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WO2018168889A1 - Procédé de fabrication de composé polyéther - Google Patents

Procédé de fabrication de composé polyéther Download PDF

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Publication number
WO2018168889A1
WO2018168889A1 PCT/JP2018/009838 JP2018009838W WO2018168889A1 WO 2018168889 A1 WO2018168889 A1 WO 2018168889A1 JP 2018009838 W JP2018009838 W JP 2018009838W WO 2018168889 A1 WO2018168889 A1 WO 2018168889A1
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Prior art keywords
polyether compound
group
producing
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molecular weight
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English (en)
Japanese (ja)
Inventor
吉田　幸生
妙子 中野
忠 氣仙
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers

Definitions

  • the present invention relates to a method for producing a high molecular weight polyether compound, a method for producing a viscosity index improver containing the polyether compound, and a method for producing a lubricating oil composition.
  • Polyether compounds such as polyalkylene glycols (hereinafter also simply referred to as “PAG”) are widely used as raw materials for polyurethane products such as elastomers, adhesives and sealants, and functional oils.
  • PAG is produced, for example, by addition polymerization of oxirane monomers such as ethylene oxide and propylene oxide to an initiator having active hydrogen atoms such as various alcohols.
  • an alkali metal alkoxide catalyst, a double metal cyanide complex, or the like is generally used (see, for example, Patent Document 1).
  • these catalysts when these catalysts are used, unsaturated alcohols are produced by side reactions, and the alcohols serve as initiators, so that it is generally difficult to produce high molecular weight PAGs.
  • Patent Document 2 in order to obtain a high molecular weight PAG in a short reaction, oxirane is polymerized in the presence of an alkali metal alkoxide catalyst and aluminum organyl, and at the time of the polymerization, crown ether and cryptand are used. It is disclosed that they are not used together.
  • Patent Document 3 discloses a method using a trialkylaluminum and an onium salt initiator in order to obtain a polymer containing an oxirane monomer unit having a high molecular weight and a narrow molecular weight distribution.
  • Patent Documents 2 and 3 only disclose a PAG having a weight average molecular weight (Mw) of less than 100,000, and further high molecular weight is desired in order to obtain a high-performance viscosity index improver. .
  • the present invention has been made in view of the above problems, and an object of the present invention is to produce a high molecular weight polyether compound.
  • component (A) organoaluminum
  • component (B) onium salt
  • An organoaluminum (A) and an onium salt (B) A method for producing a polyether compound, comprising a step of polymerizing an oxirane monomer using a molar ratio [A / B] of component (A) to component (B) of 3 or more and 60 or less. .
  • R 1 represents a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms having 1 to 4 bonds
  • R 7 O is derived from an oxirane monomer.
  • R 8 represents a structural unit, and R 8 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an oxygen-containing hydrocarbon group having 1 to 10 carbon atoms.
  • m is a value at which the weight average molecular weight of the polyether compound is 100,000 or more
  • n is an integer of 1 or more and 4 or less.
  • a plurality of R 7 Os may be the same as or different from each other. When n is 2 or more, a plurality of R 8 may be the same or different from each other.
  • a method for producing a viscosity index improver comprising a step of diluting the polyether compound obtained by the production method according to [1] or the polyether compound according to [2] with a base oil.
  • a method for producing a lubricating oil composition comprising a step of blending the polyether compound obtained by the production method according to [1] above or the polyether compound according to [2] above into a lubricating base oil.
  • a viscosity index improver comprising the polyether compound obtained by the production method according to [1] or the polyether compound according to [2].
  • a lubricating oil composition comprising the polyether compound obtained by the production method according to the above [1] or the polyether compound according to the above [2] and a lubricating base oil.
  • [7] A method in which the polyether compound obtained by the production method described in [1] above or the polyether compound described in [2] above is added to a lubricating oil composition to improve the viscosity index.
  • a refrigerator filled with the lubricating oil composition obtained by the production method according to [4] or the lubricating oil composition according to [6].
  • An internal combustion engine filled with the lubricating oil composition obtained by the production method according to [4] or the lubricating oil composition according to [6].
  • An industrial apparatus filled with the lubricating oil composition obtained by the production method according to [4] or the lubricating oil composition according to [6].
  • the present invention will be described using embodiments.
  • Method for producing polyether compound In the method for producing a polyether compound according to an embodiment of the present invention, the organic aluminum (A) and the onium salt (B) are mixed in a quantity ratio [A / B] of the component (A) and the component (B). It is a method for producing a polyether compound having a step of polymerizing an oxirane monomer using a molar ratio of 3 or more and 60 or less.
  • the organoaluminum (A) is preferably a trialkylaluminum, more preferably a trialkylaluminum having an alkyl group having 1 to 18 carbon atoms, and even more preferably a trialkylaluminum having an alkyl group having 1 to 8 carbon atoms.
  • Component (A) serves as a catalyst in the polymerization reaction in the production method.
  • the alkyl group in component (A) may be branched or linear. Moreover, the alkyl groups contained in one molecule may be the same or different from each other.
  • Component (A) is preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum or triisobutylaluminum, more preferably triisobutylaluminum.
  • a component (A) may be used independently and may be used in combination of 2 or more type.
  • the trialkylaluminum may be diluted with a solvent such as hexane or toluene.
  • the amount of component (A) used is such that the amount ratio [A / B] of component (A) to component (B) is 3 to 60 in terms of molar ratio.
  • the ratio [A / B] is 3 or more and 60 or less in terms of molar ratio, a high molecular weight polyether compound can be produced.
  • the ratio [A / B] is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, and preferably 50 or less, more preferably 40 or less, in terms of molar ratio. More preferably, it is 30 or less.
  • the polymerization reaction of the oxirane monomer is carried out under the conditions of 10 ° C.
  • the ratio [A / B] is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, and preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less. It is.
  • Onium salt (B) serves as a polymerization initiator in the polymerization reaction in the production method.
  • Examples of the component (B) include a halogen-free onium salt and a halogen-containing onium salt, and a halogen-free onium salt is preferable.
  • the halogen-free onium salt is an onium salt having no halogen atom in the onium salt.
  • the onium salt serving as a polymerization initiator does not have a halogen atom, the resulting polyether compound does not contain a halogen atom at the polymerization initiation terminal. Therefore, it is preferable when obtaining a polyether compound having a lower halogen content.
  • the halogen-free onium salt includes, for example, a halogen-free ammonium salt, and preferably includes a compound represented by the following general formula (1).
  • R 1 is a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms having 1 to 4 bonds
  • R 2 is a linear or branched carbon atom having 4 or more carbon atoms. 8 or less alkyl group
  • n is an integer of 1 or more and 4 or less.
  • n is an integer of 1 or more and 2 or less, and R 1 preferably has 1 or more and 2 or less bonding portions, and n is 1.
  • R 1 is more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
  • the carbon number of R 2 is preferably 4 or more and 6 or less, and more preferably 4.
  • R 1 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, linear or branched alkyl groups such as tert-pentyl group, n-hexyl group, methylpentyl group and isohexyl group; from polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and pentaerythritol A linear or branched saturated hydrocarbon group having 2 or more and 4 or less bonds, exemplified by a residue excluding a hydroxyl group.
  • R 2 examples include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isobutyl, sec-butyl, tert-butyl, isopentyl, Examples thereof include linear or branched alkyl groups such as neopentyl group, tert-pentyl group, methylpentyl group, isohexyl group and 2-ethylhexyl group, preferably linear or branched butyl group, linear or branched octyl Groups and the like.
  • a plurality of R 2 may be the same as each other or different from each other.
  • a plurality of R 2 are preferably the same as each other.
  • the halogen-free onium salt is synthesized, for example, by reacting an alkali metal alkoxide with a quaternary ammonium salt.
  • the alkali metal alkoxide can be obtained by alkoxylating an alcohol with an alkali metal hydride.
  • the alkyl group of the alcohol to be used is changed according to the carbon number of R 1 , and those having 1 to 6 carbon atoms are used.
  • the alkyl group may be linear or branched.
  • an alcohol having a valence of 1 to 4 is used.
  • propane and pentaerythritol examples include propane and pentaerythritol.
  • the quaternary ammonium salt include tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctylammonium chloride, and tetraoctylammonium bromide.
  • Halogen-containing onium salt As said halogen-containing onium salt, a halogen-containing ammonium salt is mentioned, for example, Preferably, the compound represented by following General formula (2) is mentioned.
  • X represents a halogen atom
  • R 3 to R 6 each independently represents an alkyl group having 1 to 8 carbon atoms.
  • the halogen atom represented by X includes at least one halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom. Preferably it is a chlorine atom.
  • the alkyl group having 1 to 8 carbon atoms represented by R 3 to R 6 is independently more preferably 1 to 5 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and is preferably linear.
  • alkyl group having 1 to 8 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, sec-butyl group, Examples thereof include a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a methylpentyl group, an isohexyl group, and a 2-ethylhexyl group.
  • a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable.
  • a plurality of R 3 to R 6 are preferably the same as each other.
  • halogen-containing onium salt examples include, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, and preferably composed of these.
  • At least one selected from the group more preferably at least one selected from the group consisting of tetrabutylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, and tetrabutylammonium chloride, more preferably tetrabutylammonium chloride or tetra Butylammonium bromide.
  • Component (B) may be used in an amount that varies depending on the molecular weight of the desired polyether compound, but is preferably 0.005 mol% or more and 0.150 mol% with respect to all monomers in the reaction system. Or less, more preferably 0.010 mol% or more and 0.100 mol% or less, still more preferably 0.010 mol% or more and 0.060 mol% or less, still more preferably 0.010 mol% or more and 0.030 mol% or less. It is. By making the usage-amount of onium salt more than these lower limits, it becomes possible to advance a polymerization reaction appropriately by using onium salt as an initiator. Moreover, the molecular weight of the polyether compound obtained becomes high enough by setting it as these upper limit values or less.
  • the halogen-containing onium salt may be used in an amount that varies depending on the desired molecular weight. Preferably it is 0.0002 mass% (2 mass ppm) or more and 1.000 mass% (10,000 mass ppm) or less with respect to the total amount with containing onium salt, More preferably, it is 0.0010 mass% (10 mass ppm) ) Or more and 0.5000 mass% (5,000 mass ppm) or less, more preferably 0.0020 mass% (20 mass ppm) or more and 0.2000 mass% (2,000 mass ppm) or less, still more preferably 0.00.
  • a component (B) may be used independently and may be used in combination of 2 or more type.
  • the oxirane monomer is a compound having a hetero 3-membered ring (hereinafter also referred to as “3-membered ether structure”) composed of 2 carbon atoms and 1 oxygen atom.
  • the oxirane monomer those having no halogen atom in the molecule are preferably used.
  • the oxirane monomer include ethylene oxide, alkylene oxide having a chain or branched alkyl group, alkylene oxide having a chain or branched alkenyl group, alicyclic epoxide, alkyl glycidyl ether, and aromatic epoxide. Can be mentioned.
  • the alkylene oxide having a chain or branched alkyl group is not particularly limited as long as the alkyl group is a compound in which the alkyl group is bonded to a carbon atom of a three-membered ring ether structure.
  • propylene oxide 1,2-epoxy Butane, 1,2-epoxyisobutane, 2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxy
  • the alkylene oxide having a chain or branched alkenyl group is not particularly limited as long as it is a compound in which the alkenyl group is bonded to a carbon atom of a 3-membered ring ether structure.
  • 2-vinyloxirane, 2-allyl Examples include oxirane, 2-isopropenyloxirane, 2- (3-butenyloxirane), 2- (5-hexenyloxirane), and 2- (7-octenyloxirane).
  • An alkylene oxide having a chain or branched alkyl group and an alkenyl group may be used, and examples thereof include 2-methyl-2-isopropenyloxirane and 2-methyl-2-allyloxirane.
  • Examples of the alicyclic epoxide include compounds in which a cycloalkyl group is bonded to a carbon atom of a 3-membered ring ether structure.
  • 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2 -5 carbon atoms such as epoxycycloheptane, 1,2-epoxycyclooctane, 1,2-epoxycyclononane, 1,2-epoxycyclodecane, 1,2-epoxycycloundecane, 1,2-epoxycyclododecane, etc.
  • the alicyclic epoxide of 12 or less is mentioned.
  • alkyl glycidyl ether examples include methyl glycidyl ether, ethyl glycidyl ether, and butyl glycidyl ether
  • aromatic epoxide examples include styrene oxide and phenyl glycidyl ether. These may be used alone or in combination of two or more.
  • the polyether compound has a structure similar to that of a conventionally used PAG, and various In various fields. For example, in the lubricating oil field, it is suitably used as a viscosity index improver.
  • ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyisobutane, and 2,3-epoxybutane preferably one or more selected from the group consisting of ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyisobutane, and 2,3-epoxybutane, more preferably ethylene oxide, propylene oxide.
  • 1,2-epoxybutane more preferably propylene oxide, 1,2-epoxybutane or a mixture thereof, and still more preferably propylene oxide.
  • the oxirane monomer may be an oxirane monomer having a halogen atom.
  • the oxirane monomer having a halogen atom include a compound containing at least one halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom and a three-membered ring ether structure.
  • epihalohydrins such as epifluorohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, ⁇ -methylepichlorohydrin; p-chlorostyrene oxide, dibromophenylglycidyl ether, Tetrafluoroethylene oxide, hexafluoropropylene oxide, perfluorophenyl glycidyl ether and the like can be mentioned.
  • epihalohydrin is preferable and epichlorohydrin is more preferable.
  • the synthesis of the polyether compound is performed by ring-opening polymerization of an oxirane monomer in the presence of the component (A) and the component (B).
  • the polymerization reaction is usually performed by mixing these raw materials in the reaction system.
  • the raw materials are mixed, for example, by adding the onium salt (B) dissolved in the oxirane monomer to the organoaluminum (A) previously charged in the reaction system, and then further adding the oxirane monomer. Preferably it is done.
  • the organic aluminum (A) is further charged, and the onium salt previously dissolved in the oxirane monomer with respect to the mixture of the solvent and the organic aluminum (A).
  • the polymerization reaction may be performed by adding an oxirane monomer to a mixture of the organoaluminum (A) and the onium salt (B) previously charged in the reaction system, or the onium salt (B) and An organic aluminum (A) may be added to a mixture of oxirane monomers.
  • the polymerization reaction is not particularly limited, but it is preferably performed in the presence of a solvent. By carrying out in the presence of a solvent, it becomes easy to control polymerization, and it becomes easy to produce a high molecular weight polyether compound.
  • the solvent is not particularly limited as long as it is inert to the raw material.
  • chain saturated hydrocarbon solvents such as n-pentane, n-hexane, n-heptane and n-octane; isooctane
  • Branched-chain saturated hydrocarbon solvents such as cycloaliphatic saturated hydrocarbon solvents such as cyclopentane and cyclohexane
  • saturated hydrocarbon solvents such as benzene and toluene
  • aromatic hydrocarbon solvents such as benzene and toluene
  • monoethers Ether solvents such as diether, triether, tetraether, polyvinyl ether, polyalkylene glycols, and the like.
  • examples of the monoether include dialkyl ethers in which the alkyl group has 1 to 12 carbon atoms.
  • a dialkyl diether having an alkyl group having 1 to 12 carbon atoms is used, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol and the like.
  • dialkyl ethers of alkanediols examples of the triether and tetraether include trivalent or tetravalent alcohol alkyl ethers such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
  • solvents it is preferable to use a saturated hydrocarbon solvent from the viewpoint of easy production of a higher molecular weight polyether compound.
  • solvents may be used alone or in combination of two or more.
  • the “solvent” refers to a solvent added to the reaction system in order to synthesize the polyether compound by polymerizing the oxirane monomer.
  • solvents which are previously contained in additives other than the oxirane monomer such as catalyst (component (A)) and polymerization initiator (component (B))
  • Solvents containing agents are not included in the “solvent” mentioned here.
  • the molar amount of the monomer with respect to 1 L of the solvent is preferably 0.10 mol / L or more and 10.00 mol / L or less, more preferably 1.00 mol / L or more and 8.00 mol / L or less, More preferably, it is added to the reaction system so as to be 1.00 mol / L or more and 4.00 mol / L or less.
  • the amount of the solvent used in the reaction system is such that the molar amount of the oxirane monomer relative to 1 L of the solvent is preferably 0.50 mol / mol from the viewpoint of making it easier to produce a high molecular weight polyether compound.
  • L or more more preferably 1.00 mol / L or more, further preferably 2.00 mol / L or more, still more preferably 2.50 mol / L or more, and preferably 8.00 mol / L or less. More preferably, it is 6.00 mol / L or less, More preferably, it is 5.00 mol / L or less, More preferably, it is 4.50 mol / L or less.
  • Conditions for carrying out the polymerization reaction of the oxirane monomer can be appropriately set according to the type of raw material used, the target molecular weight, and the like.
  • the pressure during the polymerization reaction is usually atmospheric pressure.
  • the temperature at which the oxirane monomer is polymerized can be, for example, -30 ° C. or more and 100 ° C. or less, but for example, higher than the weight average molecular weight (Mw) of 100,000 or more. From the viewpoint of obtaining a polyether compound having a molecular weight, it is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 20 ° C. or higher, still more preferably ⁇ 15 ° C. or higher, and preferably 30 ° C.
  • a high-molecular weight polyether compound can be obtained even under mild conditions of about room temperature. From the viewpoint of workability and safety during the polymerization reaction, and from the viewpoint of industrialization, it is preferable to polymerize the oxirane compound under milder conditions to obtain a high molecular weight polyether compound.
  • the temperature at which the oxirane monomer is polymerized in the production method is preferably ⁇ 10 ° C. or more, more preferably ⁇ 5 ° C. or higher, more preferably 0 ° C. or higher, even more preferably 5 ° C. or higher, even more preferably 10 ° C. or higher, and preferably 40 ° C. or lower, more preferably 35 ° C. or lower, still more preferably 30 ° C. Below, more preferably 25 ° C. or less.
  • the polymerization time is preferably 0.5 hours or more and 24 hours or less, more preferably 1 hour or more and 15 hours or less, and further preferably 2 hours or more and 10 hours or less.
  • the polymerization reaction may be stopped, for example, by adding water, alcohol, acidic substance, basic substance, or a mixture thereof to deactivate the catalyst (component (A)).
  • the polyether compound may be recovered by removing impurities and volatile components by a conventional method such as filtration and distillation under reduced pressure in the recovery step.
  • the catalyst (component (A)) may be removed by pressure filtration using an adsorbent, or may be removed by washing with high-temperature alkaline water and then with pure water without using an adsorbent. .
  • the terminal of the obtained polyether compound becomes a hydroxyl group
  • the terminal hydroxyl group may introduce a functional group with a modifier.
  • the terminal of the polyether compound introduces a hydrocarbon group having 1 to 10 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 10 carbon atoms by esterifying or etherifying a hydroxyl group.
  • the hydrocarbon group includes an alkyl group
  • the oxygen-containing hydrocarbon group includes an acyl group. Details of these hydrocarbon group and oxygen-containing hydrocarbon group are the same as those for R 8 described later.
  • a polyether compound having a weight average molecular weight (Mw) of 100,000 or more can be produced.
  • Mw weight average molecular weight
  • the polyether compound is useful in various fields. For example, in the lubricating oil field, it is suitably used as a viscosity index improver for improving the viscosity index. More preferably used as a viscosity index improver for a refrigerator oil composition.
  • the weight average molecular weight (Mw) of the polyether compound obtained by the production method is preferably 100,000 or more, more preferably 200,000 or more, further from the viewpoint of effectively expressing the effect of the obtained polyether compound. Preferably it is 300,000 or more. In addition, from the viewpoint of easy handling and ease of production of the obtained polyether compound, it is preferably 1,000,000 or less, more preferably 600,000 or less, and still more preferably 550,000 or less. In addition, the value of the said weight average molecular weight (Mw) is a value measured using the method as described in the Example mentioned later.
  • the polyether compound according to an embodiment of the present invention is a compound represented by the following general formula (3) or (4), and has a weight average molecular weight (Mw) of 100,000 or more, preferably 1,000,000. It becomes the following.
  • R 1 and n are each the same as R 1 and n in the general formula (1), the same applies to its preferred embodiment.
  • R 7 O is a structural unit derived from an oxirane monomer
  • m is a value at which the weight average molecular weight of the polyether compound is 100,000 or more, and preferably 1,000,000 or less.
  • R 8 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an oxygen-containing hydrocarbon group having 1 to 10 carbon atoms.
  • a plurality of R 7 Os may be the same as or different from each other.
  • n is 2 or more, a plurality of R 8 may be the same or different from each other.
  • X, R 7 O, and R 8 are the same as X in General Formula (2) and R 7 O and R 8 in General Formula (3), respectively.
  • the preferred embodiment is also the same.
  • r is a value with which the weight average molecular weight of the polyether compound is 100,000 or more, and preferably a value with 1,000,000 or less.
  • a plurality of R 7 Os may be the same as or different from each other.
  • R 7 in the general formulas (3) and (4) is, for example, a divalent hydrocarbon group having 2 to 27 carbon atoms or a divalent hydrocarbon group having 2 to 27 carbon atoms having an oxygen atom. Can be mentioned. These may be used alone in one molecule or in combination of two or more.
  • the oxirane monomer is preferably ethylene oxide or an alkylene oxide having a chain alkyl group. Accordingly, in the general formulas (3) and (4), R 7 O is preferably —CR 9 2 CR 9 2 O— (wherein R 9 independently represents a hydrogen atom or a chain alkyl group).
  • a total number of carbon atoms of 2 or more and 27 or less, and the total number of carbon atoms is more preferably 2 or more and 20 or less, still more preferably 2 or more and 12 or less. Preferably they are 2 or more and 4 or less.
  • R 7 O -CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (CH 2 CH 3) O -, - CH 2 C (CH 3 ) 2 O—, —CH (CH 3 ) CH (CH 3 ) O—.
  • -CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (CH 2 CH 3) O- is more preferable.
  • the polyether compound when the total carbon number of R 7 O is 2 or more and 4 or less, the polyether compound is easily used in various fields.
  • a viscosity index improver in the lubricating oil field, as a viscosity index improver. It is preferably used and more preferably used as a viscosity index improver for use in refrigerator oil compositions.
  • the hydrocarbon group having 1 to 10 carbon atoms in R 8 may be linear, branched or cyclic.
  • the hydrocarbon group is preferably an alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a branched or linear butyl group, a branched or linear pentyl group, a branched or linear hexyl group, A branched or straight chain heptyl group, a branched or straight chain octyl group, a branched or straight chain nonyl group, a branched or straight chain decyl group, a cyclopentyl group, a cyclohexyl group, etc.
  • Examples of the oxygen-containing hydrocarbon group having 1 to 10 carbon atoms in R 8 include an acyl group having 2 to 10 carbon atoms, a chain aliphatic group having an ether bond, and a cyclic aliphatic group having an ether bond (for example, , Tetrahydrofurfuryl group) and the like.
  • the hydrocarbon group moiety of the acyl group having 2 to 10 carbon atoms may be linear, branched or cyclic.
  • the hydrocarbon group portion of the acyl group is preferably an alkyl group, and examples thereof include those having 1 to 9 carbon atoms among the alkyl groups that can be selected as R 8 described above.
  • R 8 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom. Is an atom. If in one molecule R 8 have multiple to R 8 may be the same as each other in each molecule, it may be different.
  • the polyether compound represented by the general formula (4) is more preferably a polyether compound represented by the following general formula (5).
  • X, R 8 and r are each the same as the X, R 8 and r in the general formula (4), it is the same preferred embodiments thereof.
  • R 10 represents a single bond or a methylene group
  • R 11 represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 24 carbon atoms.
  • Y represents a single bond or an oxygen atom.
  • the plurality of R 10 may be the same as or different from each other.
  • the plurality of R 11 may be the same as or different from each other.
  • a plurality of Y may be the same as each other or different from each other.
  • R 10 is preferably a single bond.
  • R 11 is preferably a hydrogen atom or an alkyl group having 1 to 24 carbon atoms.
  • the alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and is preferably linear.
  • alkyl group having 1 to 24 carbon atoms examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
  • they are a hydrogen atom, a methyl group, an ethyl group, or a propyl group, More preferably, they are a hydrogen atom or a methyl group, More preferably, it is a methyl group.
  • Y is preferably a single bond. Further, although there are a plurality of Y, the plurality of Y may be the same or different from each other.
  • the case where R 10 and Y are both single bonds means that R 11 is directly bonded to the carbon atom in the main chain of the polyether compound represented by the general formula (5).
  • the general formula (5) is preferably the same plurality of R 10 with each other, a plurality of R 11 are the same and, at the same plurality of Y with each other.
  • a polyether having a molecular structure represented by the general formula (3), (4) or (5) As a compound, it was difficult to obtain a polymer having a weight average molecular weight (Mw) of 100,000 or more.
  • Mw weight average molecular weight
  • the polyether compound is preferably obtained by the method for producing a polyether compound.
  • the polyether compound having a structure represented by the general formula (3), (4) or (5) having a weight average molecular weight (Mw) of 100,000 or more has various characteristics due to its high molecular weight.
  • the high molecular weight polyether compound can improve the viscosity index of the lubricating oil composition by being blended with the lubricating oil composition, but the weight average molecular weight (Mw) should be 100,000 or more.
  • the viscosity index can be further increased.
  • the polyether compound has a weight average molecular weight (Mw) of preferably 150,000 or more, more preferably 200,000 or more, and more preferably 300,000 or more.
  • the polyether compound can more easily exhibit various characteristics obtained when it is made into a polymer. For example, when used as a viscosity index improver, the viscosity index can be further increased.
  • the polyether compound has a weight average molecular weight (Mw) of 1,000,000 or less because the production and handleability thereof are easier. Examples of handleability include the viewpoint of good or bad solubility in a lubricating base oil or a base oil for dilution contained in a viscosity index improver described later. From the viewpoint of production and handling of the polyether compound, the weight average molecular weight (Mw) of the polyether compound is more preferably 800,000 or less, still more preferably 600,000 or less, and still more preferably 550,000 or less. It is.
  • the polyether compound preferably has a molecular weight distribution (Mw / Mn) represented by a ratio of its weight average molecular weight (Mw) to number average molecular weight (Mn), preferably 10.0 or less, more preferably 5. It is 0 or less, more preferably 3.0 or less, and still more preferably 2.5 or less.
  • the lower limit is not particularly limited, but is preferably 1.1 or more, more preferably 1.3 or more, still more preferably 1.4 or more, and still more preferably 1.5 or more.
  • the said weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be measured by the method as described in an Example.
  • m in the general formula (3) and r in the general formulas (4) and (5) each independently represent an integer with which the weight average molecular weight (Mw) of the polyether compound is 100,000 or more, Preferably, it is an integer such that the weight average molecular weight (Mw) of the polyether compound is 150,000 or more, more preferably 200,000 or more, still more preferably 300,000 or more, and preferably 1,000,000 or less, More preferably, it is an integer that is 800,000 or less, more preferably 600,000 or less, and still more preferably 550,000 or less.
  • the polyether compound represented by the general formula (3) is preferably obtained by the method for producing a polyether compound using a halogen-free onium salt represented by the general formula (1) as a polymerization initiator. Is.
  • the polyether compound represented by the general formula (4) or (5) is preferably a halogen-containing onium salt represented by the general formula (2) as a polymerization initiator, It is obtained by the method.
  • the halogen atom content in the polymer molecule measured by combustion ion chromatography is preferably 0.1000% by mass (1,000 ppm by mass).
  • the polyether compound represented by General formula (4) or (5) it is preferable that it is a polyether compound which has a halogen atom only in the molecular terminal.
  • terminal halogens are less likely to be eliminated and the risk of acid generation can be reduced. Further, the risk of the polymer being decomposed by the acid can be reduced.
  • halogen atom chlorine atom
  • content of the halogen atom (chlorine atom) in the said polymer molecule can be measured with a combustion ion chromatograph method, for example with the following apparatus and conditions.
  • Sample combustion / equipment Product name “AQF-100”, manufactured by Mitsubishi Chemical Analytech Co., Ltd./ Combustion conditions
  • Combustion furnace set temperature Pre-stage 800 ° C., post-stage 1,000 ° C.
  • the lubricating oil composition includes a lubricating base oil and the polyether compound, and preferably includes a lubricating base oil and a polyether compound obtained by the production method. .
  • the lubricating oil composition improves the viscosity index by containing a polyether compound having a high molecular weight as described above.
  • the polyether compound is generally 0.01% to 50% by mass, preferably 0.1% to 30% by mass, more preferably 0.1% to 15% by mass. Contained.
  • the lubricating base oil is not particularly limited as long as it is generally used as a base oil for lubricating oil, and includes mineral oil, synthetic oil, or a mixture thereof, and an oxygen-containing base oil is preferable.
  • the oxygen-containing base oil include aliphatic monoesters, aliphatic diesters, aliphatic triesters, polyol esters (POE), aliphatic monoethers, aliphatic diethers, aliphatic triethers, aliphatic And tetravinyl ether and aliphatic polyvinyl ether (PVE).
  • POE polyol esters
  • PVE polyol esters
  • the lubricating base oil is not particularly limited, but usually has a 100 ° C.
  • kinematic viscosity in the range of 0.5 mm 2 / s to 50 mm 2 / s and in the range of 1 mm 2 / s to 25 mm 2 / s. Some are preferred.
  • the kinematic viscosity was measured using a glass capillary viscometer according to JIS K2283-2000.
  • the lubricating oil composition is an antioxidant, an oily agent, an extreme pressure agent, a detergent / dispersant, a viscosity index improver other than the polyether compound, a rust preventive agent, a metal antibacterial agent as long as the effect of the polyether compound is not impaired.
  • You may contain additives, such as an activator and an antifoamer. You may use these individually by 1 type or in combination of 2 or more types.
  • the said lubricating oil composition may consist of the said lubricating base oil and the said polyether compound, without mix
  • the lubricating oil composition may be composed of at least one selected from the group consisting of the above-mentioned lubricating base oil, polyether compound, and the aforementioned additives.
  • the lubricating oil composition is preferably used as a refrigerating machine oil. That is, the lubricating oil composition is used by filling the inside of the refrigerator together with the refrigerant, and is suitably used, for example, for lubricating a sliding portion such as a compressor provided in the refrigerator.
  • the lubricating oil composition is used in internal combustion engines such as gasoline engines and diesel engines, transmissions, shock absorbers, various gear structures, various bearing mechanisms, and other various industrial devices. May be.
  • an embodiment of the present invention includes a refrigerator filled with the lubricating oil composition.
  • An embodiment of the present invention includes an internal combustion engine filled with the lubricating oil composition, and examples of the internal combustion engine include a gasoline engine and / or a diesel engine. Moreover, as one Embodiment of this invention, the industrial apparatus with which the said lubricating oil composition was filled is mentioned. Examples of the industrial device include one or more selected from the group consisting of a transmission, a shock absorber, various gear structures, and various bearing mechanisms.
  • the lubricating oil composition is produced by blending the lubricating base oil with the polyether compound and other various additives used as necessary, preferably the lubricating base oil. It is manufactured by blending the polyether compound obtained by the above production method and other various additives used as necessary. That is, the method for producing a lubricating oil composition according to an embodiment of the present invention is a production method having a step of blending the polyether compound into a lubricating base oil, and preferably a polysilicic acid obtained by the production method. It is a manufacturing method which has the process of mix
  • the polyether compound is preferably used as an additive for improving the viscosity index of a lubricating oil composition, and more preferably used as a viscosity index improver for refrigerating machine oil. That is, an embodiment of the present invention is a method of adding the polyether compound to a lubricating oil composition to improve the viscosity index, and preferably the polyether compound obtained by the production method is used as a lubricating oil composition. It is a method of improving the viscosity index by adding to a product.
  • the said viscosity index improver may consist of the said polyether compound single-piece
  • the viscosity index improver may contain a base oil for diluting the polyether compound in addition to the polyether compound. As the base oil, various base oils listed in the lubricating base oil can be used.
  • the method for producing a viscosity index improver is a production method including a step of diluting the polyether compound with a base oil, and preferably a polyether compound obtained by the production method.
  • a production method having a step of diluting with a base oil is used suitably for a lubricating oil composition, and is suitably used by a refrigerator oil composition.
  • the polyether compound can be used in various applications other than the lubricating oil application, and can be used as a raw material for polymer materials such as urethane constituting elastomers, resins, rubbers and the like. Urethane is used for sealants, adhesives and the like, for example.
  • the following physical properties of the polyether compound were measured according to the following procedure.
  • Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC).
  • GPC uses two TSKgel SuperMultipore HZ-M manufactured by Tosoh Corporation as a column, performs measurement using tetrahydrofuran as an eluent, and a refractive index detector as a detector, and uses polystyrene as a standard sample as a weight average molecular weight (Mw) and a number.
  • the average molecular weight (Mn) was determined.
  • the molecular weight distribution (Mw / Mn) was calculated using the obtained weight average molecular weight (Mw) and number average molecular weight (Mn) values.
  • Example 1 A thermometer, a stirring blade (four inclined paddles), and a 20 mL and 100 mL dropping funnel were attached to a 1 L four-necked separable flask, and the inside of the separable flask was replaced with nitrogen. Under a nitrogen atmosphere, 500 mL of n-heptane (manufactured by Wako Pure Chemical Industries, Ltd., trade name “super dehydrated heptane”) was charged into the separable flask as a solvent. The separable flask was immersed in a thermostatic chamber whose refrigerant temperature was controlled at 15 ° C. or higher and 18 ° C.
  • tetrabutylammonium methoxide (component (B)) as a polymerization initiator was added to a 20 mL 2-neck pear flask with a three-way cock as a polymerization initiator. .6 mg (0.2765 mmol) was charged. After the pear-shaped flask was taken out of the glove box, 10 mL (0.143 mol) of propylene oxide was added and dissolved in a nitrogen atmosphere to prepare a propylene oxide solution of tetrabutylammonium methoxide.
  • the propylene oxide solution of tetrabutylammonium methoxide was charged into a 20 mL dropping funnel provided in the separable flask, and 90 mL (1.287 mol) of propylene oxide was charged into the other 100 mL dropping funnel.
  • a propylene oxide solution of tetrabutylammonium methoxide in the 20 mL dropping funnel was dropped into the separable flask whose internal temperature was controlled at 20 ° C. over 10 minutes.
  • Example 2 In Example 1, polyether compound 2 was obtained in the same manner as in Example 1 except that 0.83 mmol was used instead of 4.2 mmol of component (A) triisobutylaluminum.
  • Example 3 In Example 1, polyether compound 3 was obtained in the same manner as in Example 1 except that 8.3 mmol was used instead of 4.2 mmol of component (A) triisobutylaluminum.
  • Example 4 A polyether compound 4 was obtained in the same manner as in Example 1 except that 2.1 mmol of component (A) triisobutylaluminum was used instead of 4.2 mmol.
  • Example 5 A polyether compound 5 was obtained in the same manner as in Example 4 except that 300 mL of n-heptane as a solvent was used instead of 500 mL in Example 4.
  • Example 6 A polyether compound 6 was obtained in the same manner as in Example 4 except that 700 mL of n-heptane as a solvent was used instead of 500 mL in Example 4.
  • Example 7 In Example 4, the refrigerant temperature in the constant temperature layer was controlled to 25 ° C. or higher and 28 ° C. or lower, and the internal temperature of the separable flask during the polymerization reaction of propylene oxide was controlled to 30 ° C. instead of 20 ° C. Except that, polyether compound 7 was obtained in the same manner as in Example 4.
  • Example 8 In Example 7, polyether compound 8 was obtained in the same manner as in Example 7 except that 4.2 mmol of component (A) triisobutylaluminum was used instead of 2.1 mmol.
  • Example 9 In Example 7, polyether compound 9 was obtained in the same manner as in Example 7 except that 8.3 mmol was used instead of 2.1 mmol of component (A) triisobutylaluminum.
  • Example 10 In Example 4, instead of controlling the internal temperature of the separable flask at 20 ° C. during the polymerization reaction of propylene oxide by controlling the refrigerant temperature in the constant temperature layer to ⁇ 5 ° C. or more and ⁇ 2 ° C. or less. Except having controlled, it carried out similarly to Example 4 and obtained the polyether compound 10.
  • Example 11 polyether compound 11 was obtained in the same manner as in Example 10 except that 4.2 mmol of component (A) triisobutylaluminum was used instead of 2.1 mmol.
  • Example 12 polyether compound 12 was obtained in the same manner as in Example 10 except that 8.3 mmol was used instead of 2.1 mmol of component (A) triisobutylaluminum.
  • the polymerization reaction was performed in the presence of organoaluminum (component (A)) and onium salt (component (B)) in the amounts of component (A) and component (B).
  • a high molecular weight polyether compound could be produced by carrying out under the condition that the ratio [A / B] was 3 to 60 in terms of molar ratio.
  • it was confirmed that a high molecular weight polyether compound can be produced under mild conditions such as 0 ° C. or higher and 30 ° C. or lower.
  • the polyether compound according to one embodiment of the present invention and the polyether compound obtained by the production method are used in a lubricating oil composition used for a refrigerator, an internal combustion engine, a gear structure, a bearing mechanism, a transmission, a shock absorber, and the like.
  • a viscosity index improver it is preferably used as a viscosity index improver, and more preferably used as a viscosity index improver in a refrigerator oil composition.
  • It can also be used as various raw materials such as urethane constituting adhesives and sealants.

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  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne un procédé de fabrication de composé polyéther qui présente une étape au cours de laquelle un monomère d'oxirane est polymérisé à l'aide d'un aluminium organique (A) et d'un sel d'onium (B), de sorte que le rapport massique du composant (A) et du composant (B) 〔Ａ／Ｂ〕 est supérieur ou égal à 3 et inférieur ou égal à 60 en termes de rapport molaire.
PCT/JP2018/009838 2017-03-15 2018-03-14 Procédé de fabrication de composé polyéther Ceased WO2018168889A1 (fr)

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CN113736548A (zh) * 2021-09-28 2021-12-03 珠海格力节能环保制冷技术研究中心有限公司 一种制冷剂与冷冻机油的组合物和空调系统
WO2024006723A1 (fr) 2022-06-30 2024-01-04 The Procter & Gamble Company Articles absorbants et procédés et appareils pour fabriquer des articles absorbants comprenant des parties frangibles

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WO2024006723A1 (fr) 2022-06-30 2024-01-04 The Procter & Gamble Company Articles absorbants et procédés et appareils pour fabriquer des articles absorbants comprenant des parties frangibles

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