KR960014930B1 - Lubricating oil for compression-type refrigerators and polyoxyalkyleneglycol derivative - Google Patents

Abstract

None.

Description

Lubricants and Polyoxyalkylene Glycol Derivatives for Compressed Refrigerators

1 is a ¹³ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 1. FIG.

2 is a ¹³ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 5. FIG.

3 is a ¹³ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 7. FIG.

4 is a ¹³ C-NMR spectrum of the polyoxy alkylene glycol obtained in Production Example 10.

5 is a ¹³ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 11.

6 is a ¹³ C-NMR spectrum of the polyoxy alkylene glycol obtained in the reference example.

7 is a ¹³ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 13.

8 is a ¹³ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 14.

9 is a ¹ C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 1. FIG.

10 is a ¹ H-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 4. FIG.

11 is a ¹ H-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 10.

12 is a ¹ H-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 11. FIG.

The present invention relates to lubricating oils for compressed refrigerators and to novel polyoxy alkylene glycol derivatives.

More specifically, 1,1,1,2, which may be a substitute for chlorofluorocarbons (CFCs), such as other dichlorine difluoro ethane (hereinafter referred to as R-12), of refrigerants that are problematic due to environmental pollution. To lubricants for compression type refrigerators having good compatibility with hydrofluorocarbons such as tetrafluoroethane (hereinafter referred to as R-134a) and excellent lubricity and new polyoxyalkylene glycol derivatives effective as the lubricants. It is about.

Hydrofluol carbon herein means hydrofluorocarbons (HFC) represented by R-134a and hydrochlorofluorocarbons (HCFC) represented by R-22. Generally, a compression type refrigerator is composed of a compressor, a condenser, an expansion valve, and an evaporator, and has a structure in which a mixed liquid of a refrigerant and lubricating oil circulates in this sealed system.

Such compressors also depend on the type of equipment, but in general, the temperature reaches 50 ° C or higher in the compressor and -40 ° C in the cooler. It is necessary to circulate in this system without phase separation in the temperature range. If phase separation occurs during operation of the refrigerator, it has a significant adverse effect on the life and efficiency of the device.

For example, in the compressor part, refrigerant and lubricant are separated from the moving parts due to poor lubrication, which leads to a significant shortening of the life of the device. On the other hand, when phase separation occurs in the evaporator, a lubricant having high viscosity exists in the heat exchange efficiency. It leads to degradation.

In addition, since the lubricating oil for the refrigerator is used for the purpose of lubricating the movable part of the refrigerator, the lubricating performance is also important.

In particular, since the temperature inside the compressor becomes high, it is important to maintain the oil film necessary for lubrication. The viscosity required depends on the type of compressor used and the conditions of use, but usually, the viscosity of the lubricant before mixing with the refrigerant is preferably 2-50 cSt at 100 ° C.

If the viscosity is lower than this, the oil film becomes thin and easily causes lubrication defects. If the viscosity is high, the efficiency of heat exchange decreases. Conventionally, R-12 is widely used as a refrigerant of a compression type refrigerator, and various mineral oils and synthetic oils satisfying the above-described required characteristics have been used as lubricants.

However, since R-12 is likely to cause environmental pollution, such as destroying the ozone layer, its regulations have become strict in the world. For this reason, hydrofluorocarbon represented by R-134a has attracted attention as a new refrigerant. This hydrofluorocarbon, in particular R-134a, is less likely to destroy the ozone layer and can be replaced with R-12 without changing the structure of the conventional refrigerator.

When a hydrofluorocarbon such as R-134a, which is used instead of R-12, is used as the refrigerant of the compressed refrigerator, as a lubricant, of course, it has excellent compatibility with hydrofluorocarbons such as R-134a and the required performance. It is required to have excellent lubrication performance that satisfies the requirements.

However, lubricating oils that have been used with conventional R-12 have poor compatibility with hydrofluorocarbons such as R-134a, and therefore new lubricating oils suitable for these compounds are needed. In this case, it is particularly desired to change the structure of the device in the replacement of the R-12, especially in the automobile air conditioner, and it is not desirable to greatly change the structure of the field value because of the lubricant. Accordingly, there is a need for a lubricant having extremely good compatibility with hydrofluorocarbons such as R-134a.

As lubricating oils having compatibility with R-134a, for example, ulcon LB-165 and ulcon LB-525 (both manufactured by Union Carbide Co., Ltd.) of polyalkylene glycol are known, and these lubricating oils are at least -50 deg. It is reported that R-134a is compatible with the total composition ratio at low temperatures. [Research Disclosure] No. 17463 (October 1978). Moreover, the high viscosity refrigeration oil composition based on polyoxy fluorene glycol mono butyl ether is also known (Japanese Unexamined-Japanese-Patent No. 57-42119).

However, these lubricating oils are polyalkylene glycol derivatives having one end of polypropylene glycol as a hydroxyl group and the other end having n-butyl ether bonds, which have relatively good compatibility with R-134a on the low temperature side, but are compatible on the high temperature side. It is also known that this is not sufficient, for example, the aforementioned ulcon LB-525 causes phase separation with R-134a at room temperature (US Pat. No. 4,755,316).

On the other hand, polyoxyalkylene glycols having at least two hydroxyl groups in one molecule have been proposed as having good compatibility with R-134a (US Pat. No. 4,755,316). However, compatibility in this polyoxyalkylene glycol is not necessarily sufficient. It is also known that polyoxyalkylene glycols exhibit a temperature dependence that, once the mixture with hydrofluorocarbons is heated from low to high temperature, it is generally phase separated or once the mixture is compatible.

Moreover, it is also known that compatibility will fall when the molecular weight of polyoxyalkylene glycol increases. On the other hand, it is proposed to use R-134a and a compound which can dissolve it in an absorption chiller (Japanese Patent Laid-Open No. 56-79175). However, this absorption refrigerator is completely different from the compression type refrigerator described above, and furthermore, the tetraethylene glycol dimethyl ether described in the examples of the above publication is not suitable as a lubricating oil of the compression type refrigerator because of its remarkably low viscosity. As such, a phenomenon has been found that no lubricant for a compression type refrigerator having sufficient compatibility with R-134a and excellent lubrication performance has yet been found, and its development is strongly desired.

It is an object of the present invention that the compatibility with hydrofluorocarbons such as R-12 or R-134a, which can be a substitute for R-12, a refrigerant which is a problem due to environmental pollution, or other difficult hydrofluorocarbons, can be used in the entire operating temperature range. The present invention provides a lubricant for a compression type refrigerator, which is good over and has excellent lubricating performance. Another object of the present invention is to provide a novel polyoxy alkylene glycol derivative effective for lubricants for compression type refrigerators.

That is, the present invention is a general formula,

[Formula 1]

[R ¹ -R ⁴ are each a hydrogen, a monovalent hydrocarbon group of 1 to 10 carbon atoms or general formula (II)

[Formula 2]

(R ⁵ and R ⁶ each represent hydrogen, a C 1-10 monovalent hydrocarbon group or a C 2-20 alkoxy alkyl group, and R ⁷ represents a total carbon number 3 having a C 2-5 alkylene group and an alkyl group as a substituent) A substituted alkylene group having 4 to 10 carbon atoms having a substituted alkylene group or an alkoxy alkyl group as a substituent, n is an integer of 0-20, and R ⁸ represents a monovalent hydrocarbon having 1 to 10 carbon atoms). And at least one of R ¹ -R ⁴ is a group represented by the general formula (II)], to provide a lubricating oil for a compressed refrigerator having a polyoxy alkylene glycol derivative having at least one structural unit represented as a main component. .

Moreover, this invention has the above-mentioned structural unit, has a hydroxyl group, a C1-C10 acyloxy group, a C1-C10 alkoxy group, or aryloxy, respectively, at the terminal position, and the kinematic viscosity in 100 degreeC is 1-. It is to provide a polyoxy alkylene glycol derivative which is 100 cSt.

The lubricating oil for compressed refrigerators of the present invention contains at least one structural unit represented by general formula (I). Wherein R ¹ -R ⁴ are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or general formula (II)

[Formula 2]

Will be displayed.

The monovalent hydrocarbon group having 1 to 10 carbon atoms is generally an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl having 7 to 10 carbon atoms. Group. Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, various nonyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various decyl groups, vinyl groups, Alkenyl groups, cyclopentyl groups, cyclohexyl groups, such as aryl groups, propenyl groups, isopropenyl groups, various butenyl groups, pseudopentenyl groups, various hexylyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, and various desenyl groups And aryl groups such as cycloalkyl group phenyl groups, various tolyl groups, various xylyl groups, naphthyl groups, and aralkyl groups such as benzyl groups, 1-phenylethyl groups, 2-phenylethyl groups, and 2-phenylethyl groups.

Among these, monovalent hydrocarbons having 6 or less carbon atoms are preferable, and alkyl groups having 3 or less carbon atoms, particularly methyl groups, are most suitable. In General Formula (II), R ⁵ and R ⁶ each represent hydrogen, a C 1-10 monovalent hydrocarbon group, or a C 2-20 alkoxy alkyl group, but the monovalent hydrocarbon group generally has 1 C 1. An alkyl group of -10, an alkenyl group of 2 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, an allyl group of 6 to 10 carbon atoms, or an arylalkyl group of 7 to 10 carbon atoms.

Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, vinyl groups, Kenyl groups, cyclopentyl groups, cyclohexyl groups, such as allyl groups, propenyl groups, isopropenyl groups, various butenyl groups, various pentenyl groups, various hesenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, and various desenyl groups Aryl groups such as cycloalkyl groups, phenyl groups, various tolyl groups, various xylyl groups, naphthyl groups, or arylalkyl groups such as benzyl groups, 1-phenylethyl groups and 2-phenylethyl groups, methoxymethyl groups, ethoxymethyl groups, n- Propoxymethyl group, isopropoxymethyl group, various butoxymethyl groups, various pentoxymethyl groups, various hexoxymethyl groups, various heptopmethylmethyl groups, various octoxymethyl groups, various nonyloxymethyl groups, 1-methoxyethoxy, 2-methoxy Ethyl group, 1-ethoxyethyl group, 2- Methoxyethyl group, various propoxyethyl groups, various butoxyethyl groups, various phenoxyethyl groups, various nucleosoethyl groups, various heptopethyl ethyl groups, various octoxyethyl groups, various methoxypropyl groups, various ethoxypropyl groups, various propoxypropyl groups , Various butoxypropyl groups, various pentoxypropyl groups, various hexoxypropyl groups, various heptoxyethyl groups, various methoxybutyl groups, various ethoxybutyl groups, various propoxybutyl groups, various butoxybutyl groups, various pens Methoxybutyl group, various hexoxybutyl groups, various methoxypentyl groups, various ethoxypentyl groups, various propoxypentyl groups, various butoxypentyl groups various pentoxypentyl groups, various methoxyhexyl groups, various ethoxyhexyl groups Alkoxy such as various propoxyhexyl groups, various butoxyhexyl groups, various methoxyheptyl groups, various ethoxyheptyl groups, various propoxyheptyl groups, various methoxyoctyl groups, various ethoxyoctyl groups, and various methoxynonyl groups Alkyl groups I can lift it.

Among these, alkyl having 3 or less carbon atoms or alkoxy alkyl groups having 6 or less carbon atoms is preferable. As R ⁵ and R ⁶ , hydrogen is most suitable among them.

R ⁷ represents an alkylene group having 2 to 5 carbon atoms, a substituted alkylene group having 3 to 5 carbon atoms having an alkyl group as a substituent, or an alkoxy alkyl group as a substituent, and a substituted alkylene group having ⁴ to 10 carbon atoms, specifically, an ethylene group, 1-methylethylene group, 2-methylethylene group, ethylethylene group: 1,1-dimethyl ethylene group: 1,2-dimethylethylene group: n-propyl ethylene group: isopropylethylene group: 1-ethyl-2-methyl Ethylene group: 1-ethyl-1-methylethylene group: trimethylene group, tetramethylene group: pentamethylene group: (methoxymethyl) ethylene group: (ethoxymethyl) ethylene group: (methoxyethyl) ethylene group: 1 -Methoxymethyl-2-methylethylene group: 1,2-: (bismethoxymethyl) ethylene group: 1,1- (bismethoxymethyl) ethylene group: (ethoxyethyl) ethylene group: 1,2- (Bisethoxyethyl) Ethylene group: 1,1- (bisethoxyethyl) Ethylene group: 2-methoxy-1,3-propylene group, etc. are mentioned, Preferably it is C6 or less Teal is a group and a substituted ethylene group.

Moreover, as R <^7> , an ethylene group, 1-methylethylene group, 2-methyl ethylene group, and trimethylene group are the most suitable among these. Moreover, n which shows the repeating number of the unit of R <^7> O is an integer of 0-20, Preferably it is an integer of 0-3.

R ⁸ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, but generally an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or carbon atoms The arylalkyl group of 7-10 is shown.

Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, vinyl groups, Alkenyl, cyclopentyl, and cyclohexyl groups such as allyl, propenyl, isopropenyl, various butenyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups and various desenyl groups And an aryl group such as a cycloalkyl group, a phenyl group, various tolyl groups, various xylyl groups, naphthyl group, such as a real group, or an allylalkyl group, such as a benzyl group, 1-phenylethyl group, and 2-phenylethyl group.

Among these, hydrocarbons having 6 or less carbon atoms are preferable, and hydrocarbons having 1-3 carbon atoms are particularly preferable. Moreover, it is group represented by at least ¹ general formula (II) among R <^1> -R <^4> in general formula (I) mentioned above. In particular, one of R ¹ and R ³ is a group of general formula (II), and it is preferable that the other one of R ¹ , R ³ and R ² , R ⁴ are each hydrogen or a monovalent hydrocarbon group having 1-10 carbon atoms. Do. Moreover, it is also preferable that two of R <^1> -R <^4> is group represented by general formula (II).

The polyoxyalkylene glycol derivative which is the main component of the lubricating oil of the present invention contains at least one structural unit represented by the general formula (I), but more specifically, a homopolymer of the structural unit of the general formula (I). , Interpolymers of two or more different structural units contained in general formula (I) and other structural units different from those of general formula (I), for example, of general formula (III)

[Formula 3]

Three types of interpolymers of the structural units represented by [R ^{31 to} R ³⁴ each represent hydrogen or an alkyl group having 1 to 3 carbon atoms] can be classified.

Very suitable examples of the homopolymers described above include 1-200 structural units A represented by the general formula (I), and the terminal groups each have a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or And aryloxy groups.

On the other hand, a very suitable example of the interpolymer has 1-200 of two types of structural units A and B represented by general formula (I), or 1-200 of structural unit A represented by general formula (I). It has 1-200 structural units C represented by a dog and general formula (II), and a terminal group consists of a hydroxyl group, a C1-C10 acyloxy group, a C1-C10 alkoxy group, or an allyloxy group, respectively. .

These hybrid polymers may be composed of alternating hybrid polymerization between structural unit A and structural unit B (or structural unit C), random hybrid polymerization, block interpolymers, or copolymers in which the structural unit B is graft bonded to the main chain of the structural unit A. There are many things.

The above-mentioned polyoxy alkylene glycol derivative used for the lubricating oil of this invention can be manufactured, for example by the following method.

(A) method

General Formula,

[Formula 4]

When the oxirane compounds represented by [wherein R ¹ -R ⁴ are the same as described above] are mixed or polymerized by mixing two or more types of compounds represented by formula (IV) alone, a polyoxyalkylene glycol derivative is obtained. Lose. In addition, the compound represented by the formula (IV) and a general formula,

[Formula 5]

Polyoxyalkylene glycol derivatives can be prepared by mixing and copolymerizing an alkylene oxide having 2 to 8 carbon atoms such as ethylene oxide or porophilene oxide represented by the formula (wherein R ³¹ -R ³⁴ is as described above). .

Although there are various kinds of oxirane compounds represented by the general formula (IV) depending on the type of R ¹ -R ⁴ , specifically, glycidyl methyl ether: ethylglycidyl ether, propyl glycidyl ether, and butyl glycine Dyl ether: 2-ethylhexyl glycidyl ether: 2-methyloctyl glycidyl ether: vinyl glycidyl ether: allyl glycidyl ether: phenylglycidyl ether: sec-butylphenyl glycidyl ether: 4, 7-dioxa-1,2-epoxyoctane: 1,2-epoxy-4,7,10-trioxa undecane: 1,2-epoxy-4,7,10,13-tetraoxatetradecane: 4, 7-dioxa-1,2-epoxy-5-methyloctane: 4,7-dioxa-1,2-epoxy-6-methyloctane: 6,9-dimethyl-1,2-epoxy-4,7, 10-trioxoundane: 1,2-epoxy-4,7,10,13-tetraoxa-6,9,12-trimethyl tetradecane, 1,2-epoxy-5-methyl-4,7,10- Trioxoundane: 1,2-epoxy-8-methyl-4,7,10-trioxoundane: 2,7-diox-4,5-epoxyoctane: 4,5-epoxy-9- Til-2,7,10-trioxoundecan: 4,5-epoxy-2,7,10,13-tetraoxatetradecane: 7,8-epoxy-2,5,10,13-tetraoxa tetradecane : 3,12-dimethyl-7,8-epoxy-2,5,10,13-tetraoxatetradecane: 1,2-epoxy-3-methoxy-5-oxahexane: 4,8-dioxa-1 , 2-epoxy-6-methoxynonane: 4,7-dioxa-1,2-epoxy-5- (2-oxapropyl) -octane: 3,5-bis (2-oxapropyl) -4,7 Dioxa-1,2-epoxyoctane: 3,6-bis (2-oxapropyl) -4,7-dioxa-1,2-epoxy-octane: 6,9-bis (2-oxapropyl) 1,2-epoxy-4,7,10-oxoundecan. Moreover, as an initiator of superposition | polymerization, well-known, such as water, alkali hydroxide, a 1-6 valent alcohol: alkoxide: thiol: 2,2'- thiodiethanol: sodium alkoxide of 2, 2- thiodiethanol, a phenol, a phenoxide, an amine, etc. Compounds can be used.

(B) method

In the homopolymer of the oxirane compound represented by at least one general formula (IV) obtained in the above-mentioned method (A), the oxirane compound represented by the general formula (IV) represented by the general formula (IV) The target polyoxy alkylene glycol derivative can be prepared by polymerizing an alkylene oxide having 2 to 8 carbon atoms. In this case, two kinds of reactions can be carried out continuously in one reaction vessel.

(C) method

Polyoxyalkylene glycols are obtained by polymerizing alkylene glycols having 2 to 8 carbon atoms represented by general formula (V), followed by oxirane compounds represented by general formula (IV) or the oxirane compounds and general formula The target polyoxyalkylene glycol derivative can be produced by polymerizing with the alkylene oxide of (V). In this case, two kinds of reactions can be carried out continuously in one container.

By freezing all or part of the terminal hydroxyl groups of the polyoxyalkylene glycol obtained by the method of (A)-(C) with esters or ethers, the solubility is improved, the hygroscopicity is reduced, the viscosity index is improved, and the lubricity is improved. You can improve the performance as well again. The hydrocarbon in the ester and ether residues preferably has 1 to 10 carbon atoms. In addition, in order to maintain the thickness of the oil film required for lubrication, the lubricating oil of the present invention has a kinematic viscosity of 1-100 cSt. In particular, 2-50 cSt is preferable.

In order to produce the polyoxyalkylene glycol derivative of this kinematic viscosity range, it is preferable to select a raw material initiator and reaction conditions in the above-mentioned (A)-(C) method.

However, it can adjust to the kinematic viscosity of a preferable range, even if it mixes several types other than the said kinematic viscosity range. The polyoxyalkylene glycol derivative obtained in this way may be used independently, and may be used in combination of 2 or more type. Again, this may be mixed to improve the performance of other lubricants.

When lubricating oil mainly composed of this polyoxyalkylene glycol lubricator is used as a lubricating oil of a compression type refrigerator, a state in which it is mixed with hydrofluorocarbon (such as R-134a) as a refrigerant (that is, the polyoxyalkylene glycol derivative) And a mixture of hydrofluorocarbons).

In addition, the lubricant of the present invention includes various additives conventionally used in lubricating oils such as load-bearing additives, chlorine trapping agents, antioxidants, metal deactivators, antifoaming agents, clean dispersants, viscosity index improvers, oily agents, antiwear additives, Extreme pressure agents, rust inhibitors, corrosion inhibitors, pour point depressants and the like can be added as desired.

Examples of the load-bearing additives described above include monosulfides, polysulfides, sulfoxides and sulfones, thio sulfinates, sulfide oils and fats, thiocarbonates, thiophenes, thiazoles, and methanesulfonic acid esters. Phosphoric acid esters, such as organosulfur compounds, phosphate monoesters, phosphate diesters, phosphate triesters, and (tricrezyl phosphate), phosphorous acid monoesters, phosphorous acid diesters, and phosphorous acid triesters Polyphosphoric esters such as phosphite esters, thiophosphoric esters such as thiophosphoric acid triesters, higher fatty acid hydroxy aryl fatty acids, fatty acid polyhydric alcohol esters such as carboxylic acid-containing polyhydric alcohol esters, metal soaps, Of fatty acid esters such as acrylic acid esters of organic chlorine such as chlorinated hydrocarbons, chlorinated carboxylic acid derivatives, fluorinated papers Of organic fluorine such as aliphatic carboxylic acids, fluorinated ethylene resins, fluorinated alkyl polysiloxanes, unsaturated graphites, alcohols such as higher alcohols, naphthenates (lead naphthenate), fatty acid salts (lead fatty acids), and thiophosphates (Dialkyl zinc dithiophosphate), thiocarbamates, organic molybdenum compounds, organotin compounds, organic germanium compounds and boric acid esters.

Examples of the chlorine trapping agent include glycidyl ether-containing compounds, epoxidized fatty acid monoesters, epoxidized fats and oils, and epoxy cycloalkyl group-containing compounds.

Examples of the antioxidant include phenols (2,6-di-t-butyl-p-cresol) aromatic amines (α-naphthylamine).

Examples of the metal fluorinating agents include benzotriazole derivatives. Antifoaming agents include silicone oil (dimethyl polyoxane), polymethacrylates and the like.

Examples of the viscosity dispersant include sulfonates, phenates, succinic acid imides, and the like.

Examples of the viscosity index improver include polyacrylate, polyisobutylene, ethylene-propylene, interpolymers, styrene-diene hydrogenated interpolymers, and the like.

The lubricating oil of the present invention has excellent compatibility with refrigerants and lubricating performance, and is used for compressed ceramics, but unlike conventional lubricating oils, hydrofluorocarbons such as R-134a (specifically, 1,1 in addition to R-134a described above) -Dichlorol-2,2,2-trifluoroethane (R-123): 1-chloro-1,1-difluoroethane (R-142a): 1,1-difluoroethane (R- 152a): Compatibility with chloro difluoroethane (R-22) or trifluoromethane (R-23) is good.

Therefore, the lubricating oils of the present invention are very suitable for their hydrofluorocarbons, especially for compression type refrigerators using R-134a as a refrigerant.

Moreover, it can also mix and use with the other compression type lubricating oil for the purpose of improving compatibility with a refrigerant | coolant.

Next, the polyoxyalkylene glycol derivative of the present invention has a structural unit represented by the general formula (I) described above, and has a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms at each terminal position, or It has an aryloxy group and has a kinematic viscosity of 1-100 cSt at 100 ° C. Especially as this polyoxy alkylene glycol derivative, the following three types of compound group of (a), (b), and (c) are mentioned.

(a) general formula (I- (a))

R ¹¹ -R ¹⁴ are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or general formula (II- (a))

(R <^5> , R <^6> and R <^8> are as above-mentioned, R <^17> has a C3-C5 alkylene group, the C3-C5 substituted alkylene group which has an alkyl group as a substituent, or the total carbon number which has an alkoxy substituent 4-10 Is a substituted alkylene group, n represents an integer of 1-20), and at least one of R ¹¹ -R ¹⁴ is a group represented by the general formula (II- (a)). 1-200 structural units, each having a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group, and having a kinematic viscosity of 1 to 100 cSt at 100 ° C ( Derivative (a)).

(b) general formula (I- (b))

[R ²¹ -R ²⁴ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms or a general formula (II- (b)).

A group represented by (R ⁵ -R ⁸ and n 'are as described above) and at least one of R ²¹ -R ²⁴ is a group represented by General Formula (II- (b)). General formula (III)

[Formula 3]

[R ³¹ -R ³⁴ each represent hydrogen, an alkyl group having 1-3 carbon atoms] is a copolymer having 1-200 structural units each, a hydroxyl group at each terminal position, an acyloxy group having 1-10 carbon atoms, Having a C1-C10 alkoxy group or an aryloxy group, and having a kinematic viscosity in 100 degreeC 1-100 cSt (derivative (b)).

(c) general formula (I- (c))

[R ⁴¹ -R ⁴⁴ are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or general formula (II)

[Formula 2]

(R ⁵ -R ⁸ and n are the same as described above), and at least two of R ⁴¹ -R ⁴⁴ are groups represented by the general formula (II). 1-200 structural units represented by It has a C1-C10 acyloxy group, a C1-C10 alkoxy group, or an aryloxy group, respectively, and a kinematic viscosity in 100 degreeC is 1-100 cSt in the terminal position (derivative (c)).

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Production Example 1]

3.0 g (0.056 mol) of powdered sodium methoxide was added to a 200 ml stainless steel autoclave to which a stirrer and a liquid introduction tube were attached, sealed, and heated to 110 ° C., a mixture of glycidyl methyl ether and propylene oxide under stirring ( 120 g was injected into the autoclave over 13 hours from the liquid introduction tube by molar ratio 1: 3). After dissolving 120 ml of water and 240 ml of methanol in the reaction mixture, the solution was passed through a column of 200 ml of cation exchange resin to remove sodium ions. After removing the methanol water, it was dried under vacuum pressure (0.4mm Hg) at 100 ° C. for 1 hour to remove polyoxyalkylene glycol (Glycidyl methyl ether propylene oxide interpolymer) (one end group is methoxy group and the other end). 115 g of this receiver was obtained.

The nuclear magnetic resonance ( ¹³ C-NMR) spectrum (solvent: heavy chloroform) is shown in FIG. 1 in the carbon isotope of this polyoxy alkylene glycol. Further, the polyoxyalkylene proton nuclear magnetic resonance ⁽¹ H-NMR) spectrum of the glycol: represents a (heavy chloroform solvent) of claim 9, FIG.

[Production Example 2]

3.0 g of powdered sodium methoxide was added to a 200 ml stainless steel autoclave to which a stirrer and a liquid introduction tube were attached and sealed, and heated at 110 ° C., 100 g of glycidyl methyl ether was stirred for 9 hours from the liquid introduction tube. Injected over autoclave. After dissolving by adding 200 ml of water 100ml ethanol to the reaction mixture, the solution was passed through a column of 200ml of cation exchange resin and then passed through a column of 200ml of anion exchange resin to remove sodium ions.

After methanol and water were removed, the resultant was dried under vacuum pressure (0.4 mmHg) at 100 ° C. for 1 hour, and polyoxy alkylene glycol (the one end group is a methoxy group and the other end is a hydroxyl group) of the desired glycidyl methyl ether polymer. ) 89 g.

[Manufacture example 3]

50 g of polyoxyalkylene glycol inducer, which is a copolymer of glycidyl methyl ether and propylene oxide, obtained in Formulation Example 1 in a 300 ml three-necked flask with a stirrer and a distillation head, 28% by weight of sodium mitoxide, methanol solution 10 g (0.052 mol of sodium methoxide) and 80 ml of toluene were added and heated to remove methanol and about 30 ml of toluene.

After cooling, the contents were transferred to an autoclave of 200 ml stainless steel with stirrer, 15 g (0.11 mol) of methyl iodide was added and sealed, and the temperature was raised from 50 ° C to 75 ° C over 4,5 hours while stirring. It kept at 90 degreeC for 2.5 hours.

After cooling to room temperature, the reaction mixture was dissolved in a mixture of 200 ml of water and 100 ml of methanol, and passed through a column of 200 ml of a cation exchange resin followed by 200 ml of anion exchange resin to remove sodium ions and iodide ions.

After methanol and water were removed, a vacuum pump was dried under reduced pressure (0.4 mmHg) for 1 hour at 100 ° C. to obtain 43 g of a polyoxyalkylene glycol derivative (methoxy group at both ends) as a target glycidyl methyl ether propylene oxide interpolymer. Got it.

[Production Example 4]

In Preparation Example 1, 2.0 g (0.37 mol) of sodium methoxide and 60 g of a mixture of glycidyl methyl ether and propylene oxide (molar ratio 1: 3) were used and injected into the autoclave over 8,5 hours. The same procedure as in Production Example 1 was performed to obtain 58 g of a polyoxyalkylene glycol derivative (one end of which is a methoxy group and the other end of which is a hydroxyl group) which is a target glycidyl methyl ether propylene oxide interpolymer.

¹ H-NMR spectrum (solution: heavy chloroform) of this derivative is shown in FIG.

Production Example 5

In the preparation example 2, except that 2.0 g (0.037 mole) of sodium methoxide was used and 100 g of glycidyl methyl ether was injected into the autoclave over 10 hours, the same procedure as in Preparation Example 2 was performed. 93 g of polyalkylene glycols (the one end of which is a methoxy group and the other end of which are hydroxyl groups) which are cylyl methyl ether polymers were obtained. ¹³ C-NMR spectrum (solution: heavy chloroform) of this polyalkylene glycol is shown in FIG.

[Manufacture example 6]

To 2,2'-thiodiethanol 7.68 (0.062 mol), 20 g of a 28% by weight methanol solution of sodium methoxide (0.10 mol of sodium methoxide) and 50 cc of toluene were added, followed by stirring at 70 ° C for 4 hours to remove methanol. Further, under vacuum pump pressure reduction (0.3 mmHg), unreacted 2,2'-thiodieethanol and toluene were removed at 100 ° C for 1 hour, and 9.5 g of sodium alkoxide of 2,2'-thiodieethanol was removed. Got it.

6.14 g of sodium alkoxide was added to a 200 ml stainless steel autoclave to which a stirrer and a liquid introduction tube were attached and sealed, and heated at 110 ° C., 100 g of glycidyl methyl ether was stirred for 14,5 hours from the liquid introduction tube. Inject into the autoclave throughout.

After cooling the autoclave, 28 g (0.18 mole) of methyl iodide was added thereto, heated at 60 ° C. for 2.5 hours, and salts were removed by the same method as in Preparation Example 3, and polyoxy alkylene, a glycidyl methyl ether polymer of interest. 93 g of glycol derivatives (methoxy groups at both ends) were obtained.

[Manufacture example 7]

1.94 g (0.028 mole) of potassium methoxyside in Preparation Example 1 and addition reaction of 4,7-dioxa-1,2-epoxyoctane (epichlorohydrin and 2-methoxyethanol in the presence of sulfuric acid) 4,7-dioxa-1 by the same procedure as in Production Example 1, except that 50 g of the obtained chlorohydrin was obtained and then treated with alkali again and then injected into an autoclave over 20 hours. 48 g of polyoxy alkylene glycol derivatives (one end of which is a methoxy group and the other of which is a hydroxyl group) which is a, 2-epoxyoctane polymer were obtained. The ¹³ C-NMR spectrum (solution: heavy chloroform) of this polyalkylene glycol is shown in FIG.

[Manufacture example 8]

1.94 g (0.028 mol) of potassium methoxide in Preparation Example 1 and 4,7-dioxa-1,2-epoxy-5-methyloctane (epichlorohydrin and 1-methoxy-2-propanol) Synthesis by addition reaction in the presence of sulfuric acid to obtain chlorohydrin and further treatment with alkali) The same procedure as in Production Example 1 was carried out except that the mixture was injected into an autoclave over 19 hours using 50 g of 4, 44 g of polyoxy alkylene glycol derivatives (a methoxy group at one end and a hydroxyl group at the other end) of 7-dioxa-1,2-epoxy-5-methyloctane polymer were obtained.

[Manufacture example 9]

In Preparation Example 1, 1.24 g (0.018 mol) of potassium methoxide and 50 g of 4,7-dioxa-1,2-epoxy-5-methyloctane were used and injected into an autoclave over 20 hours. The same procedure as in Production Example 1 was conducted except that the desired polyoxyalkylene glycol derivative was a 4,7-dioxa-1,2-epoxy-5-ethyloctane polymer (one end of which was a methoxy group and the other end of which Hydroxyl group) 45 g was obtained.

[Production Example 10]

In Preparation Example 1, 1.5 g (0.028 mol) of sodium methoxide and 50 g of a mixture of 4,7-dioxa-1,2-epoxyoctane and propylene oxide (molar ratio 1: 2.7) were used, and the resultant was used for 10 hours. A polyoxyalkylene glycol derivative (one end of which is the desired 4,7-dioxa-1,2-epoxyoctane-propylene oxide interpolymer) was subjected to the same operation as in Production Example 1 except that it was injected into an okoto clave. 45g of methoxy groups and the other end of hydroxyl group) were obtained. ¹³ C-NMR spectrum (solution: heavy chloroform) of this polyalkylene glycol is shown in FIG. 4, and ¹ H-NMR spectrum (solvent: heavy chloroform) is shown in FIG.

[Production Example 11]

In Preparation Example 1, 1.5 g (0.028 mol) of sodium methoxide and 50 g of a mixture of 4,7-dioxa-1,2-epoxyoctane and ethylene oxide (molar ratio 3: 1) were used, and at 9 hours, The same procedure as in Production Example 1 was conducted except that the resultant was injected into an autoclave, and a polyoxyalkylene glycol derivative (one end) which is a target 4,7-dioxa-1,2-epoxyoctane-etale oxide interpolymer 44g of this methoxy group and the other end of the hydroxyl group) were obtained.

¹³ C-NMR spectrum (solution: heavy chloroform) of this polyalkylene glycol is shown in FIG. 5, and ¹ H-NMR spectrum (solvent: heavy chloroform) is shown in FIG.

[Manufacture example 12]

The desired procedure was carried out in the same manner as in Production Example 2, except that 4.5 g (0.083) mol of sodium methoxide was used and 100 g of glycidylmethyl ether was injected into the autoclave over 10 hours. 97 g of polyalkylene glycols (the one end of which is a methoxy group and the other end of which are hydroxyl groups) which are cedyl methyl ether polymers were obtained.

[Production Example 13]

In Preparation Example 1, 1.94 g (0.028 mol) of potassium methoxide and 2,7-dioxa-4,5-epoxyoctane (1,4-dichloro-2-butene and sodium methoxide were reacted to react 1,4-dimethol). The same procedure as in Production Example 1 was carried out except that 50 g of methoxy-2-butene was obtained and then brominated with N-bromuccisinimide and synthesized by treatment with sodium hydroxide in an autoclave over 19 hours. 38 g of polyalkylene glycol (the one end of which is a methoxy group and the other end of which is a hydroxyl group) which is the target 2,7-dioxa-4,5-epoxyoctane polymer were obtained.

The ¹³ C-NMR spectrum (solution: heavy chloroform) of this polyalkylene glycol is shown in FIG.

Production Example 14

In Preparation Example 1, 1.29 g (0.019 mol) of potassium methoxide and 50 g of a mixture of 2,7-dioxa-4,5-epoxyoctane and glycidyl methyl ether (molar ratio 2: 1) were prepared in 23 hours. The same procedure as in Production Example 1 was conducted except that the resultant was injected into an autoclave, and a polyalkylene glycol which is a copolymer of the desired 2,7-dioxa-4,5-epoxyoctane and glycidyl methyl ether (one side) 22 g of terminal was obtained by methoxy group and the other terminal by hydroxyl group).

¹³ C-NMR spectrum (solvent: heavy chloroform) of this polyalkylene glycol is shown in FIG.

[Production Example 15]

In Preparation Example 1, 1.0 g (0.014 mol) of potassium methoxide and 4,8-dioxa-1,2-epoxy-methoxynonane (allylglycidyl ether were hydrated to give a diol and 2 was dissolved using sodium methoxide. Obtain sodium salt and methoxylize by reaction with iodine and methyl, 4,8-dioxa-6-methoxy-1-nonene, bromohydrin with N-bromosuccinimide and sodium hydroxide Synthesis by treatment) The target 4,8-dioxa-1,2-epoxy-6-methoxy-nonane polymer was produced in the same manner as in Production Example 1 except that 50 g of the compound was injected into the autoclave over 13 hours. 43 g of phosphorus polyoxy alkylene glycol (one end was a methoxy group and the other end was a hydroxyl group) was obtained.

[Production Example 16]

In Preparation Example 1, 1.0 g (0.014 mol) of potassium methoxide and 38 g of 4,8-dioxa-1,2-epoxy-methoxynonane were injected into an autoclave over 10 hours, and the same procedure as in Preparation Example 1 was performed. The operation was carried out to obtain 43 g of a polyoxyalkylene glycol (the one end of which is a methoxy group and the other end of which is a hydroxyl group) which is a target 4,8-dioxa-1,2-epoxy-6-methoxy-nonane polymer.

[Production Example 17]

1.2 g (0.017 mol) of potassium methoxide and 4,7-dioxa-1,2-epoxy-5- (2-oxapropyl) octane (glycidyl methyl ether and methanol in the preparation of Example 1 were reacted in the presence of sulfuric acid To obtain 2,6-dioxa-4-hydroxymethyl, reacted with epichlorohydrin in the presence of sulfuric acid, and then treated with sodium hydroxide), 39 g of which was injected into the autoclave over 19 hours. Polyoxy alkylene glycol which is the target 4,7-dioxa-1,2-epoxy-5- (2-oxapropyl) octane polymer by operation similar to manufacture example 1 (one terminal is a methoxy group, and the other terminal is 29 g of this hydroxyl group was obtained.

[Example 1-17 and Comparative Example 1-6]

The usability of the compound obtained in manufacture example 1-17, the polypropylene glycol whose one end is a butyl ether group (butoxy group), and the other is a hydroxyl group, and both ends are a hydroxyl group was measured.

A predetermined amount of sample was added to the pressure-resistant glass ampoules so that 10% and 20% by weight of R-134a (1,1,1,2-tetrafluoroethane) was added to the vacuum pipe and the R-134a gas pipe. Connected.

The ampoules were vacuum degassed at room temperature, cooled with liquid nitrogen, and a predetermined amount of R-134a was collected. The ampoules were then sealed and the temperature was raised from −40 ° C. in a thermostat to measure the temperature at which phase separation began. The higher the phase separation temperature, the more preferable. The results are shown in Table 1. In addition, the measurement of the average molecular weight was performed using GPC (gel permeation chromatography) (standard substance: polyethylene glycol).

The ratio (weight%) of polyol sialylene glycol with respect to (, 1,1,2- heterofluoroethane is shown.

[Reference Example]

Powdered sodium methoxide 3.0g (0.056 mol) was added to a 200 ml stainless steel autoclave to which a stirrer and a liquid introduction pipe were attached, and it was sealed, and it heated and stirred at 110 degreeC, and 120 g of propylene oxides were 13 hours from a liquid introduction pipe. Inject into the autoclave over. After dissolving 120 ml of water and 240 ml of methanol in the reaction mixture, the solution was passed through a column of 200 ml of cation exchange resin and then passed through a column of 200 ml of anion exchange resin to remove sodium ions.

Methanol and water were removed, and it dried under reduced pressure (0.4 mmHg) at 100 degreeC by the vacuum pump for 1 hour, and obtained 115 g of polyoxy alkylene glycol (one terminal is a methoxy group and the other hydroxyl group) which is a propylene oxide polymer.

Of this polyalkylene glycol C-NMR spectrum (solvent: heavy chloroform) is shown in FIG. It can be seen from FIGS. 1-8. In other words, FIG. 1 is different from any of FIGS. 2 and 6.

This indicates that the polyoxy alkylene glycol obtained in Preparation Example 1 is not a simple mixture of the glycidyl methyl ether polymer of Preparation Example 5 and the propylene oxide polymer of Reference Example.

중의 -CH₂-에 의한 피이크가 73ppm 부근에

중의 주사슬의 -CH₂-에 의한 피이크가 74ppm 부근에 다시 또 곁사슬중의 -CH₂-에 따른 피이크가 68.5-70ppm 부근에 분산해서 보인다. 한편, 제2도로부터 제조예 5의 생성물중의 주사슬의 -CH₂-에 의한 피이크 69.5ppm 부근에이다.Again, in Figure 1,

Peak by -CH ₂ -in the vicinity of 73 ppm

The peak due to -CH ₂ in the back side chain addition in the vicinity of 74ppm - - of the peak in the main chain -CH ₂ according to show dispersed at 68.5-70ppm. On the other hand, the -CH ₂ in the main chain of the of the product of preparation 5, in the second road-a peak at 69.5ppm by.

단위와

단위가 결합하고 있는 것, 즉 혼성중합체인 것을 알았다.Therefore, the polymer of Preparation Example 1,

Unit and

It was found that the units were bonded, that is, interpolymers.

Moreover, the peak of a methoxy group was seen in 59 ppm vicinity. As mentioned above, it confirmed that the product of manufacture example 1 was a glycidyl methyl ether propylene oxide interpolymer. 4 is different from any of 3rd and 6th degrees.

This indicates that the polyoxy alkylene glycol obtained in Production Example 10 is not a simple mixture of the 4,7-dioxa-1,2-epoxyoctane polymerization of Production Example 7 and the propylene oxide polymer of Reference Example.

중의 -CH₂-에 의한 피이크가 72-77ppm 부근에 보였다.That is, in Figure 4,

Peaks due to -CH ₂ -were found to be around 72-77 ppm.

중의 -CH₂-에 의한 피이크가 68-72.5ppm에 분산해서 보였다. 한편, 제3도에 있어서 4,7-디옥사-1,2-에폭시-5-메틸옥탄 단독중합체중의 -CH₂-에 기인하는 피이크는 68.8-72.0ppm으로 분산해서 보이지만 68-70ppm 부근에 있어서 제3도와도 제6도와도 패터먼이 다르기 때문에 단순한 혼합물이 아닌 것을 알 수 있다.In addition,

The peak by -CH ₂ -in the dispersion was dispersed at 68-72.5 ppm. On the other hand, in FIG. 3, the peak attributable to -CH ₂ -in the 4,7-dioxa-1,2-epoxy-5-methyloctane homopolymer is dispersed at 68.8-72.0 ppm, but appears to be around 68-70 ppm. In Fig. 3 and 6, the patternman is different, so it can be seen that it is not a simple mixture.

Moreover, the peak by the methyl group of the main chain resulting from the 4,7-dioxa-1,2-epoxy unit of the interpolymer was seen around 79 ppm. Again, it appeared in the vicinity of 59 ppm of the peak size of the methoxy group.

As described above, it was confirmed that 4,7-dioxa-1,2-epoxy-propylene oxide interpolymer was present in the product of Production Example 10.

-CH₂-에 기인하는 피이크가 69-72.5ppm에 보였다.In Figure 5,

Peaks attributable to -CH ₂ -were seen at 69-72.5 ppm.

에 기인하는 피이크가 78.5ppm 부근에 보였다.In addition,

The peak attributable to was seen at around 78.5 ppm.

에 기인하는 피이크는 78.5ppm 부근에 보이지만 제5도에 패터언과 다르다.On the other hand, in FIG. 3, the 4,7-dioxa-1,2-epoxy-5-methyloctane homopolymer

The peak due to appears around 78.5 ppm but differs from the patternion in FIG.

Also in the -CH ₂ -CH ₂ -CH ₂ -O- - the peak attributable to the looked at 70.6ppm. Thus, it was confirmed that the product of Preparation Example 11 was not a mixture of simple homopolymers, and 4,7-dioxa-1,2-epoxy-ethylene oxide mixture was present therein. 8 is different from any of 2nd and 7th degrees. This indicates that the polyoxy alkylene glycol obtained in Production Example 14 is not a simple mixture of the glycidyl methyl ether polymer of Production Example 5 and the 2,7-dioxa-4,5-epoxyoctane polymer of Production Example 13.

및

중의 주사슬의 -CH₂-에 기인하는 피이크가 68.5-71ppm에 곁사슬의 -CH₂-에 기인하는 피이크가 71-74ppm에 보였다.Again, again in Figure 8

And

The peak attributable to -CH ₂ -in the main chain was 68.5-71 ppm and the peak attributable to -CH ₂ -in the side chain was 71-74 ppm.

On the other hand, the peak attributable to -CH ₂ -of the homopolymer of 2,7-dioxa-4,5-epoxyoctane from FIG. 7 was found at 70-74.5 ppm, and no peak was found at 68.5-70 ppm.

The second peak, which initiated the CH ₂ of the side chain of a homopolymer road from the glycidyl ether is near 69.5ppm but does not coincide with the eighth-degree peak. Thus, it was confirmed that 2,7-dioxa-4,5-epoxyoctane-glycidylmethylether interpolymer was present in the product of Production Example 14.

의 양성자를 합한 적분갑으로부터 말단의

를 보정한 값으로부터 구한 조성비

=3.0 : 1이었다.The integral value of the proton from FIG. 9 for the polymer of Preparation Example 1

From the integral sum of protons

Composition ratio obtained from the value which corrected

= 3.0: 1.

=2.9 : 1이었다.About the polymer of the manufacture example 4, the composition ratio calculated | required from FIG. 10 like the polymer of the manufacture example 1 is

= 2.9: 1.

의 양성자를 합한 적분값으로부터 말단의

를 보정한 값으로부터 구한 조성비는,

=2.3 : 1이었다.For the polymer of Preparation Example 10, the integral value of the protons from FIG.

From the integral of the protons

The composition ratio found from the value that corrected

= 2.3: 1.

의 양성자의 적분값으로부터 말단의

를 보정한 값과

의 양성자의 적분값으로부터 구한 조성비는

=3.4 : 1이었다.From FIG. 12 for the polymer of Preparation Example 11,

From the integral of the proton of

With the corrected value

The composition ratio found from the integral value of the proton of

= 3.4: 1

Claims (21)

[Formula 1]

[R <^1> -R <^4> is a C1-C10 monovalent hydrocarbon group or general formula (II), respectively.

(R ⁵ and R ⁶ each represent hydrogen, a C 1-10 monovalent hydrocarbon group or a C 2-20 alkoxy alkyl group, and R ⁷ represents a total carbon number 3 having a C 2-5 alkylene group and an alkyl group as a substituent) And a substituted alkylene group having 4 to 10 carbon atoms having a substituted alkylene group or an alkoxyalkyl group as a substituent, n is an integer of 0 to 20, and R ⁸ represents a monovalent hydrocarbon having 1 to 10 carbon atoms. a group, R ¹ is a group of at least one ~R ⁴ is represented by the general formula (II), polyoxyethylene alkyl at least one of R ¹ ~R ⁴ is one having a structural unit represented by the general formula (II) at least Lubricating oil for compressed refrigerators, mainly composed of lenglycol derivatives. The compound of the formula (I) according to claim 1, wherein R ¹ to R ⁴ in General Formula (I) are each represented by hydrogen, a methyl group, or General Formula (II), and one or two of R ¹ to R ⁴ are represented by General Formula (II) Lubricant oil for compressed refrigerators, which is the origin indicated by). The compound according to claim 1 or 2, wherein R ⁵ and R ⁶ in General Formula (II) each represent hydrogen, and R ⁷ represents an ethylene group, a 1-methylethylene group, a 2-methylethylene group, or a trimethylene group. Lubricating oil for compressed refrigerators, wherein R ⁸ is a hydrocarbon group having 1 to 3 carbon atoms and n represents an integer of 0 to 3; The polyoxyalkylene glycol derivative of claim 1 wherein [Formula 1]

Lubricating oil for compression type refrigerators, which is a homopolymer having a structural unit represented by (R ¹ to R ⁴ are the same as defined in claim 1). The method according to claim 4, wherein R ¹ to R ⁴ in General Formula (I) are each a group represented by hydrogen, a methyl group, or General Formula (II), and one or two of R ¹ to R ⁴ are represented by General Formula (II). Lubricant oil for compressed refrigerators, which is the origin indicated by). The compound according to claim 4 or 5, wherein R ⁵ and R ⁶ in General Formula (II) each represent hydrogen, and R ⁷ represents an ethylene group, a 1-methylethylene group, a 2-methylethylene group, or a trimethylene group. Lubricating oil for compressed refrigerators, wherein R ⁸ is a hydrocarbon group having 1 to 3 carbon atoms and n represents an integer of 0 to 3; The method of claim 1, wherein the polyoxyalkylene glycol derivative is a general formula, [Formula 1]

Lubricating oil for compression type refrigerators, which is a copolymer having at least two types of structural units represented by (R ¹ to R ⁴ are the same as defined in claim 1). 8. A compound according to claim 7, wherein R ¹ to R ⁴ in General Formula (I) are each represented by hydrogen, a methyl group or General Formula (II), and one or two of R ¹ to R ⁴ are represented by General Formula (II). Lubricant oil for compressed refrigerators, which is the origin indicated by). The compound according to claim 7 or 8, wherein R ⁵ and R ⁶ in General Formula (II) each represent hydrogen, and R ⁷ represents an ethylene group, a 1-methylethylene group, a 2-methylethylene group, or a trimethylene group. Lubricating oil for compressed refrigerators, wherein R ⁸ is a hydrocarbon group having 1 to 3 carbon atoms and n represents an integer of 0 to 3; The method of claim 1, wherein the polyoxyalkylene glycol derivative is a general formula, [Formula 1]

The structural unit represented by (R ¹ to R ⁴ are the same as defined in claim 1) and the general formula, [Formula 3]

Lubricating oil for compression type refrigerators, which is a copolymer having at least one structural unit each represented by (R ³¹ to R ³⁴ each represent hydrogen or an alkyl group having 1 to 3 carbon atoms). The compound represented by formula (I) according to claim 10, wherein R ¹ to R ⁴ in General Formula (I) are each represented by hydrogen, a methyl group or General Formula (II), and one or two of R ¹ to R ⁴ are represented by General Formula (II). Lubricant oil for compressed refrigerators, which is the origin indicated by). The compound according to any one of claims 10 or 11, wherein R ⁵ and R ⁶ in General Formula (II) each represent hydrogen, and R ⁷ is an ethylene group, a 1-methylethylene group, or a 2-methylethylene group. Or a trimethylene group, R ⁸ represents a hydrocarbon group of 1 to 3 carbon atoms, and n represents an integer of 0 to 3; The polyoxyalkylene glycol derivative according to any one of 2,4,5,7,8,10 and 11, wherein the polyoxyalkylene glycol derivative has a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, and a carbon atom having 1 to 10 carbon atoms, respectively. A lubricating oil for compressed refrigerators having an alkoxy group, an aryloxy group having 6 to 10 carbon atoms, and having a kinematic viscosity at 100 ° C of 1 to 100 cSt. The lubricating oil for compressed refrigerators according to any one of claims 2, 4, 5, 7, 8, 10 and 11, wherein the compressed refrigerator uses 1,1,1,2-tetrafluoroethane as a refrigerant. . A lubricating oil composition for a refrigeration refrigerator comprising the polyoxyalkylene glycol according to any one of claims 1 to 13 and tetrafluoroethane. The lubricating oil composition for a compressed refrigerator according to claim 15, wherein the amount of the polyoxyalkylene glycol derivative is sufficient to impart lubricity. A method for improving lubricity in a compressed refrigerator, wherein the polyoxyalkylene glycol derivative according to any one of claims 1 to 13 is used as a lubricant and tetrafluoroethane is used as a refrigerant. A compressor type refrigerator system comprising a compressor, a refrigerant made of tetrafluoroethane, and a lubricant made of the polyoxyalkylene glycol derivative according to any one of claims 1 to 13. [Formula (I- (a))]

[R ¹¹ -R ¹⁴ are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or general formula (II- (a))

(R <^5> , R <^6> and R <^8> are as above-mentioned, R <^17> has a C3-C5 alkylene group, the total C3-C5 substituted alkylene group which has an alkyl group as a substituent, or a total carbon number which has an alkoxy alkyl group as a substituent A substituted alkylene group of -10, n represents an integer of 1 to 20), and at least one of R ¹¹ to R ¹⁴ is a group represented by the general formula (II- (a)). 1 to 200 constituent units to be represented, each having a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group, and having a kinematic viscosity of 1 to 100 cSt at 100 ° C. Polyoxyalkylene glycol derivatives. General formula (I- (b))

[R ²¹ -R ²⁴ each represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or general formula (II- (b)).

A group represented by (R ⁵ -R ⁸ and n 'are as described above) and at least one of R ²¹ -R ²⁴ is a group represented by General Formula (II- (b)). General formula (III)

[R ³¹ to R ³⁴ each represent hydrogen, or an alkyl group having 1 to 3 carbon atoms] each having a structural unit having 1 to 200 structural units, each having a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, A polyoxyalkylene glycol derivative having a C1-C10 alkoxy group and a C6-C10 aryloxy group, and having a kinematic viscosity at 100 ° C of 1 to 100 cSt. General formula (I- (c))

[R ⁴¹ -R ⁴⁴ are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or general formula (II)

(R ⁵ -R ⁸ and n are the same as described above), and at least two of R ⁴¹ -R ⁴⁴ are groups represented by the general formula (II). The polyoxyalkylene glycol derivative which has a C1-C10 acyloxy group, a C1-C10 alkoxy group, or an aryloxy group, respectively, and has a kinematic viscosity at 100 degreeC in 1-100 cSt at a terminal position.

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