JPH03205492A - Lubricating oil for compression refrigerator - Google Patents

Abstract

PURPOSE:To obtain the title lubricating oil excellent in compatibility with a hydrochlorofluorocarbon compound and lubricating performance by using a specified polyoxyalkylene glycol derivative as a principal component. CONSTITUTION:The title lubricating oil composed mainly of a polyoxyalkylene glycol derivative having at least one structural unit shown by formula I [wherein R<1> to R<4> are each H, a 1-10C hydrocarbon group or a group of formula II (wherein R<5> and R<6> are each H, a 1-10C hydrocarbon group or 2-20C alkoxyalkyl; R<7> is 2-5C alkylene, alkyl-substituted 2-5C alkylene or alkoxyalkyl- substituted 4-10C alkylene; n is 0 to 20; R<8> is a 1-10C hydrocarbon group), provided that at least one of them is a group of formula II] (e.g. a glycidyl methyl ether/propylene oxide copolymer).

Description

[Detailed Description of the Invention] r Industrial Application Field] The present invention relates to a novel lubricating oil for compression type refrigerators. More specifically, the 1,1,1,2-
Tetrafluoroethane (hereinafter referred to as Freon 134a)
Regarding lubricating oils for compression type refrigerators that are mainly composed of polyoxyalkylene glycol derivatives that have good compatibility with hydrogen-containing fluorocarbon compounds such as, and have excellent lubrication performance.
It is 4.

[Prior art and problems to be solved by the invention] Generally, a compression type refrigerator is a compressor. It consists of a condenser, a valve, and an evaporator, and a liquid mixture of refrigerant and lubricating oil circulates within this sealed system. In such compression refrigerators, although it depends on the type of equipment, the temperature inside the compressor is generally 50°C or higher, while the temperature inside the cooler is -
Since the temperature is approximately 40°C, it is necessary for the refrigerant and lubricating oil to circulate within this system without phase separation within the temperature range of 40°C to +50″C.

If phase separation occurs during operation of the refrigerator, it will have a significant negative impact on the lifespan and efficiency of the equipment. For example, if phase separation occurs between the refrigerant and lubricating oil in the compressor, the moving parts will suffer from poor lubrication, causing seizures and other problems that will significantly shorten the life of the equipment.On the other hand, if phase separation occurs in the evaporator, , the presence of highly viscous lubricating oil reduces the efficiency of heat exchange.

Furthermore, since lubricating oil for refrigerators is used for the purpose of lubricating the moving parts of refrigerators, lubrication performance is naturally important. In particular, since the temperature inside the compressor is high, it is important to have a viscosity that can maintain the oil film necessary for lubrication. The required viscosity varies depending on the type of compressor used and the operating conditions, but the viscosity of the lubricating oil before mixing with the refrigerant is usually 100' (i
2 to 50 cSt is preferable. If the viscosity is lower than this, the yuzu film becomes thinner and lubrication failure is likely to occur, and if it is higher than this, the efficiency of heat exchange decreases.

Conventionally, Freon 12 has been widely used as a refrigerant in compression type refrigerators, and various mineral oils and synthetic oils that meet the above-mentioned required characteristics have been used as lubricating oils. However, since Freon-12 has the potential to cause environmental pollution such as depleting the ozone layer, its regulations have recently become stricter worldwide. Therefore, hydrogen-containing fluorocarbon compounds typified by fluorocarbon 134a have been attracting attention as new refrigerants. This hydrogen-containing fluorocarbon compound,
In particular, Freon 134a is preferable as a refrigerant for compression type refrigerators because it has little risk of destroying the ozone layer and can be substituted for Freon 12 without changing the structure of conventional refrigerators. .

When a hydrogen-containing fluorocarbon compound such as the above-mentioned Freon 1348 is used as a refrigerant in a compression type refrigerator instead of Freon 12, it naturally has excellent compatibility with the hydrogen-containing fluorocarbon compound such as Freon 134a as a lubricating oil. A material with excellent lubrication performance that can satisfy the above-mentioned performance requirements is required.

However, the lubricating oil that has been used with conventional Freon 12 does not have good compatibility with hydrogen-containing fluorocarbon compounds such as Freon 134a, so a new lubricating oil suitable for these compounds is required. In this case, especially in automotive air conditioners, it is desired to make almost no changes to the structure of the device when replacing Freon 12, and it is not desirable to make major changes to the structure of the current device for lubricating oil. do not have. Therefore, a lubricating oil is required that has extremely good compatibility with hydrogen-containing fluorocarbon compounds such as fluorocarbon 134a.

As lubricating oils that are compatible with Freon 134a, for example, Urukon LB-165 and Urukon LB-525 (both trade names manufactured by Union Carbide), which are made of polyalkylene glycol, are known. It has been reported that oil is miscible with Freon 134a at a low temperature of at least 50°C [Research Disclosure +
arch DiSclosure)” No. 17463 (
October 1978)]. Furthermore, a high viscosity refrigerating machine oil composition using boroxybrobylene glycol heptabutyl ether as a base oil is also known (Japanese Patent Publication No. 42119/1983).

However, these lubricating oils are polyalkylene glycol derivatives in which polypropylene glycol has a hydroxyl group at one end and an n-butyl ether bond at the other end, and has relatively good compatibility with Freon 134a at low temperatures. However, it is known that the compatibility is not sufficient at high temperatures, and for example, the above-mentioned C) Iicon LB-525 undergoes phase separation from Freon 134a at room temperature (US Pat. No. 4,755. 316 Specification).

On the other hand, polyoxyalkylene glycol having at least two hydroxyl groups in one molecule has been proposed as having good compatibility with Freon 134a (=8).
(U.S. Pat. No. 4,755,316).

However, the compatibility of this polyoxyalkylene glycol is not necessarily sufficient.

It is known that polyoxyalkylene glycol exhibits temperature dependence in that when a mixture with a fluorocarbon compound is heated from a low temperature to a high temperature, the mixture that had phase-separated in one phase becomes compatible, and then phase-separates again. It is being Furthermore,
It is also known that as the molecular weight of polyoxyalkylene glycol increases, its compatibility decreases.

On the other hand, it has been proposed to use Freon 134a and compounds that can dissolve it in absorption refrigerators (Japanese Patent Application Laid-open No.
6-79175>. However, this absorption refrigerator has a completely different mechanism from the compression refrigerator described above, and the tetraethylene glycol dimethyl ether described in the examples of the above-mentioned publication has a significantly low viscosity.
It is unsuitable as a lubricating oil for compression refrigerators.

As described above, a lubricating oil for compressor type refrigerators that has sufficiently good compatibility with Freon 134a and has excellent lubrication performance has not yet been found, and its development is strongly desired. was.

In response to such demands, the present invention has developed a system that is compatible with hydrogen-containing fluorocarbon compounds such as fluorocarbon 134a, which can be used as a substitute for fluorocarbon 12, which is a refrigerant that has become a problem due to environmental pollution, or other fluorocarbon compounds that are difficult to decompose. The purpose of this invention is to provide a lubricating oil for compression type refrigerators that is good over the entire operating temperature range and has excellent lubrication performance.

[Means for Solving the Problems] The present inventor has conducted extensive research in order to develop a lubricating oil for compression type refrigerators that has both excellent compatibility with hydrogen-containing fluorocarbon compounds such as Freon 134a and lubrication performance. As a result, it was found that a product mainly composed of polyoxyalkylene glycol having a specific group was suitable for the above purpose, and based on this knowledge, the present invention was completed.

That is, the present invention provides a compound represented by the general formula (1) RIR3 C-C10- (1) R2R4 (R+ to R4 are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or the general formula (It ) R5 C-Cl-(R70)l, -Ra --- (It)
R6 (Rs and R6 each represent hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms, and R7 is an alkylene group having 2 to 5 carbon atoms. An alkyl group is used as a substituent. represents a substituted alkylene group having a total of 2 to 5 carbon atoms or a substituted alkylene group having a total of 4 to IO carbon atoms having an alkoxyalkyl group as a substituent, and n is 0 to 2.
The integer of 0 and R6 represent a monovalent hydrocarbon having 1 to 10 carbon atoms. ) 11 and at least one of R'-R' is a group represented by general 2(n)]. The Company mainly provides lubricating oil for compression type refrigerators.

The lubricating oil for compression type refrigerators of the present invention contains at least one structural unit represented by the general formula (1). Here, R I and R 4 in the formula are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or general formula (II) R5 -C-0-(R70), -R8... (II) R
6. Among these, 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 IO carbon atoms, and a cycloalkyl group having 6 to 10 carbon atoms. It represents an aryl group having 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Specifically, the methyl group. Ethyl group, n-probyl group. Isobrovir group.
Various butyl groups. Various bentyl groups, various hexyl groups, various hebutyl groups, various octyl groups. Various nonyl groups, various alkyl groups such as decyl groups, vinyl groups, allyl groups, brobenyl groups, isoprobenyl groups. 1. Various 7'tenyl groups 2. Various pentenyl groups, various hexenyl groups 3. Various heptenyl groups, various octenyl groups, various nonenyl groups. Alkenyl groups such as various decenyl groups, cyclobentyl groups. Cycloalkyl groups such as cyclohexyl groups, phenyl groups, and various tolyl groups. Examples include various xylyl groups, aryl groups such as naphthyl groups, and aralkyl groups such as benzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups. Among these, a monovalent hydrocarbon group having 6 or less carbon atoms is preferred, and an alkyl group having 3 or less carbon atoms is particularly optimal.

In general formula (II), R% and R6 each represent hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms; Specifically, an alkyl group having 1 to 10 carbon atoms. It represents 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 arylalkyl group having 7.1 lO carbon atoms. Specifically, methyl group, ethyl group, n-probyl group, isoprobyl group and various butyl groups. Alkyl groups such as various bentyl groups, various hexyl groups, various hebutyl groups, various octyl groups, various nonyl groups, various decyl groups, vinyl groups, allyl groups, and bropenyl groups.
Isobropenyl group, various butenyl groups, various pentenyl groups 2 various hexenyl groups, various heptenyl groups. Alkenyl groups such as various octenyl groups, various nonenyl groups, various decenyl groups, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, fenyl group, various tolyl groups, various xylyl groups,
Aryl group such as naphthyl group, arylalkyl group such as henzyl group, 1-phenylethyl group, 2-phenylethyl group, methoxymethyl group, etc.
-Propoxymethyl group, isobroboxymethyl group. Various butoxymethyl groupsVarious pentoxymethyl groups. Various hexoxymethyl groups, various heptoxymethyl groups, various octoxymethyl groups, various nonyloxymethyl groups, 1-methoxyethyl groups, 2-methoxyethyl groups. 1-ethoxyethyl group. 2-ethoxyethyl group, various propoxyethyl groups. Various butoxyethyl groups, various pentoxyethyl groups. Various hexoxyethyl groups. Various hep-1 xyethyl groups. Various octoxyethyl groups, various MeI-xybrobyl groups, various ethoxybrobyl groups, various proboxyprobyl groups, various butoxypropyl groups, various bentoxyprobyl groups. Various hexoxypyl groups. Various hebutoxyethyl groups. Various types of xybutyl groups, various types of xybutyl groups, various propoxybutyl groups, various butoxybutyl groups, 2 various bentoxybutyl groups, various hexoxybutyl groups, various methoxybentyl groups, various ethoxybentyl groups. Various propoxybentyl groups, various butoxypentyl groups, various bentoxypentyl groups. various) }xyhexyl group. Various ethoxyhexyl groups, various propoxyhexyl groups. Various butoxyhexyl groups, various methoxyheptyl groups. Examples include alkoxyalkyl groups such as various ethoxyheptyl groups, various propoxyheptyl groups, various methoxyoctyl groups, various ethoxyoctyl groups, and various methoxyheptyl groups. Among these, an alkyl group having 3 or less carbon atoms or an alkoxyalkyl group having 6 or less carbon atoms is preferred.

R7 is an alkylene group having 2 to 5 carbon atoms. A substituted alkylene group having a total of 2 to 5 carbon atoms having an alkyl group as a substituent or a total carbon number of 4 having an alkoxyalkyl group as a substituent
~10 substituted alkylene groups, specifically ethylene group; 1-methylethylene; ethylethylene group; 1,1
-dimethylethylene group; 1,2-dimethylethylene group;
n-propylethylene group; isobropylethylene group: 1
Ethyl-2-methylethylene group; 1-ethyl 1-methylethylene group; trimethylene group; TeI-ramethylene 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. Examples include i(bisethoxyethyl)ethylene group; 2-methoxy-1,3-propylene group, and preferably ethylene group and substituted ethylene group having 6 or less carbon atoms.

Rl1 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, but is generally an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms.
alkenyl group. cycloalkyl group having 5 to 10 carbon atoms,
It represents an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 7 to 10 carbon atoms. Specifically, methyl group, ethyl group. n-propyl group, isopropyl group, various butyl groups. Various bentyl groups, various hexyl groups, various hebutyl groups, various octyl groups. Various nonyl groups. Alkyl groups such as various decyl groups, vinyl groups, allyl groups, propenyl groups, isobrobenyl groups. Various butenyl groups. Various bentenyl groups, various hexenyl groups, various hebutenyl groups, various octenyl groups,
Alkenyl groups such as various nonenyl groups and various decenyl groups, cycloalkyl groups such as cyclopentyl and cyclohexyl groups, phyllyl groups, various tolyl groups, and various xylyl groups. Examples include aryl groups such as naphthyl groups, and aralkyl groups such as Henzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups. Among these, hydrocarbon groups having 6 or less carbon atoms are preferred, and hydrocarbon groups having 3 or less carbon atoms are particularly preferred.

In addition, at least one of R 1 and R 4 in the above-mentioned general formula (1) is a group represented by general formula (I[). In particular, one of Rl and R3 is represented by the general formula (n)
A group of Rl. The remaining one of R3 and R2, R4
are each preferably hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

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 (+). ), copolymers consisting of two or more different structural units contained in general formula (1), and structural units of general formula (1) and other structural units, For example, copolymers consisting of structural units represented by the general formula (It) R9 R'' (R9 to R'2 each represent hydrogen or an alkyl group having 1 to 3 carbon atoms) can be roughly divided into three types. be able to.

A preferable example of the above homopolymer has 1 to 200 structural units A represented by the general formula (1), and the terminal groups are a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, 2 acyloxy groups having 1 to 10 carbon atoms, respectively. Examples include those consisting of an alkoxy group and an aryloxy group.

On the other hand, preferred examples of the copolymer include those having 1 to 200 of each of the two types of structural units A and B represented by the general formula (1), or having a structural unit represented by the general formula (1). A from 1 to
200 pieces and 1 to 2 structural units C represented by the general formula (n)
00, and each terminal group is a hydroxyl group and an acyloxy group having 1 to 10 carbon atoms. Examples include those consisting of an alkoxy group having 1 to 10 carbon atoms or an aryloxy group.

These copolymers are composed of alternating copolymers, random copolymers, or block copolymers of structural unit A and structural unit B (or structural unit C), or in which structural unit B is included in the main chain of structural unit A. There are various types such as grafted Graph I-copolymers.

The polyoxyalkylene glycol derivative used in the lubricating oil of the present invention can be produced, for example, by the following method.

] General formula R I R 3 without person L [wherein, R'-R' is the same as above. ] Polyoxyalkylene glycol derivatives can be obtained by polymerizing the oxirane compound represented by the following alone or by copolymerizing a mixture of two or more compounds represented by the formula (TV).

In addition, a compound represented by the formula (■) and an alkylene having 2 to 8 carbon atoms such as ethylene oxide or propylene oxide represented by the general formula 20 R'R' (in the formula, R9 to RI2 are the same as above) By mixing it with an oxide and copolymerizing it, a polyoxyalkylene glycol derivative can be produced.

There are various oxirane compounds represented by the general formula (TV) depending on the types of R I and R 4,
Specifically, glycidyl methyl ether; ethyl glycidyl ether; brobyl glycidyl ether; butyl glycidyl ether; 2-ethylhexyl glycidyl ether; 2-methyloctyl glycidyl ether; vinyl glycidyl ether; allyl glycidyl ether; phenyl glycidyl ether;, sec -butylphenyl glycidyl ether; 4.7-dioxor 1.2-eboxyoctane: 1,2-epoxy-4.7.10-}lioxaundecane; 1.2-epoxy 4.7,10.
13 Tetraoxatetradecane; 4,7-dioxa 1.
2-epoxy-5-methyloctane; 47-dioxa-
1,2-Eboxy-6-methyloctane; 6,9-dimethyl-1,2-epoxy 4,7.10-}lioxaundecane; 1,2 Eboxy-4 7.10.13-Te1
・Laoxa 6,9.12-}rimethyltetradecane: 1
, 2-epoxy-5-methyl-4 7 10-1-lioxaundecane: 1,2-epoxy-8-methyl 4,
7.10-1-Lioxaundecane: 2,7 dioxer
4.5-Eboxyoctane; 4,5 Eboxy-9-methyl-2710-1-lioxaundecane; 4,
5-Epoxy-2.7.101 3-tetraoxatetradecane; 7.8-Epoxy-2.5,10.13
-tetraoxate-1-radecane; 3,12-dimethyl-
7.8-Eboxy 2.5,10.13-tetraoxatetradecane; 1,2-epoxy-3-methoxy-5-oxahexane; 4.8-dioxar 1,2-epoxy-
6-Methoxynonane; 4 7-dioxa-12-epoxy-5-(2-oxapate)-octane; 3,5-
Bis(2-oxapipill) 4.7-dioxa-1.2
-Epoxyoctane; 3.6-bis(2-oxabrovir)-4.7dioxa-1.2-epoxy-octane;
69 bis(2-oxabropyl l-1,2-epoxy-
4.7.10-oxaundecane, etc.

In addition, as a polymerization initiator, water, alkali hydroxide,
~ Hexahydric alcohol; alkoxide; thiol; 2 2
'-thiodiethanol;22'-Thiodiethanol sodium alkoxide Known compounds such as phenol, phenoxide, and amine can be used.

11. At least one compound of the general formula (I) obtained by the method (A)
Polymerizing another type of oxirane compound represented by general formula (IV) or an alkylene oxide having 2 to 823 carbon atoms represented by general formula (V) to the homopolymer of oxirane compound represented by V) In this way, the desired polyoxyalkylene glycol derivative can be produced. In this case, it is also possible to carry out two reactions consecutively in one reactor.

Once an alkylene glycol having 2 to 8 carbon atoms represented by the L method general formula (V) is polymerized to obtain a polyoxyalkylene glycol, an oxirane compound represented by the general formula (IV) or this Oxirane compounds and general formula (V
) can be polymerized with alkylene oxide to produce the desired polyoxyalkylene glycol derivative. In this case, two types of reactions can be carried out successively in one reactor.

The polyoxyalkylene glycols obtained by such methods (A) to (C) have all or part of the terminal hydroxyl groups esterified. By introducing into ether, solubility is improved, hygroscopicity is reduced, and viscosity index is improved. It is possible to further improve the performance as a refrigerating machine oil, such as improved lubricity. The hydrocarbon group in the ester and ether 24 residues preferably has 1 to IO carbon atoms.

In addition, in order to maintain the oil film thickness necessary for lubrication, the lubricating oil of the present invention has a kinematic viscosity of 1 before mixing with the refrigerant.
1 to 100 cSt. at 00°C. , especially 2-50
cSt is preferred. Therefore, in order to produce a polyoxyalkylene glycol derivative with a kinematic viscosity in this range,
In the above methods (A) to (C), the raw material. Preferably, the initiator and reaction conditions are selected. However, even if the kinematic viscosity is outside the above range, the kinematic viscosity can be adjusted to a preferable range by mixing several types.

The polyalkylene glycol derivatives thus obtained may be used alone or in combination of two or more. It can also be used in combination with other lubricating oils to improve their performance.

The lubricating oil of the present invention also contains various additives used in conventional lubricating oils, such as load-bearing additives. Chlorine scavenger, antioxidant. Metal deactivators, defoamers, detergents and dispersants, viscosity index improvers, oil agents, anti-wear additives, extreme pressure agents. anti-rust.
Corrosion inhibitors, pour point depressants, etc. can be added as desired.

Examples of the load-bearing additives include monosulfides, polysulfides, sulfoxides, sulfones, and thiosulfinates. Organic sulfur compounds such as sulfurized oils and fats, thiocarbonates, thiophene-thiazoles, methanesulfonic acid esters, phosphoric acid monoesters, phosphoric diesters, phosphoric triesters (tricresyl phosphate), etc. Phosphite esters, phosphorous monoesters, phosphorous diesters. Phosphite I・
Phosphite esters such as lyesters, thiophosphoric acid esters such as thiophosphoric triesters, and higher fatty acids. Hydroxyaryl fatty acids, carboxylic acid-containing polyhydric alcohol esters, fatty acid-based products such as metal soaps, and polyhydric alcohol esters. Fatty acid esters such as acrylic acid esters, organic chlorine-based products such as chlorinated hydrocarbons and chlorinated carboxylic acid derivatives, and fluorinated aliphatic carboxylic acids. Fluorinated ethylene resins, fluorinated alkylborosiloxanes. Organic fluorine-based products such as fluorinated graphite, alcohol-based products such as higher alcohols, naphthene [Ilft (lead naphthenate)]
, fatty acid salts (fatty acid lead), thiophosphates (zinc dialkyldithiophosphate), thiocarbamonates. Organic molybdenum compounds. Organotin compounds. There are metal compound types such as organic germanium compounds and boric acid esters.

Glycidyl ether group-containing compounds are used as chlorine scavengers. Eboxidized fatty acid monoesters, eboxidized fats and oils.
Examples include epoxycycloalkyl group-containing compounds. Phenol is an antioxidant! (2,6-ditertiarybutyl-p-cresol), aromatic amines (α-naphthylamine), and the like. As a metal deactivator,
Examples include benzo I and lyazole derivatives. Examples of antifoaming agents include silicone oil (dimethylpolysiloxane) and polymethacrylates. Examples of cleaning and dispersing agents include sulfonates. These include phene 1, succinimide, etc. Examples of the viscosity index improver include polymethacrylate-1-, polyisobutylene-2-ethylene-propylene copolymer, and styrene-diene hydrogenated copolymer.

(Example) Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way.

Production Example 1 Remove the stirrer and liquid inlet tube and add 3.0 g (0.056 mol) of powdered sodium/lium methoxide to a 200 ml stainless steel autoclave and seal it. Heating to 110°C, a mixture of glycidyl methyl ether and propylene oxide (molar ratio 1:
20 g of 3N was injected into the autoclave through the liquid introduction tube over 13 hours.

Add 120 ml of water and 240 ml of methanol to the reaction mixture.
After dissolving the solution by applying force, the solution was poured into a cation exchange resin with 20
The mixture was passed through a 0-0 column and then an anion exchange resin 20010 column to remove sodium ions. After distilling off methanol and water, under reduced pressure with a vacuum pump (
0. 4 sag), 100"C. After drying for 1 hour, the desired polyoxyalkylene glycol (one end is a methoxy group and the other end is a hydroxyl group) is obtained. Nuclear magnetic resonance (13C-NMR) using carbon isotope of this polyoxyalkylene glycol
The spectrum (solvent: deuterated chloroform) is shown in FIG.

Further, the proton nuclear magnetic resonance (IH-NMR) spectrum (solvent: deuterated chloroform) of this polyoxyalkylene glycol is shown in FIG.

Production Example 2 Powdered sodium 1-lium methoxide 3 was placed in a 200-stainless steel autoclave equipped with a stirrer and a liquid introduction tube.
．． The autoclave was sealed, heated to 110°C, and 100 g of glycidyl methyl ether was pressurized into the autoclave through the liquid introduction tube over 9 hours while stirring.

After dissolving 100 d of water and 200 mF of methanol in the reaction mixture, the solution was passed through a column of 200 d of cation exchange resin and then a column of 200 d of anion exchange resin to remove sodium ions. After distilling off methanol and water, vacuum bomb under reduced pressure (0.4 tl)
The mixture was dried at 100° C. for 1 hour to obtain 89 g of polyoxyalkylene glycol (one terminal has a MeI-xy group and the other terminal has a hydroxyl group) which is the desired glycidyl methyl ether polymer.

Production example 3 Stirrer. 50 g of the polyoxyalkylene glycol derivative, which is the glycidyl methyl ether-propylene oxide copolymer obtained in Production Example 1, was placed in a 300 m2 three-neck glass flask equipped with a distillation head. sodium meth 1
・10 g of 28 wt% methanol solution of oxide (0.052 mol of sodium oxide) and 8 ruene
0 ml was added and heated to distill off methanol and about 30 ml of toluene.

After cooling, the contents were transferred to a 200 m stainless steel autoclave with a stirrer and 15 g of methyl iodide (0.11
mol), and after sealing, heat from 50"C to 75"C while stirring.
The temperature was raised to 90°C over 4.5 hours and held at 90°C for 2.5 hours. After cooling to room temperature, the reaction mixture was poured with 100 ml of water.
ffi and methanol 200 parts, and passed through a 200 mfl cation exchange resin column and then an anion exchange resin 200 ml column to remove sodium ions and iodine ions.

After distilling off methanol and water, use a vacuum bomb under reduced pressure (0
．． 4 mmftg) and 1 hour at 100° C. to obtain 43 g of a polyoxyalkylene glycol derivative (methoxy groups at both ends), which is the desired glycidyl methyl ether-propylene oxide copolymer.

Production Example 4 In Production Example 1, 2.0 g of sodium methoxide (
0.037 mol) and a mixture of glycidyl methyl ether and propylene oxide (molar ratio 1:
The same procedure as in Production Example 1 was carried out, except that 60 g of 3) was used and compressed in an autoclave for 8.5 hours or 31 days. Oxyalkylene glycol derivative (one terminal has a methoxy group,
The other end was a hydroxyl group) to obtain 58 g. 'H of this derivative
-NMR spectrum (solvent double chloroform) is shown in FIG.

Production Example 5 In Production Example 2, Na1, Riumme1, Naside 2.0
The desired glycidyl methyl 93 g of polyalkylene glycol (one end is a methoxy group and the other end is a hydroxyl group) which is an ether polymer was obtained. The 1''(,-NMR spectrum (solvent: deuterated chloroform) of this polyalkylene glycol is shown in FIG.

Production Example 6 2 20 g (0.10 mol of sodium methoxide) of a methanol solution of 28% by weight of sodium methoxide in 7.6 g (0.06232 mol) of 2'-thiodiethanol.
After adding 50 cc of toluene and stirring at 70°C for 4 hours, methanol was distilled off. Furthermore, under vacuum pump depressurization (
0. Unreacted 2,2'-thiodiethanol and toluene were distilled off at 3 mmHg) and 100°C for 1 hour to obtain 9.5 g of sodium alkoxide of 2,2'-thiodiethanol. This sodium alkoxide was added to a 200 ml stainless steel autoclave equipped with a stirrer and a liquid introduction tube. 1 4 g
The autoclave was sealed, heated to 110°C, and 100 g of glycidyl methyl ether was pressurized into the autoclave through the liquid introduction tube over 14.5 hours while stirring. After cooling the autoclave, 28 g (0.18 mol) of methyl iodide was added and heated at 60°C for 2.5 hours, then further heated at 90°C for 5 hours, and the salt was removed using the same method as in Production Example 3. remove,
93 g of a polyoxyalkylene glycol derivative (methoxy groups at both ends), which is the desired glycidyl methyl ether polymer, was obtained.

Production Example 7 In Production Example 1, potassium oxide 1.9 4
g (0.0 2 8 mol) and 47
Using 50 g of -dioxa-1,2-epoxyoctane (addition reaction of shrimp chlorohydrin and 2-mer xyethanol in the presence of sulfuric acid to obtain chlorohydrin, and further treating with alkali to yield), The same operation as in Production Example 1 was carried out except that the injection into the autoclave took a long time, and a polyoxyalkylene glycol derivative (one terminal was a methoxy group and the other end was a hydroxyl group) 48 g was obtained. The 13C-NMR spectrum (solvent: deuterated chloroform) of this polyalkylene glycol is shown in FIG.

Production Example 8 In Production Example 1, potassium methoxide was 1.9 4
g (0.0 2 8 mol) and 47-
Using 50 g of dioxa-1 2-epoxy-5-methyloctane (addition reaction of epichlorohydrin and 1-methoxy-2-probanol in the presence of sulfuric acid to obtain chlorohydrin, which was further treated with alkali),
The same operation as in Production Example 1 was performed except that the autoclave was pressed for 9 hours, and the desired polyoxyalkylene glycol, which is a 4,7-dioxa-1,2-epoxy-5-methyloctane polymer, was obtained. 44 g of a derivative (one end has a methoxy group and the other end has a hydroxyl group) was obtained.

Production Example 9 In Production Example 1, potassium methoxide was 1.2 4
g (0.0 1 8 mol), and 47-
Dioxa-1 2-Eboxy-5-methyloctane 50
The same operation as in Production Example 1 was carried out, except for press-fitting into the autoclave over a period of 20 hours.
．． Polyoxyalkylene glycol derivative (7-dioxa-1,2-epoxy-5-methyloctane polymer)
One end had a methoxy group and the other end had a hydroxyl group) 45 g was obtained.

3 5- Production Example 10 In Production Example 1, 1.5 g of sodium methoxide (
Using 50 g of a mixture of 2-epoxyoctane and propylene oxide (molar ratio 1:2.7), 47-dioxa-1 was pressed into Eau 1 crepe for 10 hours. Except for the above, the same operation as in Production Example 1 was carried out to obtain the desired polyoxyalkylene glycol derivative (
One end had a methoxy group and the other end had a hydroxyl group) 45 g was obtained. The C-NMR spectrum (solvent: deuterated chloroform) of this polyalkylene glycol is shown in Figure 4.
The R spectrum (solvent: deuterated chloroform) is shown in FIG.

Production Example 11 In Production Example 1, 1.5 g of sodium oxide
(0.028 mol) was used, and 50 g of a mixture of 47-dioxa-12-epoxyoctane and ethylene oxide (mole ratio 3:1) was used and compressed into O-1 crepe over 9 hours. Other than that, perform the same operation as in Production Example 1 to obtain the desired 4 to 7
-Dioxa-1 2 A polyoxyalkylene glycol derivative that is an epoxyoctane ethylene oxide copolymer (one end is a mel/xy group and the other end is a hydroxyl group) 44
I got g. l3c-N of this polyalkylene glycol
The MR spectrum (solvent double chloroform) is shown in Figure 5.
'H-NMR spectrum (solvent: deuterated chloroform) is shown in FIG.

Production Example 12 In Production Example 2, 4.5 g of sodium methoxide (
The same operation as in Production Example 2 was carried out, except that 0.083 mol) was used and 100 g of glycidyl methyl ether was compressed into au-I-crepe over 10 hours.
97 g of polyalkylene glycol (one end is a methoxy group and the other end is a hydroxyl group) which is the desired glycidyl methyl ether polymer was obtained.

Production Example 13 In Production Example 1, potassium methoxide was 1.9 4
g (0.028 mol) and 27-dioxa-
4.5-Eboxyoctane (by reacting 1,4-dichloro-2-butene with sodium methoxide to obtain 1,4-dimethoxy-2-butene, which was then converted into a fluoromydoline with N-fluoromsuccinidide, The same procedure as in Production Example 1 was carried out, except that 50 g of 7-dioxa-4 was press-injected into the O-1-crepe over 19 hours by treatment with sodium hydroxide. 5
- 38 g of polyalkylene glycol (one end is MeI-xy group, the other end is hydroxyl group) which is an epoxy octane polymer was obtained. 13 of this polyalkylene glycol
(,-NMR spectrum (solvent: deuterated chloroform) is shown in FIG. 7.

Production Example 14 In Production Example 1, 1.29 g of potassium methoxide (
0.019 mol) and 50 g of a mixture of 2,7-dioxa-4,5-eboxyoctane and glycidyl methyl ether (molar ratio 2:1) were pressed into a crepe over 23 hours. The same procedure as in Production Example 1 was carried out except that the desired 2,7-dioxer 4
．． 22 g of polyalkylene glycol (one end is a methoxy group, the other end is a hydroxyl group) which is a copolymer of 5-epoxyoctane and glycidyl methyl ether was obtained.

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

Production Example 15 In Production Example 1, 1.0 g (0
．． 014 mol) and 4,8-dioxa-1,2-epoxy-6-methoxynonane (allyl glycidyl ether is hydrated to form a diol, disodium salt is obtained using sodium methoxide, methyl iodide etc. 48-dioxa-6-methoxy-1-nonene by mer-oxylation with
The same operation as in Production Example 1 was carried out except that 50 g of 9t2) was press-fitted into the O-I crepe over 13 hours. 43 g of a certain polyoxyalkylene glycol (one end is a meh-hexyl group and the other end is a hydroxyl group) was obtained.

Production Example 16 In Production Example 1, 1.0 g of potassium methoxide (0
．． Preparation Example 1 except that 38 g of 014 mol) and 48-diotosa1,2-epoxy-6-me1-xynonane were pressed into an ole crepe for 10 hours.
Perform the same operation as 4,8-dioxa-1
．． 34 g of polyoxyalkylene glycol (one end is a mei-xy group and the other end is a hydroxyl group) which is a 2-epoxy-6-me-1-xy-nonane polymer was obtained.

Production Example 17 In Production Example 1, potassium methoxide]. 2g (0
．． 017 mol) and 4 7-dioxa1,2-epoxy-5-(2-oxabucetyl)40 octane (glycidyl methyl ether and methanol were reacted in the presence of sulfuric acid to obtain 2,6-dioxa-4-hydroxymethyl This was reacted with shrimp chlorohydrin in the presence of sulfuric acid, and then treated with sodium hydroxide to produce a mixture of 39g and 39g in an autoclave for 19 hours. The desired 4,7dioxa-1,2-epoxy-5-(2-oxapate)octane polymer, polyoxyalkylene glycol (one end is a methoxy group and the other end is (hydroxyl group) 29 g was obtained.

Examples 1 to 17 and Comparative Examples 1 to 6 Compounds obtained in Production Examples 1 to 17 and polypropylene glycol having one end being a butyl ether group (butoxy group) and the other being a hydroxyl group, and polypropylene glycol having a hydroxyl group at both ends. The compatibility of brobylene glycol was determined.

A predetermined amount of sample of Freon 134a (1.1,1,2-tetrafluoroethane) at a concentration of 10% and 20% by weight was added to a pressure-resistant glass ampoule, and this was added to the vacuum pipe and Freon 1 3 l1. a Connected to gas piping.

The ampoule was vacuum degassed at room temperature, cooled with liquid nitrogen, and a predetermined amount of Freon 134a was collected.

The ampoule was then sealed, and the temperature was raised from -40°C in a constant temperature bath, and the temperature at which phase separation began was measured.

The higher the phase separation temperature is, the more preferable it is. The results are shown in Table 1.

Note that the average molecular weight was measured using GPC (Gelber Chromatography) (standard substance: polyethylene glycol).

(Left below) Reference Example Powdered sodium methoxide 3.
0 g (0.056 mol) was added, the mixture was sealed, heated to 110°C, and 120 g of propylene oxide was pressurized into the O-1 crepe over a period of 13 hours while stirring. After the reaction mixture was dissolved by adding 120 m of water and 240 ml of methanol, the solution was passed through a column of cation exchange resin 200 and then through a column of anion exchange resin 200 to remove sodium ions. After distilling off methanol and water, under reduced pressure with a vacuum pump (0.4 mm}Ig), 1
After drying for 1 hour at 0.00 °C, 0.15 g of polyoxyalkylene glycol (one end is a methoxy group and the other end is a hydroxyl group) which is a propylene oxide polymer was obtained.

The I30-NMR spectrum of this polyalkylene glycol (solvent: deuterated chloroform) is shown in FIG.

The following can be seen from Figures 1 to 8. That is, Fig. 1 is similar to Fig. 2.
．． This is different from any of the figures shown in Figure 6.

46 This shows that the polyoxyalkylene glycol obtained in Production Example 1 is not a mere blend of the glycidyl methyl ether polymer of Production Example 5 and the propylene oxide polymer of Reference Example. Furthermore, in FIG. 1, there is a peak based on one CH2- in CH3 cHg-cH-o at around 73 ppm, CH2-0-CH3-CH. -C
The peak based on one CH2- in the main chain in H-0 is around 74 ppm, and the peak based on one CH2- in the side chain is around 6.
It appears to be dispersed around 8.5 to 70 ppm.

On the other hand, from FIG. 2, the main chain C H in the raw material of Production Example 5
The peak based on 2- is 69. It is around 5 ppm.

Therefore, the polymer of Production Example 1 has C H 3 -CH. -CH-01 unit, C H2101C H3 CH. It was found that -CH-0-1 units were bonded together, that is, it was a copolymer.

47 Also, a peak of methoxy group was observed around 59 ppm. From the above, it was confirmed that the raw material of Production Example 1 was a glycidyl methyl ether-propylene oxide copolymer.

Furthermore, FIG. 4 is different from either of FIGS. 3 and 6. In this child, the polyoxyalkylene glycol obtained in Production Example 10 is the 4 7-dioxa-
1 Indicates that it is not a mere blend of the 2-epoxyoctane polymer and the propylene oxide polymer of the reference example.

That is, in FIG. 4, a peak based on one CH2- in CH3-CH2-CH-〇1 was observed around 72 to 77I1pm. Also CH2-Cl
-CH. -CH2-0-CHICH, the peak based on one CH2- in -CH-0- is 68-7 2. 5
It was found dispersed in ppm.

On the other hand, in FIG. 3, the peak based on -CH2- in the 4.7-dioxal 12-epoxy 5-methyloctane homopolymer is 68.8 to 72. Although it can be seen dispersed at 0 ppm, the pattern in both Figures 3 and 6 is different in the vicinity of 68 to 10 ppm, indicating that it is not a mere blend.

In addition, the peak due to the methine group in the main chain caused by the 4,7-dioxa-1,2-epoxy unit of the copolymer was 79pp.
It was seen near m. Furthermore, the peak of methoxy group is 59p
Found around pm.

From the above, the raw material of Production Example 10 contains 4,7-dioxa-
1+I confirmed the presence of 2-epoxy-brobylene oxide copolymer.

In Figure 5, CH2 0 CH2 CH2 0 CH3C
The peak based on -CH2- in H2-CH-0 and -CH2-CH2-0 is 69-7 2. Found at 5 ppm.

CH. A peak based on CH1 in -CH-01 was observed around 78.5 ppm. On the other hand, in Fig. 3, 4.7-dioxa1 2-
The peak based on CH- in the epoxy-5-methyloctane homopolymer is 78. It is seen around 5 ppm, but it is different from the pattern shown in FIG. Also CH. −
CH. The peak based on 1CH2- in -01 is 7
0. It was found around 6 ppm.

Therefore, the product of Production Example 1l is not just a blend of homopolymers, but also contains 4,7-dioxa-12-
The presence of epoxy ethylene oxide copolymer was confirmed.

Figure 8 is different from both Figures 2 and 7.

This shows that the polyoxyalkylene glycol obtained in Production Example 14 is not simply a blend of the glycidyl methyl ether polymer of Production Example 5 and the 27-dioxer 4 5-epoxyoctane polymer of Production Example 13. Furthermore, in FIG. 8, CH. -〇1C H. The peak based on one CH2- of the main chain in CH2-CH-0 and CHz O CH3 CHt CH O CHz-〇1CH3 is 68.5~
At 71 ppm, there is a peak based on -CH2- in the side chain.
Found at ~74 ppm. On the other hand, from Figure 7, -C of the homopolymer of 27-dioxa-45-epoxyoctane
The peak based on H2- is 70-74. 5ppm
No peak was observed between 68.5 and 7 oppm. Moreover, from FIG. 2, the peak based on 10H2 of the side chain of glycidyl methyl ether homopolymer is 69.
Although it is around 5 ppm, it does not match the peak in FIG.

Therefore, the raw material of Production Example 14 contains 2,7-dioxa-4
The presence of 5-epoxyoctane-glycidyl methyl ether copolymer was confirmed.

1.For the person in Notice 11, the m power obtained from the value obtained by correcting the terminal 100LL from the integral value of the proton combined with the integral value of the proton of CflL CH 2-CH - 0- from Figure 9. Compared to C H 3C H. -〇1CH. CH2-CH10-: -CH. -CH-0=3.
The ratio was 0:1.

The m ratio obtained from Figure 10 in the same manner as for the polymer of Production Example 1 for person 14 is C H3 C H2 - 〇1 CH3
CH2CHO: CH2CH
O=2.9:1.

From Figure 11 for 10 people, the integral values of protons of C, 1, L CH2-CH-0- and CH3 , C.H. -C}
From the integrated value of i-0 protons, the terminal -OCH. The set ratio calculated from the corrected value is CH 3 CHt CH-〇1 ・CHz O CH2 CH2 0 CH3C
Hz CH-○ = 2.31.

Regarding Shigeto of 11th Notice 111, CH. from Figure 12. -0-CH. -CH2〇-CflLCH. -C
From the integral value of the proton of l-{-0, the terminal one OCR. The corrected value and 1 C once you C once you 0 - CH you 0 -
Cfi, - C H Yu-o - C H3C Once Yu-C
The set ratio obtained from the integrated value of the protons of H-○ is 53 CH2-CH. -○-: CH2 0 CHz CHz O CH
3CH, -CH-0 =3. It was l1.

“Effects of the Invention” The lubricating oil of the present invention has excellent compatibility with refrigerants and lubrication performance,
It is used for compression type refrigerators, but unlike conventional lubricating oils, hydrogen-containing fluorocarbon compounds such as Freon 134a (specifically, in addition to the above Freon 134a, ■,1-dichloro-2.2.2 -1 Refluoroethane (Freon-123)
il-chloro1,1-difluoroethane (Flon-14
21));1 1-difluoroethane (fluorocarbon-1 5
2 a); Chlorodifluoromethane (Freon-22
) or trifluoromethane (Freon-23), etc.)
Good compatibility with

Therefore, the lubricating oil of the present invention is suitable for use in compression type refrigerators that use these hydrogen-containing fluorocarbon compounds, particularly fluorocarbon 134a as a refrigerant.

In addition, for the purpose of improving compatibility with the refrigerant, other compression 54 It can also be used by mixing it with lubricating oil for type refrigerators.

[Brief explanation of drawings]

Figure 1 shows the I3C-NMR spectrum of polyoxyalkylene glycol obtained in Production Example 1, and Figure 2 shows Production Example 5.
l3C- of the polyoxyalkylene glycol obtained in
Figure 3 shows the 130-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 7, and Figure 4 shows the 130-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 10. Figure 5 is the I30-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 11, and Figure 6 is the +3Cl,J spectrum of the polyoxyalkylene glycol obtained in Reference Example.
MR Subek I Le, Figure 7 shows the 13C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 13, and Figure 8 shows the 13C-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 14. In addition, Fig. 9 shows the '}i-NM55R spectrum of the polyoxyalkylene glycol obtained in Production Example 1, and Fig. 10 shows the 'H-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 4. , Figure 1l is the 'H-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 10, and Figure 12 is the 'H-NMR spectrum of the polyoxyalkylene glycol obtained in Production Example 11.
-NMR spectrum. 1 JP-A-3 205492 (19) JP-A-3 205492 (21) JP-A-3 205492 (22) JP-A-3 205492 (24) JP-A-3 205492 (25)

Claims (6)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [R^1 to R^4 are each hydrogen, a monovalent hydrocarbon group with 1 to 10 carbon atoms, or general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (R^5 and R^6 each represent hydrogen, a monovalent hydrocarbon group with 1 to 10 carbon atoms, or an alkoxyalkyl group with 2 to 20 carbon atoms. and R^7 has 2 to 5 carbon atoms.
represents a substituted alkylene group having a total of 2 to 5 carbon atoms having an alkyl group as a substituent, or a substituted alkylene group having a total of 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent, and n is an integer of 0 to 20. , R^8 represents a monovalent hydrocarbon having 1 to 10 carbon atoms. ), and at least one of R^1 to R^4 is a group represented by general formula (II)] A polyoxyalkylene glycol derivative having at least one structural unit represented by A lubricating oil for compression type refrigerators whose main ingredient is lubricating oil. (2) Polyoxyalkylene glycol derivatives have the general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) [R^1 to R^4 are the same as above. ] Claim 1 which is a homopolymer having a structural unit represented by
Lubricating oil for compression type refrigerators as described. (3) Polyoxyalkylene glycol derivatives have the general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) [R^1 to R^4 are the same as above. ] The lubricating oil for compression type refrigerators according to claim 1, which is a copolymer having at least two types of structural units represented by the following. (4) Polyoxyalkylene glycol derivatives have the general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) [R^1 to R^4 are the same as above. ] Constituent units and general formulas represented by ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (III) [R^9 to R^1^2 are each hydrogen or carbon number 1 to 3
represents an alkyl group. ] The lubricating oil for compression type refrigerators according to claim 1, which is a copolymer having at least one structural unit each represented by the following. (5) The polyoxyalkylene glycol derivative has a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an allyloxy group at the terminal position, and has a kinematic viscosity of 1 to 100 at 100°C.
The lubricating oil for a compression type refrigerator according to any one of claims 1 to 4, which is cSt. (6) The lubricating oil for a compression type refrigerator according to any one of claims 1 to 5, wherein the compression type refrigerator uses 1,1,1,2-tetrafluoroethane as a refrigerant.