JPH08104687A - Multivalent etheralcohol derivative, and its production - Google Patents

Abstract

PURPOSE: To obtain the new compound useful as a polar oil, a synthetic lubricant, a freezer oil, etc., obtained from inexpensive raw materials by a simple method, and giving compositions used for freezer hydraulic fluids and excellent in compatibility, volume resistivity, etc., as freezer oils. CONSTITUTION: This compound is expressed by formula I or II [R1 is H, 1-21C linear or branched alkyl; when R1 is H, R2 is 3-7C branched alkyl, and when R1 is alkyl, R2 is 1-21C linear or branched alkyl, or R1 and R2 together form 2-13C alkylene; k1 is 0-5; p1 is 0-2; m1 is 0,1; k1 +(m1 +2)p1 =5; R3 is H, 1-8C linear or branched alkyl], e.g. 2,3,4,5-tetra-O-methyl-1,6-di-O-(3,5,5-trimethylhexyl) sorbitol. The compound is obtained by reacting a hexavalent alcohol of formula III (preferably sorbitol) with a carbonyl compound of formula IV or its derivative in the presence of an acid catalyst, and subsequently hydrogenating the obtained cyclic acetal compound, or further capping the product with alkyl groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyhydric ether alcohol derivative useful as a polar oil, an organic solvent, a lubricant, a synthetic lubricating oil, a refrigerating machine oil, etc., and an intermediate for the production thereof, a method for producing the same, and a method for producing the same. The present invention relates to a composition for a working fluid of a refrigerator, which comprises a divalent ether alcohol derivative as a base oil.

[0002]

2. Description of the Related Art Recently, dichlorodifluoromethane (CFC12), which is used in refrigerators and car coolers to protect the ozone layer, is regulated in use and may be prohibited in the future. decided. Further, subsequently, the use of chlorodifluoromethane (HCFC22) used for room air conditioners and the like is about to be regulated. Therefore, this CFC12 and HCF
As an alternative to C22, hydrofluorocarbons that do not destroy the ozone layer, such as 1,1,1,2-tetrafluoroethane (HFC134a), difluoromethane (HFC32), and pentafluoroethane (HFC12).
5) is being developed.

However, hydrofluorocarbons are CF
Since the polarity is higher than that of C12 and HCFC22, if a lubricating oil such as naphthenic mineral oil, poly α-olefin, or alkylbenzene which has been generally used as a refrigerating machine oil is used, the compatibility of these lubricating oils with hydrofluorocarbons is improved. Is poor and causes bilayer separation at low temperatures. When two-layer separation occurs, oil return deteriorates, a thick oil film adheres to the vicinity of the condenser or evaporator as a heat exchanger to hinder heat transfer, and it is important that lubrication failure and foaming at startup occur. Cause defects. Therefore, the conventional refrigerating machine oil cannot be used as the refrigerating machine oil under these new refrigerant atmospheres.

Also, regarding the lubricity, CFC12 and HC
In FC22, there was an effect that it partially decomposed to generate hydrogen chloride, and this hydrogen chloride reacted with the friction surface to form a chloride film and improve the lubricity. However, since such effects cannot be expected from hydrofluorocarbons containing no chlorine atom, refrigerating machine oil used with hydrofluorocarbons is required to have better lubricity than conventional oils.

Further, the refrigerating machine oil used together with hydrofluorocarbon must have good thermal stability in the presence of hydrofluorocarbon. Further, in addition to this, in compression type refrigerators such as electric refrigerators and room air conditioners, there are organic materials used for motors such as insulating materials and enameled wires, so as a working fluid consisting of hydrofluorocarbon and refrigerator oil, However, it is necessary that these organic materials are not adversely affected and that the electrical insulation is also good.

Hydrofluorocarbons such as 1,1,
As a refrigerating machine oil that can be used together with 1,2-tetrafluoroethane (HFC134a), US Pat.
No. 5,316, JP-A-2-129294, and the like, a polyalkylene glycol-based ether compound synthesized by adding an alkylene oxide to a polyhydric alcohol having a valence of 2 or more and having an uncapped end (abbreviated as PAG-OH) ) Is disclosed. Trimethylolpropane is exemplified as the polyhydric alcohol in the former, and glycerin is exemplified as the latter.

Further, in order to improve various defects such as compatibility of the above compound with HFC and hygroscopicity, a compound (abbreviated as PAG) in which an end of the above compound is capped is disclosed in Japanese Patent Laid-Open No. 3-2980.
-14894, JP 3-205492 A, JP 4-A
20596, JP 4-359996 A, JP 5-98 A
No. 275 is disclosed.

Since PAG-OH and PAG are more polar than naphthenic mineral oil, their compatibility with HFC134a at low temperatures is certainly good. However, US Pat.
As described in 5,316, PAG-OH
On the contrary, PAG and PAG have a problem that two-phase separation occurs when the temperature rises. Also, PAG-OH and PAG have some other problems. One is that it has poor electrical insulation. This is a very big problem and cannot be used in refrigerators for electric refrigerators and refrigerators for air conditioners in which the motor is built in the compressor. Therefore, it is suggested that these compounds are used for car air-conditioning applications without such a worry. Another problem is that it is highly hygroscopic. PAG-OH and PAG
Due to the water content, the thermal stability in the coexistence of HFC134a is deteriorated, and the PET film or the like which is an organic material is hydrolyzed.

Ester compounds and carbonate compounds have been developed in order to improve the problems of the polyether compounds such as the electric insulating property and the hygroscopic property. For example
As a refrigerating machine oil that can be used together with 1,1,1,2-tetrafluoroethane (HFC134a), US Pat.
A mixed oil of a polyether oil and an ester oil is disclosed in Japanese Patent No. 4,851,144 (Japanese Patent Laid-Open No. 2-276894) and Japanese Patent Laid-Open No. 2-158693, and Japanese Patent Laid-Open No. 3-505602 and Japanese Patent Laid-Open No. 3-5602 are disclosed.
-128991 and JP-A-3-128992 disclose ester oils. Further, carbonate oils are disclosed in JP-A-2-132178, JP-A-3-149295, and European Patent No. 421,298.

Ester-based compounds and carbonate-based compounds have excellent compatibility with hydrofluorocarbons, and also have excellent thermal stability in the presence of hydrofluorocarbons. In addition, it has extremely excellent electrical insulation properties and considerably low hygroscopicity as compared with polyether compounds.

However, the conventional working fluid CF
Compared with the C12-mineral oil type, the hydrofluorocarbon-ester oil type and the hydrofluorocarbon-carbonate oil type have higher polarities both for freon and oil, and are likely to contain water. Therefore, there is a problem that the ester oil is hydrolyzed to generate a carboxylic acid, and the generated carboxylic acid corrodes a metal and causes abrasion. In addition, the carbonate oil causes hydrolysis, produces non-condensable carbon dioxide, and causes a problem that the refrigerating capacity is lowered.

Particularly, in the room air conditioner, the refrigerant is exclusively filled in the field, so unlike the case of the refrigerator which is filled in the factory, it is almost impossible to prevent the mixing of water.
Hydrofluorocarbon-ester oil system and hydrofluorocarbon-carbonate oil system are concerned about the reliability when used for room air conditioners.

Further, in WO93 / 24435, a polyvinyl ether compound is obtained by polymerizing a vinyl ether monomer and hydrogenating it, which has good compatibility with hydrofluorocarbons,
It is disclosed that the electric insulation is also good. However, the polyvinyl ether compound is synthesized by a polymerization method, and the product has a molecular weight distribution. Therefore, some high molecular weight substances may cause the clogging of the capillary, and the compatibility with the hydrofluorocarbon may be deteriorated. It is also a cause of deterioration. In addition, it is difficult to say that the post-treatment method is complicated and an unstable vinyl ether-based monomer is used as a raw material, so that the yield is not necessarily high. In particular, those having a low degree of polymerization (polymerization degree of around 6) have a drawback that the yield is low. In addition, vinyl ether-based monomers are expensive due to their difficulty in obtaining raw materials depending on their structures.

As described above, since the polyvinyl ether compound has a molecular weight distribution, its performance may be deteriorated by a high molecular weight compound, and the availability of raw material species is limited. It has the disadvantage of being low and expensive.

As described above, the hydrofluorocarbon-PAG (PAG-OH) oil system developed so far has hygroscopicity and electrical insulation, and the hydrofluorocarbon-ester oil system and the hydrofluorocarbon-carbonate oil system have hydrolysis resistance. In addition, both systems are more likely to contain water than the conventional CFC12-mineral oil system, causing deterioration of thermal stability, deterioration of organic materials, corrosion of metals, wear, etc. As not satisfied.
Further, since the polyvinyl ether compound has a high molecular weight compound in part because it has a molecular weight distribution, it has a drawback that the compatibility is lowered, and there is a drawback that the raw material species are limited and the cost becomes high.

Therefore, in order to solve the above problems, the object of the present invention is to have excellent compatibility and thermal stability, to be free of hydrolyzability, to have an appropriate kinematic viscosity, and to have a low temperature flow. It is to provide a novel polyhydric ether alcohol derivative which has good properties and is particularly excellent in volume resistivity and can be used as a base oil of an inexpensive composition for a working fluid of a refrigerator. Another object of the present invention is to provide a method for industrially advantageously producing such a polyhydric ether alcohol derivative. Another object of the present invention is to provide a composition for a working fluid of a refrigerator, which comprises a refrigerator oil containing such a polyhydric ether alcohol derivative as a base oil and hydrofluorocarbon.

[0017]

[Means for Solving the Problems] Conventionally, as a polyhydric ether alcohol derivative having a hexavalent alcohol such as sorbitol or mannitol as an alcohol residue, for example, hexamethyl ether, hexavinyl ether, hexaoleyl ether, 1,3, 4,5,6-pentamethyl ether (monool), 2,3,4,5,6-pentabenzyl ether (monool), 1,3,5-trimethyl-6-triphenylmethyl ether (diol), 1,2,5,6-tetrakistetradecyl ether (diol), 1,4,5-triethyl ether (triol), 2,3,5-trisdodecyl ether (triol), 1,6-didodecyl ether (tetra All), 2,5-dibenzyl ether (tetraol), 1-t-butyl ether (pentol), 1-
Hexadecyl ether (pentaol) and the like are known.

However, α-branched ether alkyl groups, that is, those having a secondary or tertiary alkyl group as the ether alkyl group, or those having 3 to 17 carbon atoms and having a branched chain on either side, With regard to those having an alkyl group of ether as an alkyl group of ether, derivatives thereof have not been known so far except those which are t-butyl groups.
The present inventors have conducted intensive studies on these novel compounds in order to solve the above problems, and as a result, a polyhydric ether alcohol derivative having a specific structure and containing no alkylene oxide residue in the molecule, We have found that we can achieve the purpose.

On the other hand, as a method for producing this polyhydric ether alcohol derivative, a method is known in which a hexahydric alcohol is reacted with an alkylating agent such as dialkyl sulfate, alkyl tosylate or alkyl halide. However, in these methods, if the alkyl group of the etherifying agent is other than primary, the desired product cannot be obtained in good yield.
In particular, when the degree of etherification is increased, a large amount of by-products such as sulfate and sodium chloride is generated, which causes a problem that it is not preferable in terms of production or economically. Therefore, the present inventors have found that a hexavalent alcohol can be easily produced by reacting it with a carbonyl compound to once induce a cyclic acetal, and then hydrogenating or further alkyl-capping it. The present invention has been completed based on these findings by further research.

That is, the gist of the present invention is (1) the following general formulas (I) to (IV)

[0021]

[Chemical 17]

[0022]

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[0023]

[Chemical 19]

[0024]

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(In the formula, R ₁ is a hydrogen atom or a carbon number of 1 to
21 is a linear or branched alkyl group, and R ₂ is R
_{When 1} is a hydrogen atom, it represents a branched alkyl group having 3 to 17 carbon atoms, and when R ₁ is a linear or branched alkyl group having ₁ to 21 carbon atoms, it is a linear or branched alkyl group having 1 to 21 carbon atoms. Indicates a group. Alternatively, R ₁ and R ₂ together form an alkylene group having 2 to 13 carbon atoms. _{Two to} six pairs of R ₁ and R ₂ may be the same or different. k ₁ is 0
5, p ₁ is 0 to 2, m ₁ is 0 or 1 and k ₁ + (m ₁
+2) A number satisfying p ₁ = 5. k ₂ and n ₂ are 0
4, p ₂ is 0 to 2, m ₂ is 0 or 1 and k ₂ + (m ₂
+2) A number satisfying p ₂ + n ₂ = 4. R ₃ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. In the general formula (I), k ₁ oxymethylene group and p ₁ cyclic acetal (acetal or ketal) unit, in the general formula (II), k ₂ and n ₂ oxymethylene groups and p ₂ Cyclic acetal (acetal or ketal) unit, general formula (II
The arrangement of the oxymethylene group and the cyclic acetal (acetal or ketal) unit in I) may be random or block. (2) a polyhydric ether alcohol derivative represented by any one of (1) to (3), (2) the polyhydric ether alcohol derivative according to (1), wherein the alcohol residue of the polyhydric ether alcohol is derived from sorbitol,
(3) The following formula (V)

[0026]

[Chemical 21]

Hexahydric alcohol represented by the general formula (VI)

[0028]

[Chemical formula 22]

(In the formula, R ₁ represents a hydrogen atom or a carbon number of 1 to
21 represents a straight-chain or branched alkyl group, and R ₂ represents a straight-chain or branched alkyl group having 1 to 21 carbon atoms. ) A carbonyl compound represented by) or its reactive derivative (acetal or ketal) is reacted in the presence of an acid catalyst to produce cyclic acetals (acetal or ketal), which are hydrogenated or further alkyl-capped. General formula (VII)
A method for producing a polyhydric ether alcohol derivative represented by any of (X),

[0030]

[Chemical formula 23]

[0031]

[Chemical formula 24]

[0032]

[Chemical 25]

[0033]

[Chemical formula 26]

(In the formula, R₁Is a hydrogen atom or 1 to 1 carbon atoms
21 represents a straight-chain or branched alkyl group, R₂Is charcoal
A linear or branched alkyl group having a prime number of 1 to 21 is shown.
Or R₁, R₂Together with a carbon number of 2 to 13
Form a alkylene group. 2 to 6 pairs of R₁, R₂Are the same
Can also be different. k₁Is 0 to 5, p₁Is 0 to 2,
m₁Is 0 or 1 and k₁+ (M₁+2) p₁= 5
It is the number to add. k₂, N ₂Is 0-4, p₂Is 0 to 2, m
₂Is 0 or 1 and k₂+ (M₂+2) p₂+ N₂= 4
Is a number that satisfies. R₃Is a hydrogen atom or 1 to 8 carbon atoms
Is a linear or branched alkyl group. General formula (VII)
K at₁Oxymethylene groups and p₁Ring-shaped asse
Tars (acetal or ketal) unit, one
K in general formula (VIII)₂And n₂Oxymethyl
Group and p₂Cyclic acetals (acetal or ke
Tar) unit, oxymethyle in the general formula (IX)
Groups and cyclic acetals (acetals or ketals
The unit arrangement can be random or block
Yes. ) (4) The hexavalent alcohol represented by the formula (V) is
The polyhydric ether alcohol described in (3) above, which is rubitol.
(5) General formulas (VII) to (X)
Where R₁Is a hydrogen atom and R₂Has 1 to 13 carbon atoms
Is a linear or branched alkyl group, R₁Is the carbon number
1 to 13 linear or branched alkyl groups, R₂Charcoal
Before being a linear or branched alkyl group having a prime number of 1 to 13
Induction of polyhydric ether alcohol according to (3) or (4)
Conductor manufacturing method (6) The following general formula (XI)

[0035]

[Chemical 27]

(In the formula, R ^{1 to} R ⁶ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, provided that the total carbon atoms of R ^{1 to} R ⁶ are The number is 8 to 40.) A composition for a refrigerator working fluid, which comprises a refrigerating machine oil containing a polyhydric ether alcohol derivative as a base oil and hydrofluorocarbon,
(7) The composition for a working fluid of a refrigerator according to (6), wherein the compound represented by the general formula (XI) is a hexavalent alcohol residue provided by sorbitol, (8) the general formula (XI) Is a compound of formula (V)

[0037]

[Chemical 28]

A hexahydric alcohol represented by the following general formula (XII)

[0039]

[Chemical 29]

(In the formula, R ⁷ is a hydrogen atom or has 1 to 1 carbon atoms.
13 represents a linear, branched or cyclic alkyl group,
⁸ represents a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms. Alternatively, R ⁷ and R ⁸ together form an alkylene group having 2 to 13 carbon atoms. However, R ⁷ and R ⁸
Is an alkyl group having at least one hydrogen atom on one of the α-position of the R ⁷ and R ^8, the total number of carbon atoms in R ⁷ and R ⁸ is 1-13. ) A carbonyl compound (ketone or aldehyde) or a reactive derivative thereof (ketal or acetal) of at least one type is synthesized into a cyclic ketal or a cyclic acetal by ketalization or acetalization or transketalization or transacetalization, and Is hydrogenated to obtain a polyhydric ether alcohol, which is further alkyl-capped to synthesize the composition for a working fluid for a refrigerator according to (6) or (7), (9) a general formula (XI A) Compound having an epoxy group 0.05 to 2.
At least one selected from the group consisting of 0 part by weight, b) 0.01 to 100 parts by weight of orthoester, c) 0.01 to 100 parts by weight of acetal or ketal, and d) 0.05 to 5 parts by weight of carbodiimide. The composition for a working fluid for a refrigerator according to any one of (6) to (8), further comprising the above, (10) the following general formula (XIII _AA ) or (XIII _BB )

[0041]

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(In the formula, R ^{1 to} R ⁶ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, and R ⁷ is a hydrogen atom or 1 carbon atom. To R 13 are linear, branched or cyclic alkyl groups, and R ⁸ is a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms, or R ⁷ and R ⁸ together are 2 carbon atoms. form an alkylene group having to 13. However, the total number of carbon atoms of R ¹ and R ⁴ to R ⁸ in the general formula R ¹ to R ³ and R ⁶ to R ⁸ in (XIII _AA) or formula, (XIII _BB) Is 8 to 40, and the total carbon number of R ⁷ and R ⁸ is 1
~ 13. It is to be noted that a to e are reference numerals given to represent the arrangement of the structural units, and a to c or d to e may be arranged in any order. ) A composition for refrigerating machine working fluid, comprising a refrigerating machine oil comprising a polyhydric ether alcohol derivative as a base oil and hydrofluorocarbon, (11) a general formula (XIII _AA ) or (XIII _BB ).
The compound for a refrigerator working fluid according to the above (10), wherein the compound represented by the formula (6) has a hexahydric alcohol residue provided by sorbitol, (12) is represented by the general formula (XIII _AA ) or (XIII _BB ). Is a compound of formula (V)

[0043]

[Chemical 31]

Hexahydric alcohol represented by the general formula (XII)

[0045]

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(In the formula, R ⁷ is a hydrogen atom, or 1 to ⁷ carbon atoms.
13 represents a linear, branched or cyclic alkyl group,
⁸ represents a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms. Alternatively, R ⁷ and R ⁸ together form an alkylene group having 2 to 13 carbon atoms. However, R ⁷ and R ⁸
Is an alkyl group having at least one hydrogen atom on one of the α-position of the R ⁷ and R ^8, the total number of carbon atoms in R ⁷ and R ⁸ is 1-13. ) A carbonyl compound (ketone or aldehyde) or a reactive derivative thereof (ketal or acetal) of at least one type is synthesized into a cyclic ketal or a cyclic acetal by ketalization or acetalization or transketalization or transacetalization, and Is hydrogenated to obtain a polyvalent ether ketal alcohol or a polyvalent ether acetal alcohol, which is further alkyl-capped to synthesize (10) or (11) above.
The composition for a working fluid for a refrigerator, and (13) 0.05) a compound having an epoxy group, based on 100 parts by weight of the polyhydric ether alcohol derivative represented by the general formula (XIII _AA ) or (XIII _BB ). To 2.0 parts by weight, b) 0.01 to 100 parts by weight of orthoester, c) 0.01 to 100 parts by weight of acetal or ketal, and d) 0.05 to 5 parts by weight of carbodiimide. The above (10) to which at least one kind is further blended
(12) The composition for a working fluid of a refrigerator according to any one of the above.

The present invention will be described in detail below. For convenience, the novel polyhydric ether alcohol derivative of the present invention, a novel method for producing a polyhydric ether alcohol derivative, and a refrigerating machine working fluid composition containing a polyhydric ether alcohol derivative as a base oil and a hydrofluorocarbon, I will explain separately. In addition, the definition of the substituents in the general formulas in the present specification means those defined in each formula. For example, the definition of R ₂ is different in the general formulas (I) to (IV) and the general formulas (VI) to (X), but they are interpreted according to the respective definitions. In general formula _{(XI), (XIII AA)} , in such (XIII _BB) by the different display and R _2, such as R ² Formula (I) ~ (IV) or general formula (VI) -(X) and the like are clearly defined.

Novel polyhydric ether alcohol of the present invention
Derivative The novel polyhydric ether alcohol derivative of the present invention is a compound represented by any of the general formulas (I) to (IV).

In the general formulas (I) to (IV), R ₁ is a hydrogen atom or a linear or branched alkyl group having 1 to 21 carbon atoms. Specific examples of the linear or branched alkyl group having 1 to 21 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. , Nonyl group, undecyl group, tridecyl group, pentadecyl group, heptadecyl group, nonadecyl group, heneicosyl group and the like. As the branched alkyl group, in addition to the specific examples of the branched alkyl group having 3 to 17 carbon atoms described later, 1
-Methyloctadecyl group, 1-decylundecyl group, 2
-Methyl eicosyl group and the like can be mentioned.

In the general formulas (I) to (IV), when R ₁ is a hydrogen atom, R ₂ is a branched alkyl group having 3 to 17 carbon atoms, preferably a branched alkyl group having 3 to 12 carbon atoms. . Specific examples of the branched alkyl group having 3 to 17 carbon atoms represented by R ₂ include the following. Examples of the α-methyl branched alkyl group include an isopropyl group and 1-
Methylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1-methylhexyl group, 1-methylheptyl group, 1-methyloctyl group, 1-methylnonyl group, 1-
Examples thereof include a methyldecyl group, a 1-methylundecyl group and a 1-methylhexadecyl group.

In addition, the α-branched alkyl group is 1
-Ethylpropyl group, 1-ethylbutyl group, 1-ethylpentyl group, 1-propylbutyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-butylpentyl group ,
1-pentylhexyl group, 1-hexylheptyl group, 1
Examples include -octylnonyl group and 1-hexylundecyl group. Further, as the cyclic alkyl group at the α-position,
Cyclopentyl group, cyclohexyl group, 3- (2 ', 2', 5 '
Examples include -trimethylcyclohexyl) propyl group and 1-cyclohexylmethyl group.

Examples of α-multibranched alkyl groups having α-branch and one or more branches other than α-branch include 1,2-dimethylpropyl group, 1,2-dimethylbutyl group, 1 , 3-Dimethylbutyl group, 1-ethyl-2-methylpropyl group, diisopropylmethyl group, 1,4-dimethylpentyl group, 1-isopropylbutyl group, 1,3,3-trimethylbutyl group, 1,5-dimethyl Hexyl group, 1-ethyl-2-methylpentyl group, 1-butyl-2-methylpropyl group, 1-ethyl-3-methylpentyl group, diisobutylmethyl group, 1,5,9-trimethyldecyl group and the like. .

Examples of the β-branched alkyl group include 2-methylpropyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylbutyl group, 2-methylhexyl group, 2
-Ethylpentyl group, 2-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group and the like can be mentioned.

[Beta] -branched and [alpha] -branched, and [beta] -multi-branched alkyl groups having one or more branches other than [beta] -branch include 2,3-dimethylbutyl group and 2,4,4 Examples include -trimethylpentyl group and 2-isopropyl-5-methylhexyl group.

Examples of other branched alkyl groups having one or more branches other than α-branch and β-branch include 3-methylbutyl group, 3-methylpentyl group and 4-
Methylpentyl group, 3,3-dimethylbutyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 3,5,5-trimethylhexyl group, isodecyl group, 3,7-dimethyloctyl group , An isoheptadecyl group and the like.

No hydrogen atom is present in the β-position, and the β-position is 3
Examples of the alkyl group having a primary carbon include a 2,2-dimethylpropyl group, a 2,2-dimethylbutyl group, a 1,2,2-trimethylpropyl group, a 1-ethyl-2,2-dimethylpropyl group, 2,2-dimethylpentyl group, 2,3-dimethyl-
2-isopropyl butyl group etc. are mentioned.

In the general formulas (I) to (IV), when R ₁ is a linear or branched alkyl group having 1 to 21 carbon atoms, R ₂ is a linear or branched alkyl group having 1 to 21 carbon atoms. Becomes Preferably, R ₁ is a linear or branched alkyl group having 1 to 12 carbon atoms, and in that case,
R ₂ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. 1 to 21 carbon atoms represented by R ₂
Specific examples of the linear or branched alkyl group include those mentioned above as specific examples of R ₁ .

Alternatively, R ₁ and R ₂ together form an alkylene group having 2 to 13 carbon atoms. Specifically, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,3-dimethylpentamethylene group, 1,5-dimethylpentamethylene group, 2,2,4-trimethylpentamethylene group, 1-tert-butylpentamethylene group, 3-tert-butyl Examples include a pentamethylene group, a 1-isopropyl-3-methylpentamethylene group, a nonamethylene group and the like. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms represented by R ₃ include a methyl group, an ethyl group,
Propyl group, butyl group, isobutyl group, hexyl group, 2
Examples thereof include an ethylhexyl group, and a methyl group and an ethyl group are preferable.

As the polyhydric ether alcohol derivative represented by the above general formulas (I) to (IV), it is preferable that the alcohol residue of the polyhydric ether alcohol is derived from sorbitol. Next, general formula (I)-
Specific examples (compound name and structural formula) of the polyhydric ether alcohol derivative represented by (IV) are illustrated, but the invention is not limited thereto.

[0060]

[Chemical 33]

[0061]

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[0062]

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Novel polyhydric ether alcohol derivative
Production Method Next, the production method of the polyhydric ether alcohol derivative of the present invention will be described in detail. The production method of the present invention comprises reacting a hexavalent alcohol represented by the formula (V) with a carbonyl compound represented by the general formula (VI) (ketone or aldehyde) or a reactive derivative thereof (ketal or acetal) in the presence of an acid catalyst. This is characterized by producing cyclic acetals (acetal or ketal) by hydrogenating or further alkyl-capping them. As a result, polyhydric ether alcohol derivatives represented by the general formulas (VII) to (X) are produced. The reaction formula of the reaction is as follows.

[0064]

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In these formulas, R ₁ is a hydrogen atom or a linear or branched alkyl group having 1 to 21 carbon atoms, and when R ₁ is a hydrogen atom, R ₂ is 1 to 1 carbon atoms.
It is a linear or branched alkyl group having 21 carbon atoms, preferably a linear or branched alkyl group having 1 to 17 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 13 carbon atoms. R ₁ has 1 to ₁ carbon atoms
When it is a straight chain or branched alkyl group of 21, R ₂
Is a linear or branched alkyl group having 1 to 21 carbon atoms. Preferably, R ₁ is a linear or branched alkyl group having 1 to 13 carbon atoms, and R ₂ is a linear or branched alkyl group having 1 to 13 carbon atoms.

Examples of the linear or branched alkyl group having 1 to 8 carbon atoms represented by R ₃ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, hexyl group, 2-ethylhexyl group and the like. However, a methyl group and an ethyl group are preferable. R ₄ represents a linear or branched alkyl group having 1 to 6 carbon atoms. Y represents the residue of the alkylating agent.

That is, a hexavalent alcohol such as sorbitol or mannitol represented by the formula (V) and a carbonyl compound such as a ketone or an aldehyde represented by the general formula (VI), or a general formula (2-VI ') Cyclic acetals such as general formula (2-XIV) are produced by subjecting the reactive derivative represented by dehydration reaction or dealcoholization reaction using an acid catalyst, and hydrogenated to give the general formula (2 −X
V _A), to obtain a polyhydric ether alcohols or polyhydric ether acetal (or ketal) alcohols represented by such (2-XV _B). Alternatively, further capping with an alkyl gives a capped ether represented by the general formula (2-XVI _A ), (2-XVI _B ), or the like.

Raw material compounds used in the above reaction will be described below. Hexahydric alcohol Examples of the hexahydric alcohol used in the method of the present invention include those represented by the above formula (V), and specifically, sorbitol, mannitol, galactitol, which is hexitol obtained by reduction of hexose, Edith,
Examples thereof include taritol and allitol. Among these, sorbitol is the most preferable in terms of availability and price.

Carbonyl Compounds Carbonyl compounds represented by the general formula (VI) used in the method of the present invention include ketones and aldehydes. Among them, ketones are high-temperature decarboxylation dimerization reaction of fatty acids and catalytic oxidation of olefins. It is easily obtained by a reaction (Wacker method), oxidation of secondary alcohol, dehydrogenation, oxidation of cycloalkane, or the like. In the case of the Wacker method, the obtained ketone has a distribution, but can be separated and purified into a single product by precision distillation. Specific examples of the ketone are as follows, but are not necessarily limited to these.

As the methyl alkyl ketone, for example, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone, methyl nonyl ketone, methyl undecyl ketone, methyl heptadecyl ketone. Etc.

Examples of the dialkyl ketone include diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, dipropyl ketone, ethyl pentyl ketone, ethylhexyl ketone, dibutyl ketone, dipentyl ketone, dihexyl ketone, diundecyl ketone, diheptadecyl ketone and the like. .

As the multi-branched ketone, methyl isopropyl ketone, methyl-sec-butyl ketone, methyl isobutyl ketone, ethyl isopropyl ketone, methyl-te.
rt-butyl ketone, diisopropyl ketone, methyl isoamyl ketone, isopropyl propyl ketone, methyl neopentyl ketone, ethyl-tert-butyl ketone, 6-methyl-2-heptanone, 4-methyl-3-heptanone, 2-methyl-3-heptanone, 5-methyl-
3-heptanone, diisobutyl ketone, 6,10-dimethyl-2-undecanone and the like can be mentioned.

As cyclic ketones, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone,
2-methylcyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, 2,4-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3 , 5-Trimethylcyclohexanone, 2-tert-butylcyclohexanone, 4-
Examples thereof include tert-butylcyclohexanone, 2-isopropyl-4-methylcyclohexanone and cyclodecanone.

Examples of cyclic alkyl ketones include methylcyclohexyl ketone and 5- (2 ', 2', 5'-trimethylcyclohexyl) -2-pentanone.

The aldehyde used can be easily obtained by, for example, dehydrogenation reaction of fatty alcohol, hydroformylation reaction of olefin (oxo method), Rosemund reduction of fatty acid chloride, direct hydrogenation from fatty acid, and the like. In the case of the oxo method, a linear product and a branched product are produced, but they can be separated and purified into a single product by precision distillation. Specific examples of the alkyl aldehyde are as follows, but the alkyl aldehyde is not necessarily limited to these.

For example, as a linear alkyl aldehyde,
Examples thereof include acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptanal, octanal, decylaldehyde, dodecanal, tetradecanal, octadecanal and beheninaldehyde.

As α-branched alkyl aldehyde, isobutyraldehyde, 2-methylbutyraldehyde, 2-butyraldehyde
Examples include methylpentanal, 2-ethylbutanal, 2-methylhexanal, 2-ethylpentanal, 2-methylheptanal, 2-ethylhexanal and 2-propylpentanal. Examples of α-multi-branched alkyl groups in which α-branch has one or more branches other than α-branch are 2,3-dimethylbutanal, 2,4,4
-Trimethylpentanal, 2-isopropyl-5-methylhexanal and the like can be mentioned.

Other branched alkyl aldehydes having one or more branches other than α-branch include isovaleraldehyde, 3-methylpentanal, 4-methylpentanal and 3,3-dimethylbutanal. , 3-methylhexanal, 4-methylhexanal, 5-methylhexanal, 3,5,5-trimethylhexanal, isodecyl aldehyde, 3,7-dimethyloctanal, isooctadecanal and the like.

Examples of the cyclic alkyl aldehyde include cyclopentyl acetaldehyde and cyclohexyl acetaldehyde.

Reactive derivative of carbonyl compound As the reactive derivative of the carbonyl compound used in the present invention, the above-mentioned ketone, aldehyde and carbon number 1 to
Examples thereof include ketals and acetals represented by the general formula (2-VI ′), which are easily synthesized from the lower alcohol of 6 by an acid catalyst. Specific examples of the lower alcohol having 1 to 6 carbon atoms which gives the R ₄ residue include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, amyl alcohol, isoamyl alcohol, neopentyl. Alcohol, 1-methylbutanol, 1,1-dimethylpropanol, 1-ethylpropanol, hexanol, isohexanol, 2-ethylbutanol, 1
-Methylamyl alcohol, 1,3-dimethylbutanol, 1-ethylbutanol and the like can be mentioned.

Ketalization reaction In the present invention, the reaction between the hexavalent alcohol represented by the formula (V) and the ketone is a ketalization reaction, and the molar ratio of the ketone to the hexavalent alcohol represented by the formula (V) is from 1 to 1. 1
5, preferably 1.5 to 7.5. This reaction uses paratoluene sulfonic acid, methane sulfonic acid as a catalyst,
An acid catalyst such as sulfuric acid is used in an amount of 0.05 to 10 mol%, preferably 0.1 to 7 based on the hexavalent alcohol represented by the formula (V).
Mol%, more preferably 0.5 to 5 mol%.

This reaction is solvent-free or xylene, toluene, benzene, octane, isooctane, heptane,
40 to 160 depending on the boiling point of the ketone used in an inert solvent such as hexane, cyclohexane, pentane, ligroin, petroleum ether or a mixed solvent thereof.
It is preferable to carry out at a temperature of 60 ° C., preferably 60 to 100 ° C., while removing water produced. In some cases, it is also effective to carry out the reaction under reduced pressure. This is because when the temperature is within these ranges, the reaction proceeds favorably and the coloring due to side reaction tends to be small. Further, under a nitrogen flow condition, either a nitrogen atmosphere or a dry air atmosphere may be used. The reaction time may vary depending on various conditions, but is usually preferably 5 to 200 hours. The obtained cyclic ketal (2-XIV) and the like can be purified by operations such as adsorption treatment, crystallization and distillation after being subjected to pretreatment such as filtration and washing after being neutralized.

Acetalization Reaction The reaction between the hexavalent alcohol represented by the formula (V) and the aldehyde is an acetalization reaction, and the molar ratio of the aldehyde to the hexavalent alcohol represented by the formula (V) is 1 to 6.
It is preferably 1.5 to 3.8. In this reaction, an acid catalyst such as paratoluenesulfonic acid, methanesulfonic acid, or sulfuric acid is used as a catalyst in an amount of 0.01 to 5 mol%, preferably 0.05 to 3 mol% based on the hexavalent alcohol represented by the formula (V). , And more preferably 0.1 to 2 mol%.

This reaction is solvent-free or xylene, toluene, benzene, octane, isooctane, heptane,
It depends on the boiling point of the aldehyde used in an inert solvent such as hexane, cyclohexane, pentane, butane, ligroin, petroleum ether or a mixed solvent thereof, depending on the boiling point of the aldehyde used.
It is preferable to carry out while removing the water produced at a temperature of 0 to 130 ° C, preferably 40 to 100 ° C. In some cases, it is also effective to carry out the reaction under reduced pressure. This is because when the temperature is within these ranges, the reaction proceeds favorably and the coloring due to side reaction tends to be small. In addition, the nitrogen flow condition may be either a nitrogen atmosphere or a dry air atmosphere. The reaction time may vary depending on various conditions, but is usually preferably 1 to 30 hours. The obtained cyclic acetal (2-XIV) and the like can be purified by operations such as adsorption treatment, crystallization and distillation after being subjected to pretreatment such as filtration and washing after being neutralized.

Transketalization reaction Further , the reaction between the hexavalent alcohol represented by the formula (V) and the ketal (2-VI ') which is a reactive derivative of the ketone is a transketalization reaction, and is represented by the formula (V) The molar ratio of the ketal (2-VI ') to the hexahydric alcohol represented by is 1
-15, preferably 1.5-7.5. In this reaction, an acid catalyst such as p-toluenesulfonic acid, methanesulfonic acid or sulfuric acid is used as a catalyst in an amount of 0.05 to 10 mol%, preferably 0.1 to 10 mol% with respect to the hexavalent alcohol represented by the formula (V).
.About.7 mol%, more preferably 0.5 to 5 mol%.

This reaction is solvent-free or xylene, toluene, benzene, octane, isooctane, heptane,
In an inert solvent such as hexane, cyclohexane, pentane, ligroin or petroleum ether, or in a mixed solvent thereof, depending on the boiling points of the ketal (2-VI ') used and the lower alcohol produced, 40 to 160 ° C, preferably Is preferably carried out while removing the lower alcohol produced at a temperature of 60 to 130 ° C. In some cases, it is also effective to carry out the reaction under reduced pressure. This is because when the temperature is within these ranges, the reaction proceeds favorably and the coloring due to side reaction tends to be small. Further, under a nitrogen flow condition, either a nitrogen atmosphere or a dry air atmosphere may be used. The reaction time may vary depending on various conditions, but is usually preferably 5 to 200 hours. The obtained cyclic ketal (2-XIV) and the like can be purified by operations such as adsorption treatment, crystallization and distillation after being subjected to pretreatment such as filtration and washing after being neutralized.

[0087] Acetal is a reactive derivative of the hexahydric alcohol and an aldehyde of formula (V) in transfected acetalization present invention (2-VI ')
Is a transacetalization reaction, and the molar ratio of the acetal (2-VI ') to the hexahydric alcohol represented by the formula (V) is 1.5 to 6, preferably 2.7.
Is about 3.8. In this reaction, an acid catalyst such as paratoluenesulfonic acid, methanesulfonic acid, or sulfuric acid is used as a catalyst in an amount of 0.01 to 5 with respect to the hexavalent alcohol represented by the formula (V).
Mol%, preferably 0.05 to 3 mol%, more preferably 0.1 to 2 mol%.

This reaction is solvent-free or xylene, toluene, benzene, octane, isooctane, heptane,
In an inert solvent such as hexane, cyclohexane, pentane, butane, ligroin, petroleum ether, or a mixed solvent thereof, depending on the boiling point of the acetal (2-VI ') used and the lower alcohol produced, it is 20 to 150.
It is preferable that the reaction is carried out while removing the lower alcohol produced at a temperature of 40 ° C, preferably 40 to 130 ° C. In some cases, it is also effective to carry out the reaction under reduced pressure. This is because when the temperature is within these ranges, the reaction proceeds favorably and the coloring due to side reaction tends to be small. Further, under a nitrogen flow condition, either a nitrogen atmosphere or a dry air atmosphere may be used. The reaction time may vary depending on various conditions, but is usually preferably 1 to 30 hours. The obtained cyclic acetal (2
-XIV) and the like can be purified by operations such as adsorption treatment, crystallization and distillation after neutralization, pretreatment such as filtration and washing.

Hydrogenation reaction The hydrogenation reaction of the cyclic ketal or cyclic acetal represented by the general formula (2-XIV) is carried out by converting an ordinary hydrogenolysis catalyst such as palladium, rhodium, ruthenium or platinum into a cyclic acetal or cyclic ketal. On the other hand, 5 to 50
00ppm added, hydrogen pressure normal pressure ~ 250kg / c
m ² and the temperature may be 50 to 250 ° C., and the reaction may be performed for 1 to 30 hours. As the above-mentioned hydrocracking catalyst, one obtained by supporting 0.1 to 20% of these on carbon, alumina, silica, diatomaceous earth, titanium oxide or the like may be used. As the hydrogenolysis catalyst, palladium is particularly preferable, and the one having a pH of 5-8 is particularly preferable. In addition, it is preferable that water is removed in advance. This reaction may be carried out without a solvent or using an inert solvent such as decane, octane, isooctane, heptane, hexane and cyclohexane. Further, a hexahydric alcohol represented by the formula (V), an aldehyde or a ketone, which is a raw material of the cyclic acetal or the cyclic ketal, may be added. Further, a small amount of an acidic substance such as phosphoric acid may be added. The reaction may be a closed system or a hydrogen flow system.

In this reaction, the carbon bond between the acetal or ketal carbon and the oxygen bond is reductively cleaved to produce an ether and an alcohol, and an acetal or ketal exchange reaction occurs between the molecules. Therefore, even if the starting material is triacetal or triketal, it is usually 1
It is possible to obtain mixtures of alkyl ethers with a substitution number of ˜5. Of the alkyl ethers having the same number of substitutions, the main component is usually one in which the 1- and / or 6-position hydroxyl groups are etherified. Further, if the reaction is stopped halfway, an ether alcohol containing an acetal ring or a ketal ring can be obtained. In order to obtain those with a low degree of substitution with alkyl or alkylidene, it is advisable to hydrogenate an acetal or ketal obtained by reacting an aldehyde or a ketone or a reactive derivative thereof with a hexahydric alcohol in a ratio smaller than the equivalent amount. 6 for triacetal and triketal
A low degree of substitution can also be obtained by adding a hydric alcohol and hydrogenating.

In order to obtain an ether alcohol having a low degree of alkyl substitution, which does not contain an acetal ring or a ketal ring, the hydrogenation reaction is stopped midway and paratoluenesulfonic acid,
It may be hydrolyzed in an aqueous solution of methanol or an aqueous solution of ethanol using sulfuric acid, hydrochloric acid or the like as a catalyst. On the other hand, in order to obtain a large number of alkyl groups having a high degree of substitution, acetal or ketal may be added and hydrogenated.

The thus obtained mixture of polyhydric ether alcohols (2-XV _A ), etc. having different alkyl substitution degrees, or the mixture of polyhydric ether acetal alcohols or polyhydric ether ketal alcohols (2-XV _B ), etc. This may be used as it is for the next alkyl cap reaction, or if desired, the desired alcohol may be isolated and used for the next reaction. To isolate the desired alcohol from the reaction mixture, the catalyst is removed by filtration, and then the solvent can be distilled off, washed, recrystallized, distilled, chromatographed or the like by a conventional method alone or in combination. .

Alkyl capping reaction The polyhydric ether alcohol (2-
XV _A ) and polyhydric ether ketal alcohol or polyhydric ether acetal alcohol (2-XV _B ), etc., to the hydroxyl group moiety, sodium, NaH, NaOCH ₃ , N
A base such as aOH or KOH is made to act to form the alcoholate, followed by alkyl halide or dialkyl sulfate,
By carrying out ether capping (alkyl capping) with an alkylating agent such as alkyl tosylate, ether compounds represented by the general formulas (2-XVI _A ) and (2-XVI _B ) can be obtained.

Examples of the alkyl halide used here include the following halogenated lower alkyls. For example, as straight-chain alkyl chloride, methyl chloride, ethyl chloride,
Examples thereof include propyl chloride, butyl chloride, amyl chloride, hexyl chloride, octyl chloride and the like. Isopropyl chloride, isobutyl chloride, sec-chloride as branched alkyl chloride
Butyl, isoamyl chloride, neopentyl chloride, 1-chloride
Methylbutyl, 1-ethylpropyl chloride, isohexyl chloride, 2-ethylbutyl chloride, 1-methylamyl chloride,
1-ethylbutyl chloride, 2-ethylhexyl chloride and the like can be mentioned. Examples of linear alkyl bromide include methyl bromide, ethyl bromide, propyl bromide, butyl bromide, amyl bromide, hexyl bromide and the like. Isopropyl bromide, isobutyl bromide, sec-butyl bromide, isoamyl bromide, branched alkyl bromide, neopentyl bromide, 1-methylbutyl bromide, 1-ethylpropyl bromide, isohexyl bromide, 2-ethylbutyl bromide, 1-methylamyl bromide, 1-ethylbutyl bromide, 2-ethylhexyl bromide and the like can be mentioned.
Examples of the linear alkyl iodide include methyl iodide, ethyl iodide, propyl iodide, butyl iodide, amyl iodide and hexyl iodide. As branched alkyl iodide, isopropyl iodide, isobutyl iodide, sec-butyl iodide, isoamyl iodide, neopentyl iodide, 1-methylbutyl iodide, 1-ethylpropyl iodide, isohexyl iodide, 2-ethylbutyl iodide, Examples thereof include 1-methylamyl iodide, 1,3-dimethylbutyl iodide, 1-ethylbutyl iodide and the like. These alkyl halides are preferably primary alkyl from the viewpoint of reactivity. Further, in order to prevent chlorine, bromine and iodine from remaining, those having a boiling point of 50 ° C. or less are preferable.

Examples of dialkyl sulfate include the following di-lower alkyl sulfate. Examples of the di-linear alkyl sulfate include dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, diamyl sulfate, dihexyl sulfate and the like. Diisopropyl sulfate, diisobutyl sulfate, disec-butyl sulfate, diisoamyl sulfate, dineopentyl sulfate, di (1-methylbutyl) sulfate, di (1-ethylpropyl) sulfate, diisohexyl sulfate, di (2-ethylbutyl) sulfate as di-branched alkyl sulfate. , Di (1-methylamyl) sulfate, di (1-ethylbutyl) sulfate, and the like. These dialkyl sulfates are preferably primary alkyl groups from the viewpoint of reactivity.

Examples of the alkyl tosylates include the following lower alkyl tosylates. Examples of the straight-chain alkyl tosylate include methyl tosylate, ethyl tosylate, propyl tosylate, butyl tosylate, amyltosylate, and hexyltosylate. Isopropyl tosylate as a branched alkyl tosylate,
Isobutyl tosylate, sec-butyl tosylate, isoamyl tosylate, neopentyl silate, 1-methylbutyl tosylate, 1-ethylpropyl tosylate, isohexyltosylate, 2-ethylbutyl tosylate, 1-methylamyltosylate Rate, 1,3-dimethyl tosylate, 1-ethylbutyl tosylate and the like. These alkyl tosylates are preferably primary alkyls from the viewpoint of reactivity.

On the other hand, polyhydric ether alcohol (2-XV _A ).
Etc., and the ratio (molar ratio) of the base per 1 hydroxyl group such as polyhydric ether ketal alcohol or polyhydric ether acetal alcohol (2-XV _B ) is 1.0 to 3.0, preferably 1.0 to 1. 5, and the ratio (molar ratio) of the alkylating agent is 1.0 to 3.0, preferably 1.0 to 1.5. First, the alcoholation reaction is xylene, toluene,
In an inert solvent such as benzene, octane, isooctane, heptane, hexane, cyclohexane, pentane, ligroin, petroleum ether, dimethyl sulfoxide, 1,2-dimethoxyethane or a mixed solvent thereof,
Room temperature to 110 ° C, depending on the boiling point and stability of the solvent used
It is carried out at a temperature of room temperature to 130 ° C. while gradually dropping the alkylating agent, depending on the reactivity of the alkylating agent. The alcoholation reaction is preferably 0.5 to 2 hours, and the O-alkylation reaction is preferably 0.5 to 6 hours within a controllable range depending on the degree of heat generation. After the reaction,
After the unreacted alcoholate and the alkylating agent are decomposed with an aqueous alkali solution such as sodium hydroxide, the obtained ether compounds represented by the general formulas (2-XVI _A ) and (2-XVI _B ) are extracted, filtered, After performing a pretreatment such as washing, the product can be purified by operations such as adsorption treatment, steaming, dehydration and distillation.

A polyhydric ether alcohol derivative and a base oil
Refrigerating machine oil and cold containing hydrofluorocarbon
Composition for Refrigerator Working Fluid The composition for a refrigerator working fluid of the present invention is characterized by using the polyhydric ether alcohol derivative represented by the general formula (XI) as a base oil of a refrigerating machine oil.

In the general formula (XI), R ^{1 to} R ⁶ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms. However, R ¹
The total carbon number of R ⁶ to R ⁶ is 8 to 40.

In general, the compatibility with hydrofluorocarbons is better as the polarity of the compound is higher, and the electrical insulation is better as the polarity of the compound is lower. The balance of is important. Therefore, considering the viscosity, 3
In the case of an alkyl ether using an alcohol residue having a low valence such as a valence of 4 or a valence of 4, it is necessary to use an ether of an alkyl group having a large number of carbons in order to obtain a predetermined viscosity, and therefore the polarity becomes low, Compatibility with hydrofluorocarbon becomes poor. On the contrary, when an alcohol residue having a high valency such as a valency of 12 or 13 is used, it is necessary to use an ether of an alkyl group having a small number of carbon atoms in order to obtain a predetermined viscosity, so that the polarity becomes high, The electrical insulation is poor. Therefore, a hexavalent alcohol residue is particularly preferable for improving the above balance.

In the compound represented by the general formula (XI),
6 to give a hexavalent alcohol residue excluding R ¹ O to R ⁶ O
Examples of the polyhydric alcohol include those specifically exemplified as the raw material compounds in the above-mentioned “New method for producing polyhydric ether alcohol derivative”. Among these, sorbitol is the most preferable in terms of availability and price.

In the general formula (XI), examples of the alkyl group represented by R ^{1 to} R ⁶ which may be linear, branched or cyclic and have 1 to 14 carbon atoms include the following.

That is, as the straight-chain or branched alkyl group, the number of carbon atoms shown as R _{1 in} the above-mentioned “Novel polyhydric ether alcohol derivative of the present invention” is 1
Specific examples of the straight-chain or branched alkyl group having from 21 to 21 include those having 1 to 14 carbon atoms, as well as having no hydrogen atom at the α-position and having a tertiary carbon at the α-position. As the alkyl group, 1,1-dimethylethyl group, 1-methylcyclopropyl group, 1,1-dimethylpropyl group, 1-methylcyclobutyl group, 1,1-dimethylbutyl group, 1,1,2-trimethylpropyl group Group, 1-methylcyclopentyl group, 1,
Examples thereof include a 1-dimethylpentyl group, a 1-methyl-1-ethylbutyl group, a 1,1-diethylpropyl group, and a 1,1-diethylbutyl group.

As the cyclic alkyl group, a cycloalkyl group at the α-position is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 2-methylcyclopentyl group or a 3-methylcyclopentyl group. , 2-methylcyclohexyl group, 3
-Methylcyclohexyl group, 4-methylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2-tert-butylcyclohexyl group, 4-tert-butyl Cyclohexyl group, 2-isopropyl-4-methylcyclohexyl group, cyclodecyl group and the like can be mentioned.

Examples of the cyclic alkyl group having one or more carbon atoms include cyclopentylmethyl group, cyclohexylmethyl group, 1-methyl-4- (2'2'5'-trimethylcyclohexyl) butyl group, 1-cyclohexylethyl group and the like. Is mentioned.

Hydrogen atoms do not exist at both α-position and β-position,
Examples of the alkyl group having a tertiary carbon at both the α-position and the β-position are 1,1,2,2-tetramethylpropyl group, 1,1,2,2-tetramethylbutyl group, 1, 1,
2,2-tetramethylhexyl group and the like can be mentioned.

In order to satisfy the compatibility with hydrofluorocarbon and the electric insulation, the ratio (C / O) of the total number of carbon atoms and the total number of oxygen atoms in one molecule is in the range of 2.5 to 7.5. Preferably, and more preferably 3.0 to 7.
The range is 0, and particularly preferably the range is 4.0 to 6.0.

Therefore, the total number of carbon atoms in the alkyl group is usually 8 to 40, preferably 9 to 39, more preferably 12 to 36, and particularly preferably 18 to 30. If the total number of carbon atoms is less than 8, the electrical insulation is poor, and if the total number of carbons exceeds 40, the compatibility with hydrofluorocarbon is poor.

From the viewpoint of compatibility with hydrofluorocarbons, the structure of the alkyl group is preferably a branched or cyclic structure rather than a linear structure, and more preferably a branched structure rather than a cyclic structure. Further, an alkenyl group or an alkynyl group having an unsaturated bond is not preferable because it has poor thermal stability.

Specific examples (compound name and structural formula) of the polyhydric ether alcohol derivative represented by the general formula (XI) are shown below, but the polyhydric ether alcohol derivative is not necessarily limited to these, and the general formula The compounds represented by (XIII _AA ) or (XIII _BB ) are also included.

1) 2,3,4,5-tetra-O-methyl-1,6
-Di-O- (3,5,5-trimethylhexyl) sorbitol

[0112]

Embedded image

2) 2,4,5-Tri-O-methyl-1,3,6-
Tri-O- (3,5,5-trimethylhexyl) sorbitol

[0114]

[Chemical 38]

3) 1,6-di-O- (3,5,5-trimethylhexyl) -di-O-methyl-di-O- (3,5,5-trimethylhexyl) sorbitol

[0116]

[Chemical Formula 39]

4) 2,3,4,5,6-penta-O-methyl-1
-O- (3,5,5-trimethylhexyl) sorbitol

[0118]

[Chemical 40]

5) 2,3,4,5-tetra-O-methyl-1,6
-Di-O- (1,3-dimethylbutyl) sorbitol

[0120]

Embedded image

6) 2,4,5-Tri-O-methyl-1,3,6-
Tri-O- (1,3-dimethylbutyl) sorbitol

[0122]

Embedded image

7) 1,6-di-O- (1,3-dimethylbutyl) -di-O-methyl-O- (1,3-dimethylbutylidene) sorbitol

[0124]

[Chemical 43]

8) 1,6-di-O- (1,3-dimethylbutyl) -O-methyl-O- (1,3-dimethylbutyl) -O-
(1,3-dimethylbutylidene) sorbitol

[0126]

[Chemical 44]

9) 2,3,4,5-Tetra-O-methyl-1,6
-Di-O- (1-methylpropyl) sorbitol

[0128]

Embedded image

10) 2,4,5-Tri-O-methyl-1,3,6
-Tri-O- (1-methylpropyl) sorbitol

[0130]

Embedded image

11) 1,6-di-O- (1-methylpropyl) -di-O-methyl-O- (1-methylpropylidene) sorbitol

[0132]

[Chemical 47]

12) 1,6-di-O- (1-methylpropyl) -di-O-methyl-di-O- (1-methylpropyl) sorbitol

[0134]

Embedded image

13) 1,6-di-O- (1-methylpropyl) -di-O-ethyl-di-O- (1-methylpropyl) sorbitol

[0136]

[Chemical 49]

14) 2,4,5-Tri-O-ethyl-1,3,6
-Tri-O- (1,3-dimethylbutyl) sorbitol

[0138]

Embedded image

15) 2,3,4,5-tetra-O-methyl-1,
6-di-O- (cyclohexyl) sorbitol

[0140]

[Chemical 51]

16) 2,4,5-Tri-O-methyl-1,3,6
-Tri-O- (cyclohexyl) sorbitol

[0142]

Embedded image

17) 1,6-di-O- (cyclohexyl)
-Di-O-methyl-di-O- (cyclohexyl) sorbitol

[0144]

Embedded image

18) 2,3,4,5-Tetra-O-isopropyl-1,6-di-O- (cyclohexyl) sorbitol

[0146]

[Chemical 54]

19) O- (3,5,5-trimethylhexyl)
-Di-O- (1,3-dimethylbutyl) -tri-O- (ethyl) sorbitol

[0148]

[Chemical 55]

20) O- (3,5,5-trimethylhexyl)
-Di-O- (2-methylpropyl) -tri-O- (butyl) sorbitol

[0150]

[Chemical 56]

21) Di-O- (2-ethylhexyl)-
O- (1-methylpropyl) -tri-O- (methyl) sorbitol

[0152]

[Chemical 57]

22) Di-O- (1-isopropyl-2-
Methylpropyl) -O- (1-methylpropyl) -tri-O- (ethyl) sorbitol

[0154]

Embedded image

23) Tri-O- (1,3-dimethylbutyl)
-O- (cyclohexyl) -di-O- (methyl) sorbitol

[0156]

Embedded image

24) Di-O- (1,3-dimethylbutyl)-
Di-O- (1-methylpropyl) di-O- (2-methylpropyl)

[0158]

Embedded image

25) 2,4,5-Tri-O-ethyl-1,3,6
-Tri-O- (1-methylpropyl) sorbitol

[0160]

[Chemical formula 61]

26) 2,3,4,5,6-penta-O-methyl-
1-O- (1,3-dimethylbutyl) sorbitol

[0162]

Embedded image

27) 1,6-di-O- (1,3-dimethylbutyl) -di-O-methyl-di-O- (1,3-dimethylbutyl) sorbitol

[0164]

[Chemical formula 63]

The polyhydric ether alcohol derivative represented by the general formula (XI) as described above can be produced by various methods. For example, it can be produced by reacting an alcoholate of hexitol, which is a reactive derivative of hexitol, with an alkyl halide. However, this method is not preferable because a small amount of a halogen element such as chlorine, bromine or iodine remains in the product, which deteriorates thermal stability.

Therefore, the method shown in the above-mentioned "New method for producing polyhydric ether alcohol derivative" is an inexpensive and simple production method without using a compound containing a halogen element such as chlorine, bromine or iodine. .

That is, the production of the polyhydric ether alcohol derivative represented by the general formula (XI) is carried out by using the hexavalent alcohol represented by the formula (V) and the carbonyl compound (ketone or aldehyde) represented by the general formula (XII) A cyclic ketal or a cyclic acetal is synthesized from one or more kinds of reactive derivatives (ketal or acetal) by ketalization, acetalization, transketalization or transacetalization, and hydrogenation is performed to obtain a polyhydric ether alcohol. This is alkyl-capped and synthesized.

In the general formula (XII), R ⁷ is a hydrogen atom,
Alternatively, a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms is shown, and R ⁸ is a linear, branched or cyclic alkyl group having 1 to 13 carbon atoms. Alternatively, R ⁷ and R ⁸ together form an alkylene group having 2 to 13 carbon atoms. However, R ⁷ and R ⁸ is an alkyl group having at least one hydrogen atom on one of the α-position of the R ⁷ and R ^8, the total number of carbon atoms in R ⁷ and R ⁸ is 1-13.

The reaction scheme of this reaction is as follows, for example:

[0170]

[Chemical 64]

In this reaction, a polyhydric ether alcohol (3-
XVIII) is mainly a 2 mol adduct (3-XVIII _A ), 3
Molar adduct (3-XVIII _B ), 4-molar adduct (3-XVI _B )
II _C ) and a small amount of 1 mol adduct (3-XVIII _D ) and 5 mol adduct (3-XVIII _E ).

[0172]

Embedded image

Here, R ^{1 to} R ⁶ in the formula are represented by the general formula (X
Although having the same meaning as in I), corresponding to the above reaction scheme, each corresponds to the residue of the carbonyl compound of the general formula (XII) or the residue of its reactive derivative,
It can be represented by the following general formula. Alkyl group: -CHR ⁷ R ⁸

Such a polyhydric ether alcohol (3-XV
III) can be purified to (3-XVIII _A ) to (3-XVIII _E ) by distillation, chromatography, liquid-liquid extraction and the like. In addition, these polyhydric ether alcohols (3-XVIII _A ) ~
(3-XVIII _E ) may be isolated and used alone in the next alkylation, or may be used as a mixture in the alkylation as it is.

As the hexahydric alcohol represented by the formula (V) used in the method of the present invention, specifically, reduction of hexose as described in the above-mentioned "New method for producing polyhydric ether alcohol derivative". Examples of hexitols obtained in 1. include sorbitol, mannitol, galactitol, iditol, talitol, and allitol.

Specific examples of the carbonyl compound represented by the general formula (XII) used in the method of the present invention include the above-mentioned "new method for producing polyhydric ether alcohol derivative".
Among the compounds exemplified in the above item, those having a carbon number of 2 to 14 including carbonyl carbon can be mentioned.

As the manufacturing method, specifically, the method shown in the above-mentioned "New manufacturing method of polyhydric ether alcohol derivative" can be used. Further, in the hydrogenation reaction, polyhydric ether ketal alcohol or polyhydric ether acetal alcohol, which is a reaction intermediate, is produced as a by-product. Specific examples of such compounds include those containing a ketal ring or acetal ring such as (3-XIX _A ) to (3-XIX _C ) below and an ether bond in the same molecule.

[0178]

[Chemical formula 66]

Polyhydric ether ketal alcohol or polyhydric ether acetal alcohol (3-XIX _{A to} 3-
When a mixture of polyhydric ether alcohols (3-XVIII) containing XIX _C etc.) is obtained, this is filtered and evaporated, and then a sufficient amount of 0.1-1 N hydrochloric acid etc. By hydrolyzing in a mixed acidic aqueous solution of an acid catalyst and ethanol, a polyhydric ether alcohol (3-XVIII) containing no ketal ring or acetal ring can be obtained.

On the other hand, a mixture of polyhydric ether alcohols (3-XVIII) containing those having a ketal ring or an acetal ring may be used as it is for the next alkyl etherification in the state containing this by-product. . In that case, polyhydric ether ketal alcohol or polyhydric ether acetal alcohol (3-XIX _{A to} 3-XIX _C, etc.) is
The alkyl etherification produces an ether compound represented by the general formula (XIII _AA ) or (XIII _BB ).

In the general formulas (XIII _AA ) and (XIII _BB ),
R ^{1 to} R ⁶ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, and R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 13 carbon atoms. Or, it represents a cyclic alkyl group, and R ⁸ has 1 to 1 carbon atoms.
13 represents a linear, branched or cyclic alkyl group. Alternatively, R ⁷ and R ⁸ together form an alkylene group having 2 to 13 carbon atoms. However, the total carbon number of R ^{1 to} R ³ and R ^{6 to} R ⁸ in the general formula (XIII _AA ) or R ¹ and R ^{4 to} R ^{8 in} the general formula (XIII _BB ) is ^{8 to} 40, and R ⁷ And the total carbon number of R ⁸ is 1 to 13. In addition,
a to e are reference numerals given to represent the arrangement of the structural units, and a to c or d to e may be arranged in any order.

This ether compound also exhibits the same effect as the polyhydric ether alcohol derivative represented by the general formula (XI) as the base oil of the refrigerating machine oil for the refrigerating machine working fluid. Also used in fluid compositions. In that case, the polyhydric ether alcohol derivative represented by the general formula (XIII _AA ) or (XIII _BB ) may be used alone, or may be used as a mixture with the polyhydric ether alcohol derivative represented by the general formula (XI). May be. When used alone, at the stage of a mixture of polyhydric ether alcohols,
After isolating those having a ketal ring or acetal ring,
It may be alkyl etherified, or at the stage of the polyhydric ether alcohol derivative after alkyl etherification,
Those having a ketal ring or an acetal ring may be isolated. At that time, the isolation method and the alkyl etherification method are the same as those for the polyhydric ether alcohol derivative represented by the general formula (XI). The alkyl group and the like in the general formulas (XIII _AA ) and (XIII _BB ) are the same as those in the polyhydric ether alcohol derivative represented by the general formula (XI).

The polyhydric ether alcohol derivative represented by the general formula (XI) and (XIII _AA ) or (XIII _BB ) thus obtained is purified to remove by-products and unreacted substances. Although good, a small amount of by-products and unreacted substances may be present as long as the effects of the present invention are not impaired. For example, unhydrogenated ketals or acetals (3-XVII) generated during the reaction other than the general formula (XIII _AA ) or (XIII _BB ) may partially remain, and the unalkylated hydroxyl group may be It does not matter if it remains.

In the present invention, the general formulas (XI) and (XII
The molecular weight of the polyhydric ether alcohol derivative represented by I _AA ) or (XIII _BB ) (hereinafter referred to as “the ether compound according to the present invention”) is not particularly limited, but when it is used as a refrigerating machine oil, a compressor is used. From the viewpoints of sealing property, compatibility with hydrofluorocarbon, lubricity, etc., those having an average molecular weight of 200 to 800 are preferably used, and those having an average molecular weight of 300 to 700 are more preferably used.

Further, the ether compound according to the present invention is
The viscosity at 100 ° C. is preferably 0.5 to 30 mm ² / s, more preferably 1 to 15 mm ² / s. 10
If the viscosity at 0 ° C. exceeds 30 mm ² / s, the compatibility between this compound and hydrofluorocarbon becomes poor. The viscosity at 40 ° C. is preferably 1 to 300 mm ² / s, more preferably 5 to 100 mm ² / s. Further, among the above-mentioned viscosity ranges, it is desirable that the two-layer separation temperature at low temperature with hydrofluorocarbon is low, and the critical dissolution temperature is 10 ° C. or lower, preferably 0 ° C. or lower,
More preferably, it is -10 ° C or lower.

As a refrigerating machine oil for refrigerators and room air conditioners which require electrical insulation, the ether compound according to the present invention has a volume resistivity at 25 ° C. of 10 ¹¹ Ω · cm or more, preferably 10 ¹² Ω · cm. More preferably, it is more preferably 10 ¹³ Ω · cm or more. Further, the pour point of the ether compound according to the present invention is desirably -10 ° C or lower, preferably -20 ° C or lower in order to prevent solidification of the refrigerating machine oil at low temperature.

Refrigerating machine oils containing an ether compound as a base oil according to the present invention are mineral oils, poly-α-olefins, alkylbenzenes, ethers and polyethers other than the above, and P, as long as the compatibility with hydrofluorocarbons is not impaired.
Synthetic oils such as AG, PAG-OH, ketones, esters, perfluoropolyethers and phosphoric acid esters may be mixed. In the refrigerating machine oil containing the ether compound according to the present invention as a base oil, the above ether compounds may be used alone or in combination of two or more.

The ether compound according to the present invention may be used alone, or if necessary, various additives may be added.

For example, in a room air conditioner or the like, the refrigerant is mostly filled in the field, so that there is a high possibility that water will be mixed. The ether compound according to the present invention itself is chemically stable even in the coexistence of water and there is no problem,
The PET film or the like, which is an insulating material, may be hydrolyzed to form a PET oligomer, which may clog the capillary tube or the like. Therefore, in order to remove water, it is preferable to add a compound having an epoxy group and an additive such as an orthoester, an acetal (ketal), and a carbodiimide.

That is, a) a compound having an epoxy group, b) an orthoester in the ether compound according to the present invention,
A refrigerating machine oil containing at least one selected from the group consisting of c) acetal (ketal) and d) carbodiimide is a refrigerating machine oil having a higher degree of perfection as a refrigerating machine oil,
It is very preferable, and the refrigerator working fluid composed of the refrigerating machine oil and hydrofluorocarbon is highly complete as a refrigerator working fluid and is very preferable.

A) As a compound having an epoxy group,
It has 4 to 60 carbon atoms, preferably 5 to 25 carbon atoms. Specifically, phenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether. Glycidyl ethers such as ether and pentaerythritol tetraglycidyl ether, glycidyl esters such as phthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, 2-ethylhexanoic acid glycidyl ester, and epoxidized stearin Epoxidized fatty acid monoesters such as methyl acid and epoxidized butyl stearate,
Epoxidized soybean oil, epoxidized vegetable oils such as epoxidized linseed oil, and epoxycyclooctane, epoxycycloheptane, compounds having an epoxycyclohexyl group described later, alicyclic epoxy compounds such as compounds having an epoxycyclopentyl group, and the like. .

The compound having an epoxycyclohexyl group and the compound having an epoxycyclopentyl group used in the present invention have 5 to 40 carbon atoms, preferably 5 to 2 carbon atoms.
5, specifically, those described in JP-A-5-209171, column 11, lines 34 to 46 are not particularly limited, but preferably 1,2
-Epoxycyclohexane, 1,2-epoxycyclopentane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 2- (7-oxabicyclo [4.1.0] hept-
3-yl) -spiro (1,3-dioxane-5,3 '-[7]]
Oxabicyclo [4.1.0] heptane).

In the present invention, these compounds having an epoxy group may be used alone or in combination of two or more kinds. The addition amount thereof is usually 0.05 to 2.0 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.1 to 1. 1 part by weight with respect to 100 parts by weight of the ether compound according to the present invention.
0 parts by weight.

B) The orthoester used in the present invention has 4 to 70 carbon atoms, and more preferably 4 to 50 carbon atoms. Specifically, JP-A-6-170
No. 73, column 10, lines 7 to 41 are mentioned. The addition amount of orthoester is usually 0.01 to 1 with respect to 100 parts by weight of the ether compound according to the present invention.
The amount is 00 parts by weight, preferably 0.05 to 30 parts by weight.

C) The acetal or ketal used in the present invention has 4 to 70 carbon atoms, and more preferably 4 to 50 carbon atoms. Specific examples thereof include those described in JP-A-6-17073, column 10, line 47 to column 11, line 21. The amount of acetal or ketal added is usually 0.01 to 100 parts by weight, preferably 0.05 to 30 parts by weight, based on 100 parts by weight of the ether compound according to the present invention.

D) The carbodiimide used in the present invention is represented by the following formula. Wherein _{R 10 -N = C = N-} R 11, R 10, R 11 represents a hydrocarbon group having 1 to 20 carbon atoms, more preferably those having 1 to 12 carbon atoms. R
₁₀ and R ₁₁ may be the same or different.

Specific examples of R ₁₀ and R ₁₁ include a methyl group,
Ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, t-butyl group, pentyl group, 1-methylbutyl group, 2-
Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-
Methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,2-dimethylbutyl group, 1,3-
Dimethylbutyl group, 2,3-dimethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-ethyl- 1-methylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-
Trimethylpropyl group, cyclohexyl group, cyclopentylmethyl group, methylcyclopentyl group, heptyl group,
1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group,
1-ethylpentyl group, 2-ethylpentyl group, 2,4-dimethylpentyl group, 3,4-dimethylpentyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1-propylbutyl group, 1-isopropylbutyl group, 1,3,3-trimethylbutyl group, 1,1-diethylpropyl group, 2,2-dimethyl-1-ethylpropyl group, 1,2-dimethyl-1-ethylpropyl group, 1-
Isopropyl-2-methylpropyl group, cycloheptyl group, cyclohexylmethyl group, methylcyclohexyl group, octyl group, 1-methylheptyl group, 2-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 1,1,
3,3-tetramethylbutyl group, 1,1-diisopropylethyl group, 1-ethyl-1,2,2-trimethylpropyl group, 1,5-dimethylhexyl group, 3,5-dimethylhexyl group, 2-propyl Pentyl group, 2,4,4-trimethylpentyl group, 1-ethyl-2
-Methylpentyl group, 2,2-dimethylhexyl group, 1,1-dimethylhexyl group, cycloheptylmethyl group, dimethylcyclohexyl group, 4-methylcyclohexylmethyl group,
Cycloheptylmethyl group, cyclooctyl group, 1-cyclohexylethyl group, 2-cyclohexylethyl group, ethylcyclohexyl group, nonyl group, 1-methyloctyl group, 5-
Methyloctyl group, 1- (2'-methylpropyl) -3-methylbutyl group, 3,5,5-trimethylhexyl group, 1,1-diethyl-
2,2-Dimethylpropyl group, 3-cyclohexylpropyl group, 1,1-dimethylheptyl group, decyl group, 1-methylnonyl group, 1-propylheptyl group, 3,7-dimethyloctyl group, 2,4,6- Trimethylheptyl group, 4-cyclohexylbutyl group, butylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, undecyl group, 1-methyldecyl group, 2-methyldecyl group, 2-ethylnonyl group, dodecyl group, 1- Methyl undecyl group, 2-methyl undecyl group, 2-
Ethyldecyl group, 1- (2'-methylpropyl) -3,5-dimethylhexyl group, tridecyl group, 2,4,6,8-tetramethylnonyl group, 2-methyldodecyl group, 2-ethylundecyl group, 1-
(3'-methylbutyl) -6-methylheptyl group, 1- (1'-methylbutyl) -4-methylheptyl group, tetradecyl group, 1-methyltridecyl group, 2-methyltridecyl group, 2-ethyldodecyl group , 2- (3'-methylbutyl) -7-methyloctyl group, 2-
(1'-methylbutyl) -5-methyloctyl group, pentadecyl group, 1-hexylnonyl group, 2-methyltetradecyl group, 2-
Ethyltridecyl group, hexadecyl group, 1-methylpentadecyl group, 2-hexyldecyl group, heptadecyl group, 1-heptyldecyl group, 1- (1 ', 3', 3'-trimethylbutyl) -4,6,
6-trimethylheptyl group, 1- (3'-methylhexyl) -6-methylnonyl group, octadecyl group, 2-heptylundecyl group, 2- (1 ', 3', 3'-trimethylbutyl) -5,7 , 7-trimethyloctyl group, 2- (3'-methylhexyl) -7-methyldecyl group, alkyl groups such as 2-octyldodecyl group, phenyl group, 2- or 3- or 4-methylphenyl group, 2- Or 3-or 4-
Ethylphenyl group, 2,3- or 2,4- or 2,5- or 2,6- or
3,4- or 3,5-dimethylphenyl group, 2- or 3- or 4-isopropylphenyl group, 2- or 3- or 4-propylphenyl group, 2,3,5- or 2,3,6- Or 2,4,6- or 3,4,5-trimethylphenyl group, 2- or 3- or 4-tert-butylphenyl group,
2- or 3- or 4-sec-butylphenyl group, 4- or 5-isopropyl-3-methylphenyl group, 4-tert-amylphenyl group, 3- or 4- or 5-methyl-2-tert-butyl group Phenyl group,
Pentamethylphenyl group, naphthyl group, 2-methylnaphthyl group, 2,6-diisopropylphenyl group, 4-tert-octylphenyl group, 2,4- or 2,6- or 3,5-di-tert-butylphenyl group Group, di-sec-butylphenyl group, aryl group such as 2,6-di-tert-butyl-4-methylphenyl group, 2,4,6-tri-tert-butylphenyl group, alkylaryl group and benzyl Group, 2- or 3- or 4-methyl benzyl group, phenethyl group, sec-phenethyl group, 2,4- or 2,5- or 3,4- or 3,5-
Dimethylbenzyl group, 4-ethylbenzyl group, 2- or 3- or 4-methylphenethyl group, α- or β-methylphenethyl group, α, α-dimethylbenzyl group, 1- or 3-phenylpropyl group, α- Or β-ethylphenethyl group, 4-isopropylbenzyl group, α-isopropylbenzyl group,
α, α-dimethylphenethyl group, 1- or 3- or 4-phenylbutyl group, α-ethyl-α-methylbenzyl group, 4-butylbenzyl group, 4-tert-butylbenzyl group, 1,1-dimethyl- 3-phenylpropyl group, 1- or 3-phenyl-2,2-
Examples thereof include aralkyl groups such as dimethylpropyl group, α-propylphenethyl group, 5-phenylpentyl group, naphthylmethyl group, naphthylethyl group, 6-phenylhexyl group.

Specific examples include 1,3-diisopropylcarbodiimide, 1,3-di-tert-butylcarbodiimide, 1,3-dicyclohexylcarbodiimide and 1,3-
Examples thereof include di-p-tolylcarbodiimide and 1,3- (2,6-diisopropylphenyl) carbodiimide. Preferred are 1,3-dicyclohexylcarbodiimide, 1,3-di-p-tolylcarbodiimide, and 1,3-bis- (2,6-diisopropylphenyl) carbodiimide.

The addition amount of carbodiimide is usually 0.0 based on 100 parts by weight of the ether compound according to the present invention.
It is 1 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

In addition to the water-removing additive, triaryl phosphate and / or triaryl phosphite may be added to improve lubricity, or radical trapping ability may be added to improve thermal stability. It is also effective to add a phenolic compound or a metal deactivator having a chelating ability, or to add a benzotriazole and / or a benzotriazole derivative in order to protect the metal surface.

The triaryl phosphate or triaryl phosphite used in the present invention has 18 to 20 carbon atoms.
70, more preferably 18 to 50 carbon atoms
belongs to. Specifically, it is described in JP-A-5-209171, column 12, lines 26-41. Among them, particularly preferred are triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (2,4-di-tert-butylphenyl) phosphate, triphenyl phosphite, tricresyl phosphite. , Trixylenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite.

Here, the amount of triaryl phosphate and / or triaryl phosphite added is usually 0.1 per 100 parts by weight of the ether compound according to the present invention.
To 5.0 parts by weight, preferably 0.5 to 2.0 parts by weight.

The phenolic compound having a radical trapping ability used in the present invention has a carbon number of 6 to 100, preferably 10 to 80. In particular,
It is described in JP-A-5-209171, column 12, line 32 to column 13, line 18. Among them, particularly preferred is 2,6-di-tert-butylphenol, 2,
6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,
2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-isopropylidenebisphenol,
2,4-Dimethyl-6-tert-butylphenol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl
-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-ethylphenol, 2,6-bis (2'-hydroxy-
3'-tert-butyl-5'-methylbenzyl) -4-methylphenol, bis [2- (2-hydroxy-5-methyl-3-tert-butylbenzyl) -4-methyl-6-tert-butylphenyl ] Terephthalate, triethylene glycol-bis [3- (3,
5-di-tert-butyl-5-methyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Here, the addition amount of the phenolic compound is usually 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the ether compound according to the present invention. It is preferably 0.05 to 0.5 parts by weight.

The metal deactivator used in the present invention preferably has a chelating ability and has 5 to 50 carbon atoms, preferably 5 to 20 carbon atoms. Specifically, it is described in JP-A-5-209171, column 13, line 38 to column 14, line 8. Among them, N, N'-disalicylidene-1,2-diaminoethane, N, N'-disalicylidene-1,2-diaminopropane, acetylacetone, acetoacetic acid ester, alizarin, quinizarin and the like are particularly preferable.

The amount of the metal deactivator added is usually 0.00 based on 100 parts by weight of the ether compound according to the present invention.
It is 1 to 2.0 parts by weight, preferably 0.003 to 0.5 parts by weight.

Benzotriazole used in the present invention,
The benzotriazole derivative has 6 to 50 carbon atoms, preferably 6 to 30 carbon atoms. Specifically, JP-A-5-209171, column 13, line 9 to 2
It is described in the 9th line. Among them, benzotriazole, 5-methyl-1H-benzotriazole and the like are particularly preferable.

The addition amount of benzotriazole and / or benzotriazole derivative is usually 0.001 to 0.1 with respect to 100 parts by weight of the ether compound according to the present invention.
Parts by weight, preferably 0.003 to 0.03 parts by weight.

If necessary, lubricating oil additives such as antioxidants, extreme pressure agents, oiliness improvers and antifoaming agents other than those mentioned above may be added. For example, those that can be used as antioxidants include p, p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, and alkylphenyl-1-. Amine antioxidants such as naphthylamine and alkylphenyl-2-naphthylamine; sulfur antioxidants such as alkyl disulfide, thiodipropionate and benzothiazole; zinc dialkyldithiophosphate and zinc diaryldithiophosphate. . The amount added is 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the ether compound according to the present invention.

Examples of the extreme pressure agent and oiliness improver that can be used include zinc compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate, thiodipropionic acid esters, dialkyl sulfides, dibenzyl sulfides, dialkyl polysulfides and alkyls. Sulfur compounds such as mercaptan, dibenzothiophene and 2,2'-dithiobis (benzothiazole), phosphorus compounds such as trialkyl phosphite and trialkyl phosphate,
Chlorinated compounds such as chlorinated paraffins, molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum compounds such as molybdenum disulfide, perfluoroalkyl polyethers, trifluoroethylene chloride polymers, fluorinated graphite and other fluorinated compounds, fatty acid modification Silicon compounds such as silicone, graphite and the like. The addition amount is 0.05 based on 100 parts by weight of the ether compound according to the present invention.
10 to 10 parts by weight.

As the defoaming agent, silicone oil such as dimethylpolysiloxane and organosilicates such as diethyl silicate are used. The addition amount is 0.0 with respect to 100 parts by weight of the ether compound according to the present invention.
005 to 1 part by weight.

Further, an additive such as an organic tin compound or a boron compound which stabilizes the chlorofluorocarbon refrigerant may be added. The addition amount is 0.001 to 10 parts by weight with respect to 100 parts by weight of the ether compound according to the present invention.

The mixing ratio of the hydrofluorocarbon in the composition for refrigerator working fluid of the present invention to the refrigerating machine oil containing the ether compound of the present invention as a base oil or the refrigerating machine oil obtained by adding an additive to the base oil is: Usually, hydrofluorocarbon / oil = 50/1 to 1/20 (weight ratio), preferably 10/1 to 1/5 (weight ratio). When the ratio of hydrofluorocarbon is higher than that of hydrofluorocarbon / oil = 50/1, the viscosity of the hydrofluorocarbon / oil mixed solution becomes low, and the lubricity may deteriorate, which is not preferable. Also, hydrofluorocarbon /
When the ratio of hydrofluorocarbon is lower than that of oil = 1/20, the refrigerating capacity may be insufficient, which is not preferable.

The hydrofluorocarbon used in the present invention means difluoromethane (HFC32), 1,1-difluoroethane (HFC152a), 1,1,1-trifluoroethane (HFC143a), 1,1,1,2-tetrafluorocarbon. Fluoroethane (HFC134a), 1,1,2,2-tetrafluoroethane (HFC134), pentafluoroethane (HFC125), etc., especially 1,1,1,2-tetrafluoroethane, pentafluoroethane, difluoromethane Is preferred.

[0214]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1-1 1,6-di-O- (3,5,5-trimethylhexyl) sorbit
Synthesis 1) 1.2 Lumpur (1b): 3.4: 5.6 - tri -O- (3,5,5-trimethyl f xylylene den) sorbitol (1a) a thermometer, a reflux condenser, a Dean - Stark trap, a calcium chloride tube And, in a 3 liter reaction vessel equipped with a stirrer, D-sorbitol 170.76 g (0.937 mol) and 3,5,5-trimethylhexanal 400 g (2.
812 mol), paratoluenesulfonic acid monohydrate 1.7
8 g (0.00936 mol) and 400 ml of hexane were charged. The temperature was raised with stirring, the reaction was carried out at 79 to 81 ° C. for 8 hours, and the calculated amount of water was distilled off. After completion of the reaction, the mixture was cooled to 70 ° C., 1.99 g (0.0188 mol) of sodium carbonate was added for neutralization, the mixture was stirred at 70 ° C. for 30 minutes, 100 g of water was added, and the mixture was stirred at 60 ° C. for 30 minutes and allowed to stand. The layers were separated. After removing the lower layer, the mixture was washed with 100 g of saturated saline and evaporated to obtain 529.51 g of the crude title compound (1a).

This residue was top-cut by vacuum distillation to obtain 500.87 g of a residue, which was dissolved in 500 ml of hexane and subjected to pressure filtration (PTFE, 0.2 μm) through 25.04 g of activated clay (5% by weight relative to the residue). Then, hexane was completely evaporated from the hexane solution obtained by washing with hexane to obtain 501.14 g of the title compound (1a) (yield 96.4%). Gas chromatography purity is 96.
3% and the hydroxyl value was 27.2 (theoretical value 0).

2) 1,6-Di-O- (3,5,5-trimethylhexyl) sorbitol (1b) 487.1 g (0.878 mol) of the compound (1a) obtained in 1) was placed in a 1 liter autoclave. ) And 5% Pd
/ C (dry product: 50% water-containing product decompressed with a vacuum pump and dried at room temperature for 1 day) (N.E. ChemCat's "5% Pd carbon powder 5.0% water-containing product, E-typ.
e, pH 6.0 "), and 9.74 g (2% by weight) were charged. The temperature is raised with stirring at a hydrogen pressure of 20 kg / cm ² ,
The reaction was carried out at 190 ° C. under a hydrogen pressure of 200 kg / cm 2 for 8 hours. Hydroxyl value at the end of reaction 243.3 [Theoretical value 30
0.9 (as ether alcohol with an average alkyl substitution of 3.0)]. After completion of the reaction, isopropanol 300m
Dissolve in l, and membrane filter (PTFE, 0.2
(μm) under pressure filtration and evaporation to give 475.85 g of crude polyhydric ether alcohol mixture (crude yield 96.6%). The composition of this product by gas chromatography was 19% dialkyl and 47 trialkyl.
%, Tetraalkyl body 18%, monoalkyl body 3%, and pentaalkyl body 2%. Of this, 200 g was purified by silica gel column chromatography using hexane / ethanol = 95/5 (Vol / Vol) as a developing solvent to obtain 18.2 g of the title compound (1b). Gas chromatography purity is 90.5%; hydroxyl value is 471
(Theoretical value 517).

IR (NEAT, cm ^-1 ): 3465 (OH stretching), 2954 (CH stretching), 1473, 1395, 1368 (CH)
Deflection), 1122 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.77 to 1.35 (28H, multiplet, —CH ( CH ₃ ) CH ₂ C (CH ₃ ) ₃ ) 1.35 to 1.75 (2H , _{multiplet, -CH 2 CH (CH 3)} CH 2 C (CH 3) 3) 3.03 (4H, singlet, -OH) 3.43 to 4.02 (12H, multiplet, -CH (OH) -, -CH 2 O CH _2- ) MASS (FD): 436 (M + 1)

Example 1-2 1,3,6-tri-O- (3,5,5-trimethylhexyl) sol
Synthesis of Bitol (2) A silica gel column using 100 g of the crude polyhydric ether alcohol mixture obtained in Example 1-1 as the developing solvent in hexane / ethanol = 95/5 (Vol / Vol) as in Example 1-1. Purification by chromatography gave 32.3 g of the title compound (2). The gas chromatography purity was 93.3% and the hydroxyl value was 280 (theoretical value 301).

IR (NEAT, cm ^-1 ): 3466 (OH stretching), 2956 (CH stretching), 1473, 1395, 1368 (CH)
Deflection), 1122 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.77 to 1.35 (42H, multiplet, —CH ( CH ₃ ) CH ₂ C ( CH ₃ ) ₃ 1.35 to 1.80 (9H, _{multiplet, -CH 2 CH (CH 3)} CH 2 C (CH 3) 3) 3.40~4.00 (14H, multiplet, -C H (OH) -, -CH 2 O CH 2 -) MASS (FD): 688 (M + 1)

Example 1-3 1,3,6, x-tetra-O- (3,5,5-trimethylhexyl)
Synthesis of sorbitol (3) (x represents any of 2, 4, 5; the same applies hereinafter) 100 g of the crude polyhydric ether alcohol mixture obtained in Example 1-1 was treated in the same manner as in Example 1-1. Was purified by silica gel column chromatography using hexane / ethanol = 95/5 (Vol / Vol) as a developing solvent to give 24.0 g of the title compound (3). The gas chromatography purity was 83.5%; the hydroxyl value was 174 (theoretical value 163).

IR (NEAT, cm ^-1 ): 3465 (OH stretching), 2954 (CH stretching), 1473, 1394, 1367 (CH)
Deflection), 1120 (C-O expansion and contraction) MASS (FD): 351 (M + 1)

Example 1-4 1-O- (3,5,5-trimethylhexyl) sorbitol,
1,6-di-O- (3,5,5-trimethylhexyl) sorbit
1,3,6-tri-O- (3,5,5-trimethylhexyl
Le) sorbitol, 1,3,6, x-tetra-O- (3,5,5-to
Limethylhexyl) sorbitol, 1,3,6, x, y-penta
-O- (3,5,5-trimethylhexyl) sorbitol mixture
Product (ether alcohol with an average alkyl substitution number of 3.1)
Synthesis of (4) (y is different from x and represents any number of 2, 4, and 5. The same applies hereinafter.) 200 g of the crude polyhydric ether alcohol mixture obtained in Example 1-1 was heated under reduced pressure. (192 ° C / 0.6mmH
g) and purified by removing low-boiling components to obtain 178 g of the title compound (4) (yield 89.2%). The composition of this product by gas chromatography was 3% monoalkyl, 21% dialkyl and 53 trialkyl.
%, Tetraalkyl body 20%, and pentaalkyl body 2%. The hydroxyl value was 282 (ether alcohol having an average alkyl substitution number of 3.1).

IR (NEAT, cm ^-1 ): 3466 (OH stretching), 2955 (CH stretching), 1473, 1395, 1367 (CH)
Deflection), 1118 (C-O expansion and contraction)

Example 1-5 1-Mono-O- (3,5,5-trimethylhexyl) sorbit
1,6-di-O- (3,5,5-trimethylhexyl) so
Rubitol, 1,3,6-tri-O- (3,5,5-trimethyl
Xyl) sorbitol, 1,3,6, x-tetra-O- (3,5,5
-Trimethylhexyl) sorbitol, 1,3,6, x, y-pet
-O- (3,5,5-trimethylhexyl) sorbitol
Mixtures (ether alcohols with an average alkyl substitution of 2.0)
1 ) 1.2: 3.4: 5.6-tri-O- (3,5,5-trimethylhexylidene) sorbitol obtained in Example 1-1 in a 1 liter autoclave. (1a) 480 g (0.
865 mol), D-sorbitol 78.8 g (0.43)
3 mol) and 5% Pd / C (dry product: 50% water-containing product decompressed with a vacuum pump and dried at room temperature for 1 day) (manufactured by NE Chemcat Corporation, "5% Pd carbon powder 5.0%").
Hydrated product, E-type, pH 6.0 ") 9.74 g (2
(Wt%). The temperature is raised with stirring at a hydrogen pressure of 20 kg / cm ² , and the hydrogen pressure is 200 kg / cm at 190 ° C.
^The reaction was performed at ² for 25 hours. After completion of the reaction, dissolve in 300 ml of isopropanol and use a membrane filter (PTF
E, 0.2 μm) under pressure filtration and evaporation to give 532.0 g of crude polyhydric ether alcohol mixture (crude yield 95.1%). Heat this under reduced pressure (1
82-207 ° C./0.6 mmHg), and the residue was purified by distilling off low-boiling components to obtain 484 g of the title compound (5) (yield 91.0%). The composition of this product by gas chromatography was as follows: monoalkyl compound 34%, dialkyl compound 47%, trialkyl compound 16%, tetraalkyl compound 1
%Met. The hydroxyl value was 521 (ether alcohol having an average number of alkyl substitutions of 2.0).

Example 1-6 2,3,4,5-tetra-O-methyl-1,6-di-O- (3,5,5
-Trimethylhexyl) sorbitol (6) synthesis thermometer, reflux condenser, dropping funnel and stirrer 1
Sodium hydride (60% content,
Oily) 7.3 g (0.18 mol) was added, and hexane 50
It was washed by adding ml and stirring, and removing the supernatant by decantation. 320 ml of a 1,2-dimethoxyethane / dimethylsulfoxide = 3/1 (Vol / Vol) mixed solvent was added, and the mixture was stirred at room temperature while stirring Example 1
A solution of 17.0 g (0.039 mol) of the compound (1b) obtained in -1 in 16 ml of the same mixed solvent was added dropwise over 10 minutes, and the mixture was further stirred at 50 ° C. for 1 hour. After cooling to 40 ° C., 22.9 g (0.18 mol) of dimethyl sulfate was added dropwise at 50 ° C. or lower over 20 minutes. After further stirring at 50 ° C for 1 hour, cooling, adding 72.0 g (0.18 mol) of 10% aqueous sodium hydroxide solution, and adding at 70-80 ° C for 1 hour
Stir for hours. After cooling, 100 ml of water was added to separate the layers,
The aqueous layer was extracted twice with 150 ml of diethyl ether, and the organic layers were combined and washed three times with 100 ml of saturated saline. It was dried over anhydrous sodium sulfate and the solvent was removed by an evaporator to obtain 21.2 g of an oily substance. Further, this was purified by silica gel column chromatography using hexane / diethyl ether = 90/10 (Vol / Vol) as a developing solvent, and then distilled under reduced pressure (boiling point 179 ° C./0.35 m
mHg) to obtain 6.8 g of the title compound (6). The gas chromatography purity was 99.7%.

IR (NEAT, cm ^-1 ): 2950 (CH stretching), 1473, 1368 (CH bending), 1116 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.80- 1.33 (28H, _{multiplet, -CH (CH 3) CH 2} C (CH 3) 3) 1.33~1.80 (6H, _{multiplet, -CH 2 CH (CH 3)} CH 2 C (CH 3) 3) 3.35~ 3.80 (24H, multiplex, -CH ( O CH ₃ ) -, -CH ₂ O CH _2- )

Example 1-7 2,4,5-Tri-O-methyl-1,3,6-tri-O- (3,5,5
-Trimethylhexyl) sorbitol (7) synthesis thermometer, reflux condenser, dropping funnel and stirrer 1
Sodium hydride (60% content,
Oily) 4.9 g (0.12 mol) was added, and hexane 50 was added.
It was washed by adding ml and stirring, and removing the supernatant by decantation. 320 ml of a 1,2-dimethoxyethane / dimethylsulfoxide = 3/1 (Vol / Vol) mixed solvent was added, and the mixture was stirred at room temperature while stirring Example 1
-2. 15.3 g (0.027 mol) of compound (2) obtained in
What was melt | dissolved in 12 ml of the same mixed solvent was dripped over 10 minutes, and also it stirred at 50 degreeC for 30 minutes. Cool to 40 ° C. and add 15.5 g (0.12 mol) of dimethyl sulfate to 5
The solution was added dropwise at 0 ° C or lower over 1 hour. After further stirring at 50 ° C. for 1 hour, the mixture was cooled and 10% sodium hydroxide aqueous solution 4
8.0 g (0.12 mol) was added and the mixture was stirred at 70 to 80 ° C for 1 hour. After cooling, the layers were separated, the aqueous layer was extracted twice with 100 ml of diethyl ether, and the organic layers were combined and washed 3 times with 50 ml of saturated saline. Dry over anhydrous sodium sulfate, remove the solvent with an evaporator, and oily substance 16.9 g
I got Furthermore, this is hexane / diethyl ether = 9
Purification by silica gel column chromatography using 0/10 (Vol / Vol) as a developing solvent gave 12.6 g of the title compound (7) (purity of gas chromatography: 98.4%).

IR (NEAT, cm ^-1 ): 2956 (CH stretching), 1470, 1368 (CH bending), 1194 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.78- 1.10 (42H, _{multiplet, -CH (CH 3) CH 2} C (CH 3) 3) 1.16~1.78 (9H, _{multiplet, -CH 2 CH (CH 3)} CH 2 C (CH 3) 3) 3.23~ 3.85 (23H, multiplex, -CH ( O CH ₃ ) -, -CH ₂ O CH _2- )

Example 1-8-1 2,3,4,5,6-penta-O-methyl-1-O- (3,5,5-to)
Limethylhexyl) sorbitol, 2,3,4,5-tetra-
O-methyl-1,6-di-O- (3,5,5-trimethylhexyl
Le) sorbitol, 2,4,5-tri-O-methyl-1,3,6
-Tri-O- (3,5,5-trimethylhexyl) sorbitol
Le, di-O-methyl-1,3,6, x-tetra-O- (3,5,5-
Trimethylhexyl) sorbitol, O-methyl-1,3,
6, x, y-penta-O- (3,5,5-trimethylhexyl) so
Rubitol mixture (Ate with an average alkyl substitution of 2.0)
Methyl alcohol cap) (8-1) synthesis thermometer, reflux condenser, dropping funnel and stirrer 3
Sodium hydride (60% content,
(Oil) 117g (3.06mol) was added and hexane 40
0 ml was added and stirred, and the supernatant was washed by removing the supernatant by decantation, and 1.5 liter of toluene was added.

Mono-, di-, tri-, tetra-, penta-O- (3,5,5-trimethylhexyl) sorbitol mixture (5) (hydroxyl value 521) obtained in the same manner as in Example 1-5. , Ether alcohol having an average number of alkyl substitutions of 2.0) dissolved in 300 ml of toluene was added dropwise at 24 to 36 ° C. over 30 minutes, and further 90 to 9
The mixture was stirred at 7 ° C for 30 minutes. After cooling to 40 ° C., 386 g (3.06 mol) of dimethyl sulfuric acid was added dropwise at 60 ° C. or lower over 2.5 hours. After further stirring at 60 ° C. for 1 hour, the mixture was cooled and 898 g (3.37%) of a 15% sodium hydroxide aqueous solution was added.
Mol) was added and the mixture was stirred at 80 ° C. for 1 hour. After cooling, the layers were separated, the aqueous layer was extracted once with 300 ml of toluene, and the organic layers were combined and washed 3 times with 40 ml of saturated saline. It was dried over anhydrous sodium sulfate and the solvent was removed by an evaporator to obtain 248 g of an oily substance. Further under reduced pressure (0.7 mmH
g), the low boiling point component was distilled off by heating at 185 to 190 ° C. for 30 minutes to obtain 226 g of the title compound (8-1). The composition of this product by gas chromatography was 34% monoalkyl, 47% dialkyl, 16% trialkyl, and 1% tetraalkyl. IR (NEAT, cm ^-1 ): 2956 (C-H expansion and contraction), 1473, 1368
(C-H bending angle), 1104 (C-O expansion and contraction)

Example 1-8-2 2,3,4,5-tetra-O-methyl-1,6-di-O- (3,5,5
-Trimethylhexyl) sorbitol, 2,4,5-tri-
O-methyl-1,3,6-tri-O- (3,5,5-trimethyl
Xyl) sorbitol, di-O-methyl-1,3,6, X-teto
La-O- (3,5,5-trimethylhexyl) sorbitol,
2,3,4,5,6-Penta-O-methyl-1-O- (3,5,5-to
Limethylhexyl) sorbitol mixture (average alkyl
Methyl cap of ether alcohol with 3.1 substitution
Body) (8-2) synthesis

25.35 g (1.06 mol) of sodium hydride powder and 500 ml of toluene were placed in a 2-liter reaction vessel equipped with a thermometer, a reflux condenser, a dropping funnel and a stirrer.
Was charged. Mono-, di-, tri-, obtained in the same manner as in Example 1-4 at room temperature with stirring under a nitrogen atmosphere,
Tetra-O- (3,5,5-trimethylhexyl) sorbitol mixture (4) 100 g (0.2 mol) was added to toluene 10
What was melt | dissolved in 0 ml was dripped in 30 minutes, 200 ml of toluene was added and it heated up, and refluxed and stirred at 110 degreeC for 30 minutes. After that, the mixture was cooled to 50 ° C., and 133.22 g (1.06 mol) of dimethyl sulfate was added dropwise at 50 ° C. over 1 hour. Add 600 ml of toluene and add 1 at 80 ℃
After aging for a period of time, the mixture was cooled, and 422.5 g (1.06 mol) of a 10% aqueous sodium hydroxide solution was added to 70-80.
Stirred at 30 ° C for 30 minutes. After cooling to room temperature, the layers were allowed to stand and the lower layer was removed. The upper layer was washed 4 times with 200 ml of a saturated saline solution and then dried over anhydrous sodium sulfate to obtain 2.2 g of activated carbon (2
(% By weight relative to the theoretical yield), which was subjected to adsorption treatment, filtered, and then evaporated to obtain an oily substance, which was top-cut at an internal temperature of 200 ° C. at a pressure of 0.7 mmHg to give the title compound (8-2) 7
0.4 g was obtained (yield 64.4%). The gas chromatography had a purity of 96.1%.

2,3,4,5,6-Penta-O-methyl-1-O
3.5% by weight of-(3,5,5-trimethylhexyl) sorbitol, 2,3,4,5-tetra-O-methyl-1,6-di-O-
(3,5,5-Trimethylhexyl) sorbitol 37.6% by weight, 2,4,5-tri-O-methyl-1,3,6-tri-O-
(3,5,5-Trimethylhexyl) sorbitol 42.9% by weight, di-O-methyl-1,3,6, X-tetra-O- (3,5,5
-Trimethylhexyl) sorbitol 12.1% by weight.

Example 1-9 1,6-di-O- (1-methylpropyl) -O- (1-me
Synthesis of tylpropylidene) sorbitol (9b) 1) 1.2: 3.4: 5.6-tri-O- (1-methylpropylidene) sorbitol (9a) A thermometer, reflux condenser, Dean-Stark trap, calcium chloride tube and stirrer were added. In a provided 3-liter reaction container, D-sorbitol 336.84 g (1.849 mol), methyl ethyl ketone 800 g (11.094 mol), paratoluenesulfonic acid monohydrate 17.58 g
(0.092 mol) and 200 ml of hexane were charged. The temperature was raised with stirring, the reaction was carried out at 69 to 79 ° C. for 8 hours, and the calculated amount of water was distilled off. After completion of the reaction, the mixture was cooled to 60 ° C., 19.60 g (0.185 mol) of sodium carbonate was added for neutralization, and the mixture was stirred at 60 ° C. for 30 minutes and then water 200
g was added, and the mixture was stirred at 60 ° C. for 30 minutes, and stationary-separated. After removing the lower layer, the mixture was washed with 200 g of a saturated saline solution and evaporated to obtain 643.75 g of the crude title compound (9a).
This was distilled under reduced pressure to give the title compound (9a) 606.7.
1 g was obtained (yield 95.3%). Boiling point 136-140 ° C
/0.6 mmHg, gas chromatography purity 97.
The hydroxyl value was 3% and the hydroxyl value was 12.9 (theoretical value: 0).

2) 1,6-Di-O- (1-methylpropyl) -O- (1-methylpropylidene) sorbitol (9b) In a 1-liter autoclave, the compound (9a) 571. 5 g (1.659 mol) and 5% Pd
/ C (dried product: 50% water-containing product decompressed with a vacuum pump and dried at room temperature for 1 day) ("N.E. Chemcat""5% Pd carbon powder 50% water-containing product, E-type,
pH 6.0 ") 11.43 g (2% by weight) was charged.
The temperature was raised with stirring at a hydrogen pressure of 20 kg / cm ² to reach 19
The reaction was carried out at 0 ° C. under a hydrogen pressure of 200 kg / cm ² for 15 hours. The hydroxyl value at the end of the reaction is 403.5 [theoretical value 480.
23 (as ether alcohol with an average alkyl substitution of 3.0)]. After completion of the reaction, 200 ml of isopropanol
Dissolve in a membrane filter (PTFE, 0.2μ
m) under pressure filtration and evaporation to give 551.34 g of crude title compound (9b) (crude yield 96.5).
%). The composition of this product by gas chromatography was 16% dialkyl ether and 20% trialkyl ether.
%, Dialkyl ether monoketal 51%, trialkyl ether monoketal 10%, and tetraalkyl ether 1%. Of this, 500 g is hexane 500
Dissolved in ml and methanol / water = 200 ml / 200 ml
Wash 3 times with, methanol / water = 200ml / 100ml
Wash three times with methanol / water = 100 ml / 10
After washing 4 times with 0 ml, the upper hexane layer obtained after washing was evaporated to obtain 251.84 g of a partially purified hydrogenated product. 250 ml of hexane
And was purified by silica gel column chromatography. Fractions eluting with hexane / ethanol = 99/1 were collected and evaporated to give the title compound (9b) 1
31.92 g was obtained. Gas chromatography purity 9
7.7%; hydroxyl value 327.5 (theoretical value 322.01)
Met.

IR (NEAT, cm ^-1 ): 3492 (OH stretching), 2972, 2936, 2884 (CH stretching), 1468, 1378.
( CH bending), 1082 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.92 (9H, triplet, -CH ₂ CH ₃ ) 1.12 (6H, doublet, -CH CH ₃ ) 1.38 (3H, _{singlet, (- O-) 2 C (} CH 3) CH 2 CH 3 1.43~1.80 (6H, _{multiplet, -CH 2 CH 3) 2.85 (} 2H, singlet, -OH) 3.29~ 4.33 (10H, multiplex, -O- CH _2- , -O- CH- ) MASS (FD): 349 (M + 1)

Example 1-10 1,3,6-tri-O- (1-methylpropyl) sorbitol
Le Synthesis Example 1-9 obtained in partially purified hydrogenated product 251.84g (10) was dissolved in hexane 250 ml, and purified by silica gel column chromatography. Fractions eluting with hexane / ethanol = 95/5 were collected and evaporated to obtain 55.42 g of the title compound (10). The gas chromatography purity was 97.3%; the hydroxyl value was 453.1 (theoretical value was 480.24).

IR (NEAT, cm ^-1 ): 3464 (OH stretching), 2972, 2932, 2880 (CH stretching), 1466, 1380
( CH bending), 1086 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.92 (9H, triplet, —CH ₂ CH ₃ ) 1.13 (9H, doublet, —CH CH ₃ ) 1.32 to 1.78 (6H, multiple line, -CH ₂ CH ₃ ) 3.13 (3H, wide singlet, -OH) 3.30 to 4.02 (-O -CH _2- , -O- CH- ) MASS (FD): 351 (M + 1)

Examples 1-11 1,6-di-O- (1-methylpropyl) -di-O-methyl
Le-O- (1-methylpropylidene) sorbitol (1
1) equipped with the synthetic thermometer of 1) , reflux condenser, dropping funnel and stirrer
12.38 sodium hydride powder in a 1 liter reaction vessel
g (0.516 mol) and 300 ml of toluene were charged. Example 1 at room temperature with stirring under a nitrogen atmosphere
A solution of 70 g (0.201 mol) of the compound (9b) obtained in 9 in 100 ml of toluene was added dropwise over 20 minutes, then the temperature was raised, and the mixture was refluxed and stirred at 110 ° C. for 30 minutes. After that, it was cooled to 50 ° C and dimethylsulfate 65.08.
g (0.516 mol) was added dropwise at 50 ° C. over 1 hour.
After aging at 80 ° C for 1 hour, the mixture was cooled, 206.4 g (0.516 mol) of 10% aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 to 80 ° C for 30 minutes. After cooling to room temperature, the mixture was extracted with 200 ml of ether, washed twice with 100 ml of a saturated saline solution, dried over anhydrous sodium sulfate and evaporated to obtain 76.72 g of a viscous oily substance. This was distilled under reduced pressure to obtain 68.83 g of the title compound (11) (yield 92.1%). Boiling point 127-128 ° C / 0.4
mmHg, gas chromatography purity 99.0%, and hydroxyl value 0.67 (theoretical value 0).

IR (NEAT, cm ^-1 ): 2974, 2925 (C-H
Deflection), 1470, 1377, 1341 (C-H Deflection), 1089 (C-
O stretching) ¹ H NMR (CDCl ₃ , δppm): 0.90 (9H, triplet, -CH ₂ CH ₃ ) 1.10 to 1.20 (6H, multiplet, -CH ( CH ₃ ) CH ₂ CH ₃ 1.29 to 1.42 (3H , Multiple line, (-O-) ₂ C ( CH ₃ ) CH ₂ CH ₃ 1.42 to 1.80 (6H, multiple line, -CH ₂ CH ₃ ) 3.29 to 3.80 (14H, multiple line, -CH ₂ -O -CH ( CH ₃ ) CH ₂ CH ₃ , CH-
O- CH ₃ )

Example 1-12 2,4,5-tri-O-ethyl-1,3,6-tri-O- (1-
Methylpropyl) sorbitol (12) synthesis thermometer, reflux condenser, dropping funnel and stirrer 3
3.70 g of sodium hydride powder in a 00 ml reaction vessel
(0.154 mol) and 100 ml of toluene were charged.
Example 1-10 at room temperature with stirring under a nitrogen atmosphere.
A solution of 12 g (0.0342 mol) of the compound (10b) obtained in 1 above in 50 ml of toluene was added dropwise over 20 minutes, the temperature was raised, and the mixture was stirred under reflux at 110 ° C. for 30 minutes.
After that, it was cooled to 50 ° C. and 23.75 g of diethyl sulfuric acid
(0.154 mol) was added dropwise at 50 ° C over 45 minutes.
After aging for 2 hours at 80 ° C., the mixture was cooled, 61.6 g (0.154 mol) of 10% sodium hydroxide aqueous solution was added, and the mixture was stirred at 70-80 ° C. for 30 minutes. After cooling to room temperature, the upper layer except the lower layer was washed twice with 50 ml of a saturated saline solution, dried over anhydrous sodium sulfate and evaporated to obtain 14.8 g of a viscous oily substance. This was distilled under reduced pressure to obtain 13.69 g of the title compound (12) (yield 92.0%). Boiling point 145-146 ° C / 0.5m
mHg, gas chromatography purity 96.2%, and hydroxyl value 0.5 (theoretical value 0).

IR (NEAT, cm ^-1 ): 2974, 2932, 2878
(C-H expansion and contraction), 1467, 1377, 1341 (C-H bending angle), 11
10 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.82 to 1.08 (9H, triplet, -CH (CH ₃ ) CH ₂ CH ₃ ) 1.08 to 1.80 (24H, multiplet, -CH ( CH ₃ ) CH ₂ CH ₃ , -OCH ₂ CH
_{3) 3.21~4.00} (17H, _{multiplet, -CH- O- CH 2 -, -C} H -O CH (CH 3)
-)

Example 1-13 1,6-di-O- (1,3-dimethylbutyl) -O- (1,3-di)
Synthesis of Methyl Butylidene) Sorbitol (13b) 1) 1,2: 3,4: 5,6-Tri-O- (1,3-Dimethyl Butylidene) Sorbitol (13a) Thermometer, Reflux Cooler, Dean- In a 3 liter reaction vessel equipped with a Stark trap, a calcium chloride tube and a stirrer, D-sorbitol 363.76 g (1.997 mol) and methyl isobutyl ketone 1200 g (11.98).
1 mol), paratoluenesulfonic acid monohydrate 18.99
g (0.0998 mol) and 300 ml of hexane were charged. The temperature was raised with stirring, the reaction was carried out at 93 to 98 ° C. for 23 hours, and the calculated amount of water was distilled off. After completion of the reaction, the mixture was cooled to 60 ° C., 21.16 g (0.1996 mol) of sodium carbonate was added for neutralization, the mixture was stirred at 60 ° C. for 30 minutes, 200 g of water was added, and the mixture was stirred at 60 ° C. for 30 minutes, and allowed to stand. The layers were separated. After removing the lower layer, the organic layer was washed with 200 g of a saturated saline solution and evaporated to give 736.65 g of the crude title compound (13a).
I got 657.62 g of the residue obtained by top-cutting this product by vacuum distillation was subjected to pressure filtration (PTFE, 0.2 μm) through 33 g of activated clay (5% by weight relative to the residue) to obtain 637.44 g of the title compound (13a). Obtained (yield 74.5%). Gas chromatography purity is 96.1
%, The hydroxyl value was 34.3 (theoretical value: 0).

2) 1,6-di-O- (1,3-dimethylbutyl) -O- (1,3-dimethylbutylidene) sorbitol (13b) The compound (1) obtained in 1) above in a 1 liter autoclave. 13a) 612 g (1.428 mol) and 5% Pd /
C (dry product: 50% water-containing product decompressed with a vacuum pump and dried at room temperature for 1 day) (N.E. ChemCat "5% Pd carbon powder 50% water-containing product, E-type,"
(pH 6.0 ") 12.24 g (2% by weight) was charged.
The temperature was raised with stirring at a hydrogen pressure of 20 kg / cm ² to reach 19
The reaction was carried out at 0 ° C. under a hydrogen pressure of 200 kg / cm ² for 10 hours. Hydroxyl value at the end of reaction 366.9 [theoretical value 387.
25 (as ether alcohol having an average number of alkyl substitutions of 3.0)]. After completion of the reaction, the product was dissolved in 200 ml of hexane, filtered under pressure through a membrane filter (PTFE, 0.2 μm), evaporated, and hydrogenated (1
32.7 g of 482.73 g was obtained (crude yield: 77.8%). The composition of this product by gas chromatography was 21% dialkyl ether, 20% trialkyl ether, 37% dialkyl ether monoketal, and 8% trialkyl ether monoketal. Of this, 360 g was purified by silica gel column chromatography using hexane / ethanol = 97/3 (Vol / Vol) as a developing solvent to obtain 66.0 g of the title compound (13b). Gas chromatographic purity is 98.3%; hydroxyl value is 2
67 (theoretical value 259).

IR (NEAT, cm ^-1 ): 3436 (OH stretching), 2960, 2878 (CH stretching), 1470, 1377 (CH)
Deflection), 1092 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.80 to 1.09 (18H, multiplet, —CH ( CH ₃ ) ₂ ) 0.80 to 1.30 (9H, multiplet, —OCH ( CH ₃ ) CH _2- , (-O-) ₂ C ( CH
₃ ) CH _2- ) 1.30 to 1.65 (8H, multiple line, -CH ₂ CH (CH ₃ ) ₂ ) 1.65 to 1.92 (2H, multiple line, -CH ( CH ₃ ) ₂ ) 2.36 to 2.82 (2H, wide single line, -OH) 3.33~4.40 (10H, _{multiplet, - CH O CH 2 -,} - CH -O-) MASS (FD): 433 (M + 1)

Example 1-14 1,6-di-O- (1,3-dimethylbutyl) sorbitol
In the synthesis example 1-13 of (14), silica gel chromatography (hexane / ethanol = 95/5 (Vol /
Vol)) was carried out to purify the hydrogenated product to obtain 57.9 g of the title compound (14). Gas chromatography purity is 83.7%; hydroxyl value is 614 (theoretical value 6
41).

IR (NEAT, cm ^-1 ): 3436 (OH stretching), 2962, 2873 (CH stretching), 1470, 1377 (CH)
Deflection), 1089 (CO stretching) ¹ H NMR (CDCl ₃ , δppm): 0.85 to 1.02 (12H, multiplet, —CH (CH ₃ ) ₃ ) 1.15 (6H, doublet, —OCH (CH ₃₎ -) _1.22~1.64 (4H, _{multiplet, -CH 2 CH (CH 3)} 2) 1.64~1.90 (2H, _{multiplet, -CH (CH 3) 2)} 3.32 (4H, singlet, -OH) 3.45 ~ 4.02 (10H, multiple line, -CH O CH ₂ - ,- CH -O-) MASS (FD): 351 (M + 1)

Example 1-15 1,6-di-O- (1,3-dimethylbutyl) -di-O-methyl
Ru-O- (1,3-dimethylbutylidene) sorbitol (1
1) equipped with a synthetic thermometer of 5) , a reflux condenser, a dropping funnel and a stirrer
Sodium hydride (60% content,
(Oil) 15.6 g (0.39 mol) was added, and hexane 1
00 ml was added and stirred, and the supernatant was removed by decantation for washing. 200 ml of toluene was added, and 64.1 g (0.15 mol) of the compound (13b) obtained in Example 1-13 was added to toluene 10 at room temperature with stirring.
What was melt | dissolved in 0 ml was dripped over 15 minutes, and also it stirred at 100 degreeC for 1 hour. After cooling to 40 ° C., 49.1 g (0.39 mol) of dimethyl sulfate was added dropwise at 60 ° C. or lower over 1 hour. After further stirring at 60 ° C. for 1 hour, the mixture was cooled, and 156 g (0.39
Mol) was added and the mixture was stirred at 70 to 80 ° C. for 1 hour. After cooling, the layers were separated, the aqueous layer was extracted twice with 150 ml of diethyl ether, and the organic layers were combined and washed three times with 100 ml of saturated saline. The extract was dried over anhydrous sodium sulfate and the solvent was removed by an evaporator to obtain 68.0 g of an oily substance. Hexane / diethyl ether = 95/5 to 90/1
Purify by silica gel column chromatography using 0 (Vol / Vol) as a developing solvent to give the title compound (1
5) 56.6 g was obtained (gas chromatography purity 9
7.7%).

IR (NEAT, cm ^-1 ): 2956, 2878 (C-H
Expansion and contraction), 1470, 1374 (C-H bending angle), 1125, 1095 (C-
O stretching) ¹ H NMR (CDCl ₃ , δppm): 0.70 to 1.08 (18H, —CH ₂ CH
_{(CH 3) 2) 1.08~1.30 (} 9H, -OCH (CH 3) CH 2 -, (- O-) 2 C (CH 3) CH 2 -) 1.30~1.67 (6H, -OCH (CH 3) CH _2- , (-O-) ₂ C (CH ₃ ) CH _2- ) 1.67 to 1.96 (3H, -CH ( CH ₃ ) ₂ ) 3.22 to 4.25 (16H, -O- CH _2- , -O- CH- , -O CH ₃ )

Examples 1-16 2,3,4,5-tetra-O-methyl-1,6-di-O- (1,3-
Dimethylbutyl) sorbitol, 2,4,5-tri-O-me
Cyl-1,3,6-tri-O- (1,3-dimethylbutyl) sol
Bitol, 1,6-di-O- (1,3-dimethylbutyl) -di
-O-methyl-O- (1,3-dimethylbutylidene) sorbi
Tol, O-methyl-1,3,6-tri-O- (1,3-dimethyl)
Rubutyl) -O- (1,3-dimethylbutylidene) sorbit
, 2,3,4,5,6-penta-O-methyl-1-O- (1,3
-Dimethylbutyl) sorbitol, di-O-methyl-1,
3,6, x-Tetra-O- (1,3-dimethylbutyl) sorbit
Synthesis 1) sorbitol with ketals (16a) thermometer with methyl isobutyl ketone mixture Lumpur (16c), a reflux condenser, a Dean - Stark trap, a 3-liter reaction vessel equipped with a calcium chloride tube and a stirrer D- Sorbitol 363.76 g (1.997 mol), methyl isobutyl ketone 1200 g (11.98)
1 mol), paratoluenesulfonic acid monohydrate 18.99
g (0.0998 mol) and 300 ml of hexane were charged. The temperature was raised with stirring, the reaction was carried out at 93 to 95 ° C. for 5 hours, and 60% of the calculated amount of water was distilled off. 60 after reaction
21.16 g (0.199 g) of sodium carbonate
(6 mol) was added for neutralization, and the mixture was stirred at 60 ° C. for 30 minutes, 200 g of water was added, and the mixture was stirred at 60 ° C. for 30 minutes to perform stationary layer separation. After removing the lower layer, the solution was washed with 200 g of a saturated saline solution and evaporated to obtain 544.6 g of the title compound.
This residue was top-cut by vacuum distillation, and 486.2 g of the residue obtained was subjected to pressure filtration (PTFE, 0.2 μm) through 24.31 g of activated clay (5% by weight relative to the residue) to give the title compound (16a) 471. 3 g was obtained (yield 5
5.1%). The gas chromatography purity was 95% [total value of diketal and triketal; diketal / triketal = 33/67 (weight ratio)].

2) Hydrogenated product of ketal of sorbitol and methyl isobutyl ketone (16b) 1 g of autoclave fully dehydrated the compound (16a) obtained in 1) above, 450 g (1.120 mol) and 5% Pd / C (dry product: a product containing 50% water, dried under reduced pressure with a vacuum pump at room temperature for 1 day) (N.E.
9.0 g (2% by weight) of "5% Pd carbon powder 50% water-containing product, E-type, pH 6.0" manufactured by Chemcat Corporation was charged. The mixture was heated with stirring under a hydrogen pressure of 20 kg / cm ^2, in a hydrogen pressure 200 kg / cm ² and reacted for 20 hours at 190 ° C.. After completion of the reaction, the crude title compound (1) was dissolved in 200 ml of hexane, filtered through a membrane filter (PTFE, 0.2 μm) under pressure, and evaporated.
6b) 433 g was obtained (crude yield 95%).

Gas chromatography purity is 90% [total value of dialkyl ether, trialkyl ether, dialkyl ether monoketal, trialkyl ether monoketal, monoalkyl ether and tetraalkyl ether: dialkyl ether / trialkyl ether / dialkyl ether Monoketal / trialkyl ether Monoketal / monoalkyl ether / tetraalkyl ether = 63.5 / 16.0 / 14.7 / 2.
9 / 2.7 / 0.2 (weight ratio)] hydroxyl value 444.5

3) 2,3,4,5-Tetra-O-methyl-1,6
-Di-O- (1,3-dimethylbutyl) sorbitol, 2,4,
5-tri-O-methyl-1,3,6-tri-O- (1,3-dimethylbutyl) sorbitol, 1,6-di-O- (1,3-dimethylbutyl) -di-O-methyl -O- (1,3-dimethylbutylidene) sorbitol, 1,6, x-tri-O- (1,3-dimethylbutyl) -O-methyl-O- (1,3-dimethylbutylidene) sorbitol, 2,3,4,5,6-Penta-O-methyl-1-O- (1,3-dimethylbutyl) sorbitol, di-O-methyl-1,3,6, x-tetra-O- (1 2,3-Dimethylbutyl) sorbitol mixture (16c) 2 equipped with thermometer, reflux condenser, dropping funnel and stirrer
28.5 g of sodium hydride powder in a liter reaction vessel
(1.19 mol) 900 ml of toluene was charged. 100 g of the compound (16b) obtained in 2) above (0.79 mol as a hydroxyl group) dissolved in 100 ml of toluene was added dropwise over 30 minutes at room temperature with stirring under a nitrogen atmosphere, and then 50 ml of toluene was added to raise the temperature. At 110 ° C
The mixture was stirred under reflux for an hour. Then, the mixture was cooled to 50 ° C., and 149.9 g (1.19 mol) of dimethyl sulfate was added at 50 ° C.
Dropped over time. Add 300 ml of toluene to 80 ℃
After aging for 1 hour at room temperature, it was cooled, and 476 g (1.19 mol) of 10% sodium hydroxide aqueous solution was added to 70-80.
Stirred at 30 ° C for 30 minutes. After cooling to room temperature, the layers were allowed to stand and the lower layer was removed. The upper layer was washed 4 times with saturated brine, dried over anhydrous sodium sulfate, and evaporated to obtain 98.4 g of the title compound (16c) as an oily substance (yield 89
%). Gas chromatography was 90% pure.

2,3,4,5-Tetra-O-methyl-1,6-di-O- (1,3-dimethylbutyl) sorbitol 56.8% by weight, 2,4,5-tri-O- Methyl-1,3,6-tri-O-
(1,3-dimethylbutyl) sorbitol 14.3% by weight,
1,6-di-O- (1,3-dimethylbutyl) -di-O-methyl-O- (1,3-dimethylbutylidene) sorbitol 1
3.2% by weight, 1,3,6-tri-O- (1,3-dimethylbutyl) -O-methyl-O- (1,3-dimethylbutylidene) sorbitol 2.6% by weight, 2,3 , 4,5,6-Penta-O-methyl-1-O- (1,3-dimethylbutyl) sorbitol 2.4% by weight, di-O-methyl-1,3,6, x-tetra-O
It was 0.2% by weight of-(1,3-dimethylbutyl) sorbitol. IR (NEAT, cm ^-1 ): 2956, 2878, 2830 (C-H expansion and contraction), 1470, 1374 1350 (C-H bending angle), 1110 (C-O expansion and contraction)

Example 2-1 Kinematic viscosity at 40 ° C. and 100 ° C. of the oil used in the present invention and the oil used in the comparative product (JIS K-22
83) was measured. The results are shown in Tables 1 and 2.

[0257]

[Table 1]

[0258]

[Table 2]

Example 2-2 The fluidity at low temperature of the oil used in the present invention and the oil used in the comparative product was measured. That is, Example 1-1 was placed in a constant temperature bath of -20 ° C.
After allowing the sample used in 1. to stand for 1 hour, it was examined whether or not the sample flowed. The results are also shown in Tables 1 and 2.

Example 2-3 Compositions of oils used in the present invention products and comparative products shown in Tables 3 and 4 and 1,1,1,2-tetrafluoroethane (HFC134a), respectively. Inventive products and comparative products were prepared, and the compatibility of these products was investigated. That is,
Each oil concentration for 1,1,1,2-tetrafluoroethane 10
Vol%, 20Vol%, 30Vol%, 40Vol%
The two-phase separation temperature at low temperature was measured. The results are shown in Tables 3 and 4. As is apparent from the table, the product of the present invention was excellent in compatibility as compared with the comparative product.

[0261]

[Table 3]

[0262]

[Table 4]

Example 2-4 A shielded tube test was conducted to examine the thermal stability of the product of the present invention. That is, 10 g of oil having a water concentration of 20 ppm or less and 5 g of HFC134a were taken in advance in a glass tube, and iron, copper, and aluminum were added as a catalyst to seal the tube. After testing at 175 ° C for 14 days and 28 days, HFC1
The appearance of the composition of 34a and oil and the presence / absence of deposits were examined, and HF
After removing C134a, the acid number of the oil was measured. The results are shown in Tables 5 and 6. As is clear from the table, all the products of the present invention had a good appearance, no precipitates, and good thermal stability.

[0264]

[Table 5]

[0265]

[Table 6]

Example 2-5 A shielded tube test was conducted to examine the hydrolysis resistance of the product of the present invention and the comparative product. That is, in a glass tube, 10 g of oil having a water concentration of 3000 ppm in advance, HFC1
34a5g was taken and iron, copper, and aluminum were added as a catalyst, and the tube was sealed. After testing at 175 ° C for 14 days, HFC
The appearance of the composition of 134a and oil and the presence or absence of deposits were examined.
After removing FC134a, the acid value of the oil was measured. The results are shown in Tables 7 and 8. As is apparent from the table, the product of the present invention had a good appearance, had no precipitate, and did not cause an increase in the acid value like an ester, and was good.

[0267]

[Table 7]

[0268]

[Table 8]

Example 2-6 The volume resistivity (measured according to JIS C-2101) at 25 ° C. of the oil used in the present invention and the oil used in the comparative product was measured. The results are shown in Tables 9 and 10. As is apparent from the table, the product of the present invention was superior in volume resistivity to the comparative product.

[0270]

[Table 9]

[0271]

[Table 10]

Example 2-7 A shielded tube test was conducted in order to examine the thermal stability of the product of the present invention comprising a refrigerating machine oil obtained by adding an additive to the ether used in the present invention and hydrofluorocarbon. That is, 10 g of oil having a water content of 3000 ppm in advance and 5 g of HFC134a were placed in a glass tube, and iron was used as a catalyst.
Copper and aluminum were added and the tube was sealed. After testing at 175 ° C. for 14 days, the appearance of the composition of HFC134a and oil and the presence of deposits were examined, and after removing HFC134a, the water content of the oil was examined. The results are shown in Table 11. As is clear from the table, the product of the present invention has a good appearance and no precipitate,
Furthermore, water could be removed sufficiently.

[0273]

[Table 11]

[0274]

INDUSTRIAL APPLICABILITY According to the present invention, a novel polyhydric ether alcohol derivative which is highly useful in a wide variety of applications such as synthetic lubricating oils can be produced from an inexpensive raw material by a simple method.
Further, the composition for refrigerator working fluid of the present invention comprising a refrigerating machine oil containing the novel polyhydric ether alcohol derivative of the present invention as a base oil and hydrofluorocarbon has excellent compatibility, thermal stability and hydrolyzability. It has an appropriate kinematic viscosity, good low temperature fluidity, and particularly excellent volume resistivity. Therefore, the composition for a working fluid of a refrigerator of the present invention is preferably used as an electric motor-integrated compression refrigerating machine oil used in a refrigerator or an air conditioner.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C10N 30:00 C 30:08 40:30 (72) Inventor Togashi Hiroyasu 1334 Minato Kao, Wakayama City Kao Stock Company Research Center

Claims (13)

[Claims] 1. The following general formulas (I) to (IV): Embedded image Embedded image [Chemical 4] (In the formula, R ₁ is a hydrogen atom or a linear or branched alkyl group having ₁ to 21 carbon atoms, R ₂ is a branched alkyl group having 3 to 17 carbon atoms when R ₁ is a hydrogen atom, R _{2 1}
Is a straight-chain or branched alkyl group having 1 to 21 carbon atoms, it represents a straight-chain or branched alkyl group having 1 to 21 carbon atoms. Alternatively, R ₁ and R ₂ together form a carbon number of 2 to 1.
Forming an alkylene group of 3. _{Two to} six pairs of R ₁ and R ₂ may be the same or different. k ₁ is 0 to 5, p ₁ is 0
˜2, m ₁ is 0 or 1 and k ₁ + (m ₁ +2) p ₁ =
It is a number that satisfies 5. k ₂ and n ₂ are 0 to 4, p ₂ is 0
2, m ₂ is 0 or 1 and k ₂ + (m ₂ +2) p ₂ + n
It is a number that satisfies ₂ = 4. R ₃ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. In the general formula (I), k ₁ oxymethylene group and p ₁ cyclic acetal (acetal or ketal) unit, in the general formula (II), k ₂ and n ₂ oxymethylene groups and p ₂ The arrangement of the cyclic acetal (acetal or ketal) unit, the oxymethylene group in the general formula (III) and the cyclic acetal (acetal or ketal) unit may be random or block. ) A polyhydric ether alcohol derivative represented by any of the above. 2. The polyhydric ether alcohol derivative according to claim 1, wherein the alcohol residue of the polyhydric ether alcohol is derived from sorbitol. 3. The following formula (V): A hexahydric alcohol represented by the general formula (VI) (In the formula, R ₁ represents a hydrogen atom or a linear or branched alkyl group having 1 to 21 carbon atoms, and R ₂ represents 1 to 21 carbon atoms.
Is a linear or branched alkyl group. ) A carbonyl compound represented by) or its reactive derivative (acetal or ketal) is reacted in the presence of an acid catalyst to produce cyclic acetals (acetal or ketal), which are hydrogenated or further alkyl-capped. The method for producing a polyhydric ether alcohol derivative represented by any of the general formulas (VII) to (X). [Chemical 7] Embedded image [Chemical 9] [Chemical 10] (In the formula, R ₁ represents a hydrogen atom or a linear or branched alkyl group having 1 to 21 carbon atoms, and R ₂ represents 1 to 21 carbon atoms.
Is a linear or branched alkyl group. Alternatively, R ₁ and R ₂ together form an alkylene group having 2 to 13 carbon atoms. _{Two to} six pairs of R ₁ and R ₂ may be the same or different. k ₁ is 0 to 5, p ₁ is 0 to 2, m ₁ is 0
Alternatively, the number is ₁ and satisfies k ₁ + (m ₁ +2) p ₁ = 5. k ₂ and n ₂ are 0 to 4, p ₂ is 0 to 2, m ₂ is 0 or 1 and is a number satisfying k ₂ + (m ₂ +2) p ₂ + n ₂ = 4. R ₃ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. In the general formula (VII), k ₁ oxymethylene groups and p ₁ cyclic acetal (acetal or ketal) units, the general formula (VII
And the k ₂ and n ₂ oxymethylene groups in I) and p
_Two cyclic acetals (acetal or ketal)
The units, that is, the oxymethylene group in the general formula (IX) and the cyclic acetal (acetal or ketal) unit may be arranged randomly or in blocks. ) 4. The method for producing a polyhydric ether alcohol derivative according to claim 3, wherein the hexahydric alcohol represented by the formula (V) is sorbitol. 5. In the general formulas (VII) to (X), R ₁ is a hydrogen atom, R ₂ is a linear or branched alkyl group having 1 to 13 carbon atoms, or R ₁ is 1 to ₁ carbon atom. The method for producing a polyhydric ether alcohol derivative according to claim 3, wherein R ₂ is a linear or branched alkyl group having 13 carbon atoms and R ₂ is a linear or branched alkyl group having 1 to 13 carbon atoms. 6. The following general formula (XI): (In the formula, R ^{1 to} R ⁶ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, provided that the total carbon number of R ^{1 to} R ⁶ is 8 ~ 4
0. ) A composition for a working fluid of a refrigerator, which comprises a refrigerating machine oil containing a polyhydric ether alcohol derivative represented by the formula 4) as a base oil and hydrofluorocarbon. 7. The composition for refrigerating machine working fluid according to claim 6, wherein the compound represented by the general formula (XI) is a compound in which a hexavalent alcohol residue is provided by sorbitol. 8. A compound represented by the general formula (XI) has the formula (V): And a hexavalent alcohol represented by the following general formula (XII) (In the formula, R ⁷ is a hydrogen atom, or a straight chain having 1 to 13 carbon atoms,
Indicates a branched or cyclic alkyl group, R ⁸ has 1 carbon atom
The linear, branched or cyclic alkyl group of 13 is shown.
Alternatively, R ⁷ and R ⁸ together form an alkylene group having 2 to 13 carbon atoms. However, R ⁷ and R ⁸ are R ⁷ and R ⁸
Is an alkyl group having at least one hydrogen atom in any of the α-positions, and the total carbon number of R ⁷ and R ⁸ is 1 to 13
Is. ), A cyclic ketal or a cyclic acetal is synthesized from one or more kinds of carbonyl compounds (ketones or aldehydes) or reactive derivatives thereof (ketals or acetals) by ketalization, acetalization, transketalization or transacetalization. The composition for a working fluid of a refrigerator according to claim 6 or 7, which is synthesized by hydrogenating a compound to obtain a polyhydric ether alcohol and further alkyl-capping the same. 9. A) 0.05 to 2.0 parts by weight of a compound having an epoxy group and b) 0.01 to 0.01 to 100 parts by weight of a polyhydric ether alcohol derivative represented by the general formula (XI). 9. 6 to 8 which further comprises at least one selected from the group consisting of 100 parts by weight, 0.01 to 100 parts by weight of c) acetal or ketal, and 0.05 to 5 parts by weight of carbodiimide. The composition for a working fluid of a refrigerator according to any one of claims. 10. The following general formula (XIII _AA ) or (XII
I _BB ) [Chemical 14] (In the formula, R ^{1 to} R ⁶ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, and R ⁷ represents a hydrogen atom or 1 to 13 carbon atoms. linear, branched, or shows a cyclic alkyl group, R ⁸ is a straight chain of 1 to 13 carbon atoms, carbon atoms. Alternatively R ⁷ and R ⁸ showing a branched or cyclic alkyl group together 2-1
Forming an alkylene group of 3. However, the general formula (XIII _AA )
R ^{1 to} R ³ and R ^{6 to} R ⁸ in formula (XI
II _BB ) has a total carbon number of R ¹ and R ^{4 to} R ⁸ of 8 to
40, and the total carbon number of R ⁷ and R ⁸ is 1 to 13. It is to be noted that a to e are reference numerals given to represent the arrangement of the structural units, and a to c or d to e may be arranged in any order. ) A composition for a working fluid of a refrigerator, which comprises a refrigerating machine oil containing a polyhydric ether alcohol derivative represented by the formula 4) as a base oil and hydrofluorocarbon. 11. The composition for a working fluid of a refrigerator according to claim 10, wherein the compound represented by the general formula (XIII _AA ) or (XIII _BB ) has a hexahydric alcohol residue provided by sorbitol. 12. A compound represented by the general formula (XIII _AA ) or (XIII _BB ) is represented by the formula (V): A hexahydric alcohol represented by the general formula (XII) (In the formula, R ⁷ is a hydrogen atom, or a straight chain having 1 to 13 carbon atoms,
Indicates a branched or cyclic alkyl group, R ⁸ has 1 carbon atom
The linear, branched or cyclic alkyl group of 13 is shown.
Alternatively, R ⁷ and R ⁸ together form an alkylene group having 2 to 13 carbon atoms. However, R ⁷ and R ⁸ are R ⁷ and R ⁸
Is an alkyl group having at least one hydrogen atom in any of the α-positions, and the total carbon number of R ⁷ and R ⁸ is 1 to 13
Is. ), A cyclic ketal or a cyclic acetal is synthesized from one or more kinds of carbonyl compounds (ketones or aldehydes) or reactive derivatives thereof (ketals or acetals) by ketalization, acetalization, transketalization or transacetalization. 12. The composition for a working fluid of a refrigerator according to claim 10 or 11, which is synthesized by hydrogenating to obtain a polyhydric ether ketal alcohol or a polyhydric ether acetal alcohol, which is further alkyl-capped. 13. A compound having an epoxy group, a), based on 100 parts by weight of the polyhydric ether alcohol derivative represented by the general formula (XIII _AA ) or (XIII _BB ) 0.05 to 2.
At least one selected from the group consisting of 0 part by weight, b) 0.01 to 100 parts by weight of orthoester, c) 0.01 to 100 parts by weight of acetal or ketal, and d) 0.05 to 5 parts by weight of carbodiimide. The composition for refrigerator working fluid according to any one of claims 10 to 12, further comprising the above components.