WO2018168889A1 - Method for producing polyether compound - Google Patents

Abstract

The present invention relates to a method for producing a polyether compound, which comprises a step for polymerizing an oxirane monomer using an organic aluminum (A) and an onium salt (B) so that the molar ratio of the component (A) to the component (B), namely (A)/(B) is from 3 to 60 (inclusive).

Description

Method for producing polyether compound

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.
As a catalyst for producing PAG, an alkali metal alkoxide catalyst, a double metal cyanide complex, or the like is generally used (see, for example, Patent Document 1). However, 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.

Therefore, it has been studied to increase the molecular weight of polyether compounds such as PAG by various methods. For example, in 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.

Japanese Patent Laid-Open No. 3-195727 Special table 2007-533783 gazette JP 2013-57088 A

In recent years, it has been desired that polyether compounds such as PAG have a higher molecular weight in various fields. For example, in the lubricating oil field, the use of PAG as a viscosity index improver has been studied, but a higher molecular weight is desired in order to further improve the viscosity index. However, 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.

As a result of intensive studies, the present inventors have studied organoaluminum (A) (hereinafter also simply referred to as “component (A)”) and onium salt (B) (hereinafter also simply referred to as “component (B)”). It is found that a high molecular weight polyether compound can be obtained by polymerizing an oxirane monomer to satisfy a specific quantitative ratio [A / B] and producing a polyether compound such as PAG. The present invention was completed.
[1] 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. .
[2] A polyether compound represented by the following general formula (3) or (4), wherein the weight average molecular weight (Mw) is 100,000.

(In General Formula (3), R ¹ represents a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms having 1 to 4 bonds, and 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, and 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. )

(In the general formula (4), X represents a halogen ^{atom, R} 7 O, and ^{R 8} are each the same meaning as the ^{R 7} O and ^{R 8} in general formula (3).
r is a value at which the weight average molecular weight of the polyether compound is 100,000 or more.
A plurality of R ⁷ Os may be the same as or different from each other. )
[3] 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.
[4] 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.
[5] A viscosity index improver comprising the polyether compound obtained by the production method according to [1] or the polyether compound according to [2].
[6] 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.
[8] A refrigerator filled with the lubricating oil composition obtained by the production method according to [4] or the lubricating oil composition according to [6].
[9] 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].
[10] 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].

It becomes possible to produce a high molecular weight polyether compound.

Hereinafter, 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.

<Component (A): Organoaluminum (A)>
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. Alkyl aluminum, more preferably trialkylaluminum having an alkyl group with 2 to 6 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.
When 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.
From such a viewpoint, 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.
In the above production method, when the polymerization reaction of the oxirane monomer is carried out under the conditions of 10 ° C. to 40 ° C., preferably 20 ° C. to 30 ° C., a higher molecular weight polyether compound. 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.

<Component (B): Onium salt (B)>
The 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.

(Halogen-free onium salt)
The halogen-free onium salt is an onium salt having no halogen atom in the onium salt. When a halogen-free onium salt is used in the production method, since 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).

In the general formula (1), R ¹ is a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms having 1 to 4 bonds, and 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.

Here, as the compound represented by the general formula (1), 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. In addition, R ¹ is more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
As the number of carbon atoms in R ^1, preferably 1 to 5, 1 to 4 is more preferable. The carbon number of R ² is preferably 4 or more and 6 or less, and more preferably 4.
When the onium salt of the general formula (1) is used, R ¹ (—O ⁻ ) _n is the polymerization initiation terminal in the obtained polyether compound.

Examples of R ¹ 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.
Examples of R ² 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.
As the alcohol, an alcohol having a valence of 1 to 4 is used. For example, methanol, ethanol, propanol, 2-propanol, butanol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, trimethylol Examples include propane and pentaerythritol.
Examples of 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.

In the general formula (2), X represents a halogen atom, and R ³ to R ⁶ each independently represents an alkyl group having 1 to 8 carbon atoms.

In the general formula (2), 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.
Examples of the alkyl group having 1 to 8 carbon atoms 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. Among these, 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.
In general formula (2), a plurality of R ³ to R ⁶ are preferably the same as each other.

Examples of the halogen-containing onium salt 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.

When the halogen-containing onium salt is used as the component (B), 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. It is 0040 mass% (40 mass ppm) or more and 0.1500 mass% (1,500 mass ppm) or less. By setting the amount of the halogen-containing onium salt used to be equal to or higher than these lower limit values, it becomes possible to appropriately proceed the polymerization reaction using the halogen-containing 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.
A component (B) may be used independently and may be used in combination of 2 or more type.

<Oxirane monomer>
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. As the oxirane monomer, those having no halogen atom in the molecule are preferably used.
Examples of 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. For example, 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-epoxynonadecane, 1, -Chains or branches such as epoxy icosane, 1,2-epoxy heicosane, 1,2-epoxy docosane, 1,2-epoxy tricosane, 1,2-epoxy tetracosane, 1,2-epoxy pentacosane And an alkylene oxide having 3 to 27 carbon atoms and having an alkyl group in the form of a ring.
The alkylene oxide having a chain or branched alkyl group is preferably an alkylene oxide having 3 to 12 carbon atoms, more preferably 3 or 4 carbon atoms.

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. For example, 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. For example, 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.
Examples of the alkyl glycidyl ether include methyl glycidyl ether, ethyl glycidyl ether, and butyl glycidyl ether, and examples of the aromatic epoxide include styrene oxide and phenyl glycidyl ether.
These may be used alone or in combination of two or more.

Among the above, preferably one or more selected from the group consisting of ethylene oxide and alkylene oxide having a chain or branched alkyl group, more preferably selected from the group consisting of ethylene oxide and alkylene oxide having a chain alkyl group. 1 or more selected from the group consisting of ethylene oxide and alkylene oxide having 3 or 4 carbon atoms having a chain alkyl group.
By using at least one selected from the group consisting of ethylene oxide and a C3 or C4 alkylene oxide having a chain alkyl group, 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.
Among the above, 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. And one or more selected from the group consisting of 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.
Examples of 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. Without limitation, for example, epihalohydrins such as epifluorohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin; p-chlorostyrene oxide, dibromophenylglycidyl ether, Tetrafluoroethylene oxide, hexafluoropropylene oxide, perfluorophenyl glycidyl ether and the like can be mentioned. Among these, 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.
And after preparing the solvent mentioned later in the reaction system, 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). It is more preferable to add (B) and then further add an oxirane monomer, and the oxirane monomer to be added later is maintained so that the reaction temperature of the reaction system is maintained at a desired temperature. More preferably, the addition rate is adjusted.
In addition, 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.

<Solvent used for production of polyether compound>
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. For example, 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.

Here, examples of the monoether include dialkyl ethers in which the alkyl group has 1 to 12 carbon atoms. In addition, as the diether, 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. And dialkyl ethers of alkanediols. Examples of the triether and tetraether include trivalent or tetravalent alcohol alkyl ethers such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

Among these solvents, it is preferable to use a saturated hydrocarbon solvent from the viewpoint of easy production of a higher molecular weight polyether compound.
These 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. For example, from the viewpoint of handling of the solvent or these additives, 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.

In the solvent, 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. By making the molar amount of the monomer with respect to 1 L of the solvent not more than these upper limit values, it becomes easy to produce a high molecular weight polyether compound. Moreover, it is prevented that the size of the reaction vessel becomes unnecessarily large by setting the molar amount of the monomer with respect to 1 L of the solvent to be not less than these lower limit values.
In addition, 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. or lower, more preferably 10 ° C. or lower. More preferably, it is 0 ° C. or lower.
Heretofore, it has been difficult to obtain a higher molecular weight polyether compound having a weight average molecular weight (Mw) of 100,000 or more under mild conditions of about room temperature. However, in the method for producing a polyether compound according to one embodiment of the present invention, 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.
Therefore, from the viewpoint of obtaining a high molecular weight polyether compound under such mild conditions, 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)).
Further, after completion of the polymerization reaction, 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. .
Furthermore, although the terminal of the obtained polyether compound becomes a hydroxyl group, the terminal hydroxyl group may introduce a functional group with a modifier. For example, 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. Also good. The hydrocarbon group includes an alkyl group, and 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.

In the method for producing a polyether compound according to an embodiment of the present invention, it is possible to obtain a high molecular weight polyether compound, and furthermore, to obtain a high molecular weight polyether compound even under the mild conditions described above. Is possible. For example, a polyether compound having a weight average molecular weight (Mw) of 100,000 or more can be produced.
By setting the weight average molecular weight (Mw) to 100,000 or more, 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.

[Polyether compounds]
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.

In the general formula (3), 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. It is. 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. When n is 2 or more, a plurality of R ⁸ may be the same or different from each other.

In General Formula (4), 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.

Examples of the compound of the oxirane monomer in the general formulas (3) and (4) are as described above in the column of the production method. 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.
As described above, 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). And 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.
As the embodiment of the more preferred _{^{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—. Of _{these, -CH 2 CH 2 O -,} - CH 2 CH (CH 3) O -, - CH 2 CH (CH 2 CH 3) O- is more preferable. As described above, 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. For example, 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. can be mentioned.
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).

In the 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, and 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.
Examples of the alkyl group having 1 to 24 carbon atoms 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. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert- Butyl, isopentyl, neopentyl, tert-pentyl, methylpentyl, isohexyl, pentylhexyl, butylpentyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Be mentioned In these, Preferably 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).
In 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.

Conventionally, for example, when an oxirane monomer is polymerized under the above-mentioned relatively mild conditions such as −10 ° C. or higher, 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. However, according to the production method according to the embodiment of the present invention, it can be produced. .
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. For example, 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. Thus, 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. By making the molecular weight extremely high in this way, 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.
In addition, it is preferable that 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.

Therefore, 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.
Moreover, 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.
In the case of the polyether compound represented by the general formula (4) or (5), the halogen atom content in the polymer molecule measured by combustion ion chromatography is preferably 0.1000% by mass (1,000 ppm by mass). ) Or less, more preferably 0.0300 mass% (300 mass ppm) or less, still more preferably 0.0100 mass% (100 mass ppm) or less, and preferably 0.0001 mass% (1 mass ppm) or more. More preferably, it is 0.0010 mass% (10 mass ppm) or more, More preferably, it is 0.0050 mass% (50 mass ppm) or more.
Moreover, in the case of 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. Compared to halogens (secondary or tertiary) in the molecule, terminal halogens (primary) 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.

In addition, 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.
(1) 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.
Gas flow rate: From the outer tube of the combustion tube, oxygen = 400 mL / min From the inner tube of the combustion tube, argon or oxygen = 200 mL / min Supply amount of ultrapure water for humidification: 0.1 mL / min (2) Ion chromatograph / device: Product name “DX-120”, manufactured by Thermo Fisher Scientific Co., Ltd., Column: “Dionex (registered trademark) IonPac (registered trademark) AG12A” and “Dionex (registered trademark) IonPac (registered trademark) AS12A”, both of which are Thermo Fisher Scientific Made by Tiffic Corporation

[Lubricating oil composition]
The lubricating oil composition according to an embodiment of the present invention 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.
In the lubricating oil composition, 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. Examples of 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).
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.
In addition, the said lubricating oil composition may consist of the said lubricating base oil and the said polyether compound, without mix | blending additives other than the said polyether compound depending on a use. Of course, 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.
In addition to 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.
As described above, 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.

[Method for producing lubricating oil composition]
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 | blending an ether compound with lubricating base oil. And as above-mentioned, it is preferable that the lubricating oil composition obtained with the said manufacturing method is a refrigerator oil composition used for a refrigerator.

[Viscosity index improver]
As described above, 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.
Although the said viscosity index improver may consist of the said polyether compound single-piece | unit, in addition to the said polyether compound, you may contain another component. For example, 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.

[Method for producing viscosity index improver]
That is, the method for producing a viscosity index improver according to an embodiment of the present invention 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. Is a production method having a step of diluting with a base oil. And as above-mentioned, the viscosity index improver obtained with the said manufacturing method is used suitably for a lubricating oil composition, and is suitably used by a refrigerator oil composition.

Further, 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.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

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. or lower, and the stirring blade was connected to a three-one motor and stirred at a rotation speed of 200 rpm.
Next, 4.2 mL of triisobutylaluminum toluene solution (manufactured by Wako Pure Chemical Industries, Ltd., “1.0 mol / L triisobutylaluminum toluene solution”) as a catalyst (4.2 mmol in terms of triisobutylaluminum as component (A)). ) Charged into the separable flask.
Next, in a glove box (dew point −70 ° C. or less, oxygen 1 ppm or less), 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.
Subsequently, 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.
First, 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.
After completion of the dropwise addition of the propylene oxide solution of tetrabutylammonium methoxide, 90 mL of propylene oxide in the 100 mL dropping funnel was slowly added dropwise over 3 hours while controlling the temperature in the separable flask at 20 ° C. .
After completing the dropwise addition of 90 mL of propylene oxide in the 100 mL dropping funnel, the mixture was waited for 2 hours at the same temperature, and 2 mL of ethanol and 2 mL of 5 wt% sodium hydroxide aqueous solution were added to deactivate the catalyst to complete the polymerization reaction. .
200 ml of toluene and 20 g of “Celite” (registered trademark, manufactured by Imerys Minerals California, Inc.) are further added to the separable flask after the completion of the polymerization reaction, and coarsely filtered using a pressure filter (nitrogen pressure: 0.3 MPa). The product was filtered.
30 mg of an antioxidant (4,4′-methylene-bis (2,6-di-tert-butylphenol)) was added to the filtrate and concentrated in a vacuum dryer using a Teflon (registered trademark) pad. (The degree of vacuum was 1 Torr or less and the temperature was 120 ° C.) to obtain a polyether compound 1.

[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]
In Example 10, 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]
In Example 10, 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.

As described above, in each of Examples 1 to 12, 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.
As shown in Examples 1 to 12, 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.

By using the method for producing a polyether compound according to an embodiment of the present invention, a high molecular weight polyether compound can be obtained. Furthermore, when the said manufacturing method is used, since it becomes possible to obtain a high molecular weight polyether compound on milder conditions, it is very useful industrially.
In addition, 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. For example, 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.

Claims (14)

1. Organoaluminum (A) and 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. .
2. The method for producing a polyether compound according to claim 1, wherein the polymerization of the oxirane monomer is performed at -10 ° C or higher and 40 ° C or lower.
3. The method for producing a polyether compound according to claim 1 or 2, wherein the component (A) is trialkylaluminum.
4. The method for producing a polyether compound according to any one of claims 1 to 3, wherein the component (B) is a halogen-free onium salt.
5. The manufacturing method of the polyether compound of Claim 4 whose said halogen-free onium salt is a compound represented by following General formula (1).
   

   

   
   (In the general formula (1), R ¹ is a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms having 1 to 4 bonds, and R ² is a linear or branched carbon atom having 4 or more carbon atoms. An alkyl group of 8 or less, and n is an integer of 1 to 4.
6. The method for producing a polyether compound according to claim 5, wherein in general formula (1), n is 1 and R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms.
7. The method for producing a polyether compound according to any one of claims 1 to 6, wherein the weight average molecular weight of the polyether compound is 100,000 or more and 1,000,000 or less.
8. The oxirane monomer is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyisobutane, and 2,3-epoxybutane. The manufacturing method of the polyether compound of any one of these.
9. The polymerization of the oxirane monomer is performed in the presence of a solvent, and the molar amount of the oxirane monomer with respect to 1 L of the solvent is 0.10 mol / L or more and 10.00 mol / L or less. The method for producing a polyether compound according to any one of 1 to 8.
10. The method for producing a polyether compound according to claim 9, wherein a saturated hydrocarbon solvent is used as the solvent.
11. A method for producing a viscosity index improver, comprising a step of diluting the polyether compound obtained by the production method according to any one of claims 1 to 10 with a base oil.
12. The method for producing a viscosity index improver according to claim 11, wherein the viscosity index improver is a viscosity index improver used in a refrigerator oil composition.
13. A method for producing a lubricating oil composition, comprising a step of blending the polyether compound obtained by the production method according to any one of claims 1 to 10 into a lubricating base oil.
14. The method for producing a lubricating oil composition according to claim 13, wherein the lubricating oil composition is a refrigerating machine oil composition.