butyl chloride, cyclohexyl chloride and 2,5-dimethyl-2-chlorohexane, with t-butyl chloride being preferred.
• the molar ratio of the organoaluminum compound to the organic halide (organoaluminum compound/organic halide) used in this step is preferably 1/10 to 1/0.5, more preferably 1/5 to 1/1. 1/4 to 1/2 is more preferable.
• the ratio is 1/10 or more, the halogen content in each isomer obtained can be reduced, and the removal becomes easy. Further, when the ratio is 1/0.5 or less, the reaction can be carried out with good reproducibility.
• the concentration of the Friedel-Crafts catalyst used in this step is preferably 0.5 to 100 mmol/L, more preferably 1 to 40 mmol/L, as the molar amount of aluminum relative to the volume of the substrate (oligomer) at 25°C. 1.5 to 20 mmol/L is more preferred, and 2 to 10 mmol/L is even more preferred.
• the catalyst concentration is 0.5 mmol/L or more, the reaction can be performed with good reproducibility, and when the catalyst concentration is 100 mmol/L or less, the halogen content in each isomer obtained is reduced. can be easily removed.
• the concentration of the Friedel-Crafts catalyst specified here is the same as that used in step B1 when the Friedel-Crafts catalyst is used in step B1 and the reaction mixture obtained in step B1 is used as it is in step B2. It is the concentration by the total amount with the catalyst used.
• reaction temperature during the isomerization reaction is preferably 120 to 200°C, more preferably 130 to 190°C, even more preferably 140 to 180°C.
• the reaction temperature is 120°C or higher, the isomerization proceeds efficiently in a short period of time.
• the reaction temperature is 200° C. or lower, the desired isomer can be obtained in high yield without causing a decomposition reaction.
• the polymer (b) (olefin oligomer) obtained in the above step is isomerized, and it is believed that the structure becomes more stable. Although the details are not clear, it is believed that the isomerization reduces the quaternary carbon moiety.
• the reaction time during the isomerization reaction is preferably 1 to 240 minutes, more preferably 2 to 180 minutes, still more preferably 3 to 160 minutes, and even more preferably 5 to 140 minutes.
• the reaction time is 240 minutes or less, the desired isomer can be obtained in a high yield without causing side reactions such as polymerization reactions.
• the isomerization reaction is preferably terminated by adding an alkali such as sodium hydroxide. After finishing the reaction, it is preferable to remove the catalyst or salts derived from the catalyst by washing with water. Washing with water is preferably carried out so that the mixture, once alkaline, becomes neutral, and washing is preferably carried out so that the pH of the water used for washing is 9 or less.
• an alkali such as sodium hydroxide
• the hydrogenation step B3 is an optional step, and is a step of hydrogenating the isomer to obtain a hydrogenated isomer. Although it is preferable to subject the hydrogenated isomer obtained in this step to the mixing step C, in the method for producing an ⁇ -olefin oligomer composition of the present invention, after this step, the obtained hydrogenated isomer is It is more preferable to further have a distillation separation step B4 for obtaining a high molecular weight fraction (b11) and a low molecular weight fraction (b21) by distillation separation, and subject the high molecular weight fraction (b11) to the mixing step C.
• a distillation separation step B4 for obtaining a high molecular weight fraction (b11) and a low molecular weight fraction (b21) by distillation separation, and subject the high molecular weight fraction (b11) to the mixing step C.
• the hydrogenated isomer by gas phase hydrogenation of the isomer using a hydrogenation catalyst.
• a generally used vapor-phase hydrogenation method can be used.
• a noble metal catalyst such as palladium or platinum
• the reaction is preferably carried out at a reaction temperature of 60-100° C. and a hydrogen pressure of 0.1-1 MPa.
• a nickel-based catalyst is used, the reaction is preferably carried out at a reaction temperature of 150-250° C. and a hydrogen pressure of 1-20 MPa.
• the amount of catalyst is generally 0.05 to 50% by mass based on the isomer in any system, and the hydrogenation reaction is completed in 2 to 48 hours.
• the hydrogenation reaction proceeds rapidly by using the above-mentioned hydrogenation catalyst. Additional operations such as raising the temperature or increasing the pressure may be performed.
• distillation separation step B4 is an optional step, in which the hydrogenated isomers obtained in the hydrogenation step B3 are separated by distillation to obtain a high molecular weight fraction (b11) and a low molecular weight fraction (b21). is.
• this step may be performed before subjecting to the mixing step C, and the obtained fraction may be subjected to the mixing step C. Among them, it is preferable to subject the high molecular weight fraction (b11) to the mixing step C.
• distillation conditions may be determined so that each fraction obtained has the desired degree of polymerization (molecular weight).
• Preferred conditions are as follows.
• the distillation temperature is preferably 200-300°C, preferably 220-280°C, more preferably 230-270°C.
• the pressure is preferably 0.1-15 Pa, more preferably 0.4-7 Pa, still more preferably 0.6-4 Pa.
• the high-molecular-weight fraction (b11) obtained in the distillation separation step B4 is a fraction having more than 20 carbon atoms
• the low-molecular-weight fraction (b21) is a fraction having 20 or less carbon atoms.
• the "part of the polymer (a) or hydrogenated product thereof” in this step is preferably the polymer (a) obtained in the polymerization step A1, the high molecular weight fraction (a1 ), and at least one of the hydrogenated polymer (a11) obtained in the hydrogenation step A3.
• "a part of the polymer (b), its isomer or its hydrogenated isomer” in this step is preferably the polymer (b) obtained in the polymerization step B1, the isomerization step B2 It is at least one of the isomer obtained, the hydrogenated isomer obtained in the hydrogenation step B3, and the high molecular weight fraction (b11) obtained in the distillation separation step B4. Suitable combinations of mixtures are shown below.
• the selectivity is improved, and the resulting ⁇ -olefin oligomer composition is the desired
• the degree of polymerization is increased. This makes it possible to obtain an ⁇ -olefin oligomer composition having particularly excellent properties as a lubricating oil.
• the obtained ⁇ -olefin oligomer composition is a saturated hydrocarbon and contains stabilized isomers, it can be used as a lubricating oil that does not change in quality due to external stimuli and does not deteriorate even after long-term use. can.
• Distillation separation step D is a step of separating the mixture obtained in mixing step C into a plurality of fractions by distillation, and the method for producing an ⁇ -olefin oligomer composition includes distilling the mixture obtained in mixing step C. It is preferable to further have a distillation separation step D for separating into a plurality of fractions.
• distillation conditions may be determined so that each fraction to be obtained has the desired degree of polymerization (molecular weight).
• Preferred conditions are as follows.
• the distillation temperature is preferably 200-300°C, preferably 220-280°C, more preferably 230-270°C.
• the pressure is preferably 0.1-15 Pa, more preferably 0.4-7 Pa, still more preferably 0.6-4 Pa.
• the distillation separation step D is preferably short-path distillation. The short-path distillation causes less deterioration of the resulting ⁇ -olefin oligomer composition and provides a high-quality lubricating oil.
• the analytical methods for the ⁇ -olefin oligomer composition of the raw materials, intermediates, and products in Examples and Comparative Examples are as follows.
• Composition (carbon number distribution) A gas chromatograph (Agilent 6890N, manufactured by Agilent Technologies) was used with a solution of 0.1 g of a sample (raw material ⁇ -olefin oligomer, intermediate product, product ⁇ -olefin oligomer composition) dissolved in 25 mL of toluene. , the composition of the composition was measured under the following measurement conditions. The component corresponding to each carbon number was calculated from the obtained chromatogram, and the composition (carbon number distribution) was obtained.
• Production Example 1 (Production of hydrogenated polymer (a11) by polymerization and hydrogenation using a metallocene catalyst) (Polymerization step A1) After deaeration by nitrogen bubbling and dehydration, 600 mL of 1-decene was placed in a nitrogen-substituted stainless steel autoclave with an inner volume of 1 L, and then heated to 65°C. Next, a toluene solution of methylaluminoxane adjusted to have a methylaluminoxane concentration of 4000 ⁇ mol/L was added, and further bis(t-butylcyclopentadienyl)zirconium dichloride adjusted to have a zirconium concentration of 64 ⁇ mol/L.
• distillation separation step A2 The polymer (a) is subjected to distillation separation at 1.33 Pa and 200 to 270 ° C. using a simple distillation apparatus, and a high molecular weight fraction (a1) containing 30% by mass or more of a polymer having 30 or more carbon atoms A low molecular weight fraction (a2) containing 95% by mass or more of a polymer having 20 carbon atoms was obtained.
• Production Example 2 (Production of high molecular weight hydrogenated isomer (b11) by acid-catalyzed polymerization, isomerization and hydrogenation) (Polymerization step B1) Activated alumina (NKHO-24 (manufactured by Sumitomo Chemical Co., Ltd.) was added, and a nitrogen bubbling treatment was performed to remove moisture and the like to obtain a dried ⁇ -olefin oligomer.
• Activated alumina NKHO-24 (manufactured by Sumitomo Chemical Co., Ltd.) was added, and a nitrogen bubbling treatment was performed to remove moisture and the like to obtain a dried ⁇ -olefin oligomer.
• a three-necked flask equipped with a three-way cock, a thermometer, and a stirrer was purged with nitrogen, 1968 mL of the dried ⁇ -olefin oligomer was added, and the temperature of the dried ⁇ -olefin oligomer was lowered to 30°C by heating in an oil bath while stirring. made it As catalysts, 6.0 mmol of tert-butyl chloride and 2.0 mmol of diethylaluminum chloride (DEAC) were added.
• 6.0 mmol of tert-butyl chloride and 2.0 mmol of diethylaluminum chloride (DEAC) were added.
• a solution diluted with the above-mentioned dried ⁇ -olefin oligomer to 0.5 mol/L was prepared in advance, and these solutions were added.
• the temperature of the reaction solution rose 10 minutes after the addition of the catalyst, and stopped 2 minutes later. This indicates that the polymerization has ended.
• Example 1 (Production of ⁇ -olefin oligomer composition) (Mixing step C) The hydrogenated polymer (a11) obtained in Production Example 1 and the hydrogenated isomer obtained in the hydrogenation step B3 of Production Example 2 were mixed at a ratio of 1:0.45 (mass ratio) to obtain an ⁇ -olefin oligomer composition. got stuff Table 1 shows the composition (carbon number distribution) of the obtained ⁇ -olefin oligomer composition.
• Example 2 (Production of ⁇ -olefin oligomer composition) (Polymerization step A1 to hydrogenation step B3)
• the temperature during the polymerization reaction in the polymerization step A1 of Production Example 1 was changed from 40 ° C. to 57 ° C., and the polymer obtained under the conditions (referred to as polymer (a′)) was subjected to distillation separation step A2 and hydrogenation. It was subjected to step A3 to obtain a low molecular weight fraction (a2') and a hydrogenated polymer (a11').
• the low-molecular-weight fraction (a2') was used in the polymerization step B1 in place of the low-molecular-weight fraction (a2) to obtain a hydrogenated isomer.
• Comparative example 1 The hydrogenated polymer (a11) obtained in Production Example 1 was used as the ⁇ -olefin oligomer composition of Comparative Example 1.
• Table 1 shows the composition (carbon number distribution) of the obtained ⁇ -olefin oligomer composition.
• Comparative example 2 A hydrogenated polymer (a11) obtained in the same manner as the hydrogenated polymer (a11) of Production Example 1 except that the temperature during the polymerization reaction in the polymerization step A1 of Production Example 1 was changed from 40 ° C. to 57 ° C. ') was used as the ⁇ -olefin oligomer composition of Comparative Example 2.
• Table 1 shows the composition (carbon number distribution) of the obtained ⁇ -olefin oligomer composition.
• the 1-decene conversion rate was calculated from the composition (carbon number distribution) analysis results (gas chromatography method) of the 1-decene used in the polymerization step A1.
• the ⁇ -olefin oligomer composition obtained in the example has a ratio of 30 carbon atoms (1-decene trimer) and 40 carbon atoms (1-decene tetramer) compared to the composition of the comparative example. I know it's expensive.
• a composition containing a large amount of ⁇ -olefin oligomers having 30 carbon atoms and 40 carbon atoms is useful as a lubricating oil component. From this, it can be seen that according to the production method of the present invention, it is possible to selectively obtain an ⁇ -olefin oligomer having a carbon number that is useful as a lubricating oil.
• Example 2 by adjusting the temperature during polymerization in the polymerization step A1, it is possible to increase the component having 20 carbon atoms in the low-molecular-weight fraction (a2). C30 and C40 ⁇ -olefin oligomers can be obtained.
• Examples 3-7 (Production of ⁇ -olefin oligomer composition) (Distillation separation step D)
• the ⁇ -olefin oligomer composition obtained in Example 1 was subjected to short-path distillation under conditions of a pressure of 1 to 5 PaA and a temperature of 200 to 280° C., and fractionated into fractions (fractions) for each target kinematic viscosity.
• PaA represents "Pa (absolute pressure)".
• each fraction is 40 ° C kinematic viscosity for fraction 1, 40 ° C kinematic viscosity for fraction 2, 14 cSt for fraction 2, and 100 ° C kinematic viscosity for fraction 3, 5.8 cSt.
• Fraction 4 has a kinematic viscosity of 45 cSt at 40° C.
• Fraction 5 is the residue distilled under the above distillation conditions after removing the fractions from Fraction 1 to Fraction 4.
• Table 2 shows the results of physical property measurements of the ⁇ -olefin oligomer composition thus obtained.
• Comparative Examples 3-5 As Comparative Examples 3-5, physical properties were measured in the same manner as in Examples 4-6 for commercially available ⁇ -olefin oligomer compositions having kinematic viscosities similar to those in Examples 4-6. Table 2 shows the results of physical property measurements.
• the commercially available products used here are Durasyn 164, Durasyn 166 and Durasyn 168 manufactured by INEOS.
• Durasyn 164, Durasyn 166 and Durasyn 168 are all compositions containing various hydrocarbon compounds of different molecular structures. Each compound contained in the composition has a random branched chain. These are believed to be ⁇ -olefins oligomerized using an acid catalyst or a boron trifluoride catalyst.
• the kinematic viscosity (40°C and 100°C) and viscosity index (VI) were measured in accordance with JIS K2283:2000 using SVM3000 manufactured by Anton Paar.
• the Noack test was measured according to JPI-5S-41-2004, the low temperature cranking viscosity (CCS) (-35°C) was measured according to JIS K2010:1993, and the pour point was measured according to JIS K2269:1987.
• the ⁇ -olefin oligomer compositions obtained in the examples have similar kinematic viscosities to the ⁇ -olefin oligomer compositions of the comparative examples, they have less evaporation loss in the Noack test and low temperature cranking viscosity ( CCS viscosity) is also small, and the viscosity index (VI) is also high. From this, the ⁇ -olefin oligomer composition of the present invention can achieve both the contradictory performances of fluidity and volatility at low temperatures, and therefore has excellent performance when used as a lubricating oil.

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