JPH0726279A - Refrigerator lubricating oil and refrigerator working fluid containing the same - Google Patents

Abstract

PURPOSE:To obtain a refrigerator lubricating oil excellent in solubility in a non-chlorinated hydrofluorocarbon refrigerant and having excellent lubricity even under the use of this refrigerant by using a polyether compound of a specified formula as the principal constituent. CONSTITUTION:This refrigerator lubricating oil is composed mainly of at least one polyether compound of the formula [wherein Z is an aliphatic hydrocarbon residue which is obtained by removing hydroxy groups from a compound having 2 to 6 hydroxy groups; R<1> is a 1-8C alkyl, 1-8C alkenyl or 1-8C fluoroalkyl; A is an oxyalkylene selected from oxyethylene and oxybutylene; (a) is 1 to 5; (b) is 2 to 10; (c) is 0 to 5; (d) is 1 to 5; (e) is 2 to 10; (f) is 0 to 5; and (x) is 0 to 6, and (y) is 0 to 6, provided that (x+y) equals the number of the hydroxyl groups]. This lubricating oil exhibits excellent solubility in a non-chlorinated hydrofluorocarbon or hydrochlorofluorocarbon refrigerant from a high temperature to a low temperature and excellent in lubricity; therefore, it is suitable for an air conditioner, a refrigerator, a dehumidifier, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to various household refrigerators,
The present invention relates to a refrigerating machine lubricating oil used for industrial refrigerating machines, refrigerating warehouses and the like. In particular, the present invention relates to a refrigerating machine lubricating oil having extremely excellent solubility in a non-chlorine CFC refrigerant and excellent lubricity even under this refrigerant.

[0002]

2. Description of the Related Art Trichlorofluoromethane (CFC1) which is a conventional chlorofluorocarbon (hereinafter referred to as CFC) refrigerant.
1), dichlorofluoromethane (CFC12), 1,
2,2-Trichloro-1,1,2-trifluoroethane (CFC113) and chloropentafluoroethane (C
FC115), etc. are supposed to be completely abolished in 1996, as they cause ozone layer depletion. As alternative refrigerants, difluoromethane (HFC32), which is a non-chlorine Freon (HFC), 1,1,1-trifluoroethane (HFC134a), and pentafluoroethane (HFC125) are candidates. Depending on the use, provisionally, hydrogen-chlorine-fluorine-based CFCs having a chlorine content lower than that of CFC (referred to as HCFC), such as chlorodifluoromethane (HCFC22), dichlorotrifluoroethane (HCFC123), 1-chloro-1,
2,2,2-Tetrafluoroethane (HCFC12
4), 1-chloro-1,1-difluoroethane (HCF
C142b) and HCFC141b are used alone as a refrigerant or as a mixed refrigerant with HFC.

Conventional mineral oil-based lubricating oils do not dissolve in these HFC and HCFC refrigerants, so new lubricating oils are required. In addition, when a lubricating oil is mixed with HFC or HCFC-based CFC, the lubricity of the working fluid for the refrigerator is deteriorated as compared with the case where it is mixed with CFC-based CFC. Therefore, it is necessary to take measures against these problems. As countermeasures against this, a large number of lubricating oils such as polyoxyalkylene glycol (referred to as PAG) type and polyhydric alcohol ester type have been proposed.

Although PAG is a compound composed of carbon, hydrogen and oxygen, a PAG type lubricating oil containing fluorine has been proposed as a lubricating oil for a refrigerator of HFC134a. As such a lubricating oil, a compound having a fluorine atom-containing substituent such as a perfluorocarbon group or a perfluoroether group in the molecule (Japanese Patent Laid-Open No. 03-100097),
Formula 3 below

[Chemical 3] A compound having a repeating unit represented by the following (JP-A-02-2884)
52) or the following formula [H (CF ₂ CF ₂ ) _m CH ₂ O]
_h [CF ₃ CH ₂ O] _k [CF ₃ CF ₂ CH ₂ O]
₁ Examples include compounds having an extremely complicated structure, such as a compound represented by [PN] _n (Japanese Patent Laid-Open No. 05-70783).

[0005]

A CFC compressor is a home refrigerator such as a room air conditioner, a car air conditioner, a refrigerator, a dehumidifier, a showcase, a building air conditioner, an industrial refrigerator such as a chemical plant refrigerator, and a refrigerator. It is used in a wide variety of applications such as warehouses, and there are various types of CFC compressors. Lubricating oils for refrigerators are required to be stably dissolved with CFCs in a wide temperature range from high temperature to low temperature. For example, for freezers and refrigerators, solubility at low temperatures such as -30 ° C to -50 ° C is required. On the other hand, for room air conditioners and car air conditioners, it is sufficient that the low temperature side has solubility in the range of about -10 ° C to 0 ° C, but it is necessary to stably dissolve with CFCs at high temperatures such as + 40 ° C to + 70 ° C. is there. Also,
Lubricating oil is required to have various performances such as sealing property, lubricating property, electric insulation property, hydrolysis resistance, moisture absorption resistance, and oxidation stability in addition to solubility in CFCs. Conventionally known polyoxyalkylene glycol (PAG) type lubricating oils are generally excellent in these characteristics, but have insufficient solubility in CFCs, especially in a high temperature region, and insufficient lubricity. is there.

The object of the present invention is to maintain the excellent properties of PAG type lubricating oil while maintaining HFC refrigerant, HFC and HC.
It is an object of the present invention to provide a refrigerating machine lubricating oil that exhibits excellent solubility in a mixed refrigerant with FC, particularly in a high temperature region, and exhibits excellent lubricity.

[0007]

The present inventor has found that the HFC3
2, non-chlorine CFC refrigerants such as HFC134a, HFC125, or HCFC22, HCFC123, HC
Research to develop a PAG type lubricating oil that exhibits excellent solubility from high temperature to low temperature in hydrogen-chlorine-fluorine-based CFC refrigerants such as FC124, HCFC142b and HCFC141b or mixed refrigerants thereof, and that also has excellent lubricity. As a result of the progress, the present invention has been completed.

That is, the present inventor contains as a main component a compound having as a basic structure a polyether structure obtained by copolymerizing trifluoropropylene oxide (referred to as TFPO) and propylene oxide (referred to as PO). A lubricating oil for a refrigerator is provided, and a working fluid for a refrigerator comprising this compound and a refrigerant containing a non-chlorine CFC or a hydrogen chlorine fluorine CFC.

Hereinafter, the lubricating oil of the present invention will be described in more detail. The present invention relates to a refrigerating machine lubricating oil containing, as a main component, one or more polyether compounds selected from the group of polyether compounds represented by the general formula (1).

[0010]

[Chemical 4]

The present invention also relates to a refrigerating machine lubricating oil containing as a main component one or more polyether compounds selected from the group of polyether compounds represented by the general formula (2).

[0012]

[Chemical 5]

The basic structures of the polyether compounds represented by the general formulas (1) and (2) are both obtained by copolymerizing trifluoropropylene oxide (TFPO) and propylene oxide (PO). It has an ether structure and may be copolymerized with ethylene oxide (referred to as EO) or butylene oxide (referred to as BO), if necessary.

In the general formula (1), Z is an aliphatic hydrocarbon residue obtained by removing a hydroxyl group from a compound having 2 to 6 hydroxyl groups. The carbon number of this aliphatic hydrocarbon is preferably 2-10, more preferably 2-6. Specific examples of the compound having 2 to 6 hydroxyl groups include ethylene glycol,
There is one or more compounds selected from the group consisting of propylene glycol, trimethylene glycol, diethylene glycol, glycerol, sorbitol, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol.

R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or a fluorine-substituted alkyl group having 1 to 8 carbon atoms. These substituents are necessary in order to maintain good solubility with CFCs over a wide temperature range.
These alkyl group, alkenyl group and fluorine-substituted alkyl group may be linear or branched.

Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, tert-butyl group, pentyl group, neopentyl group, 3-methylbutyl group, hexyl group and isohexyl group. Group, heptyl group, isoheptyl group, octyl group,
Examples thereof include an isooctyl group (3-methylheptyl group, 2-ethylhexyl group and the like), 2,2,2-trifluoroethyl group, trifluoromethylethyl group and the like.

R ¹ has 1 to 6 carbon atoms, and further 1 to
It is more preferable to use a straight chain or branched chain alkyl group or a fluorine-substituted alkyl group of 5, especially 1 to 4, from the viewpoint of improving the solubility in Freon. A is one or more oxyalkylene groups selected from the group consisting of oxyethylene groups and oxybutylene groups. This oxyalkylene group contained in one molecule may be one type or two types. When both an oxyethylene group and an oxybutylene group are contained in one molecule, they may be in the form of a random copolymer or a block copolymer.

A and d represent the degree of polymerization of TFPO, which is 1 to 5, preferably 1 to 4. PO and T
The PAG-type lubricating oil obtained by copolymerizing with FPO has significantly improved solubility and lubricity at high temperature, especially in a refrigerant containing a non-chlorine flon. However, if the polymerization degrees a and d of TFPO are too large, the pour point becomes high and the viscosity becomes too high, which is unsuitable as a lubricating oil. Further, since TFPO itself is expensive, it is sufficient that TFPO is polymerized as much as necessary to improve the performance of the PAG type lubricating oil. Therefore, a and d should be 1 to 5, respectively, depending on the type of polyhydric alcohol used,
For pour points below -20 ° C, it should be below 4.

B and e are the polymerization degrees of PO and are 2 to 10 respectively. The copolymerized portion of PO is necessary in order to maintain the solubility, sealing property and lubricity of CFCs.
However, when b and e are too large, the pour point and the viscosity become too high, and therefore should be 10 or less. Further, in order to lower the pour point and maintain good lubricity, it is preferable that b and e be 3 to 7.

C and f represent the degree of polymerization of ethylene oxide or butylene oxide. Copolymerization of ethylene oxide or butylene oxide has the effect of improving lubricity to some extent. However, when the degree of polymerization increases, the pour point becomes too high. Therefore, c and f should be 5 or less, and it is preferably 3 or less to further lower the pour point.

The total value (x + y) of x and y is equal to the number of hydroxyl groups of the compound in which the residual hydroxyl group residue is Z. x
The values of y and y may be selected in the range of 0 to 6 for both x and y depending on the refrigerant used, the specifications of the refrigerator, the raw material compound of Z, and the like. In order to improve the lubricity of the polyether compound, it is preferable that x be 2 to 6 and y be 0.
On the other hand, in order to improve the electric insulation, it is preferable that the polyether compound has no or almost no hydroxyl group at the terminal, that is, x is 0, y.
Is preferably 2 to 6.

In the general formula (1), the total degree of polymerization of TFPO is represented by (ax + dy). TFPO and PO
And the total degree of polymerization of EO or BO is (ax + bx + c
x + dy + ey + fy). (Ax + dy) /
The value of (ax + bx + cx + dy + ey + fy) is 0.1
The above values are preferable from the viewpoints of improving lubricity and solubility in CFCs, and this value is 0.4 or less, particularly, 0.
When it is 3 or less, it is preferable in the sense that the rise of the pour point is suppressed.

In the general formula (2), R², R³Is water
Elementary, C1-C8 alkyl group, C1-C8 alkene
A nyl group or a fluorine-substituted alkyl group having 1 to 8 carbon atoms
It R ², R³An alkyl group, an alkenyl group,
For the fluorine-substituted alkyl group, the above-mentioned R¹About
All the explanations apply as well.

Even if R ² and R ³ are both hydrogen at the same time, good properties can be obtained in terms of lubricity and solubility in chlorine-free fluorocarbons. However, in this case, since the water absorbency becomes large, it is not preferable for applications requiring high electric insulation, for example, for hermetic refrigerators. R ² and R
^{When 3} and ³ are each an alkyl group having 1 to 8 carbon atoms or a fluorine-substituted alkyl group having 1 to 8 carbon atoms, the electrical insulating property of the polyether compound is further improved. A is an oxyalkylene group, and the above description of A in the general formula (1) applies similarly.

1 represents the degree of polymerization of TFPO, and is 1 to 6, preferably 2 to 5. The PAG type lubricating oil obtained by copolymerizing PO and TFPO has significantly improved solubility and lubricity at high temperatures, especially in a refrigerant containing a non-chlorine CFC. However, if the degree of polymerization 1 of TFPO is too large, the pour point becomes high and the viscosity becomes too high, which is unsuitable as a lubricating oil. Further, since TFPO itself is expensive, it is sufficient that TFPO is polymerized as much as necessary to improve the performance of the PAG type lubricating oil.

M is the degree of polymerization of PO and is 4 to 20. The copolymerized portion of PO is necessary in order to maintain the solubility, sealing property and lubricity of CFCs. However, if m is too large, the pour point and the viscosity will be too high.
Should be: In order to further lower the pour point and maintain good lubricity, m is preferably 6 to 20.

N represents the degree of polymerization of ethylene oxide or butylene oxide. Copolymerization of ethylene oxide or butylene oxide has the effect of improving lubricity to some extent. However, when the degree of polymerization increases, the pour point and the viscosity become too high. Therefore, n should be 5 or less, and it is preferably 3 or less to further reduce the pour point.

In the general formula (2), the degree of polymerization of TFPO is 1, and the total degree of polymerization of TFPO, PO and EO or BO is (l + m + n). l / (l + m + n)
A value of 0.1 or more is preferable from the viewpoint of improving lubricity and solubility in CFCs. Setting this value to 0.4 or less, particularly 0.3 or less suppresses an increase in pour point. It is preferable in meaning.

The polyether compound represented by the general formula (1) and the polyether compound represented by the general formula (2) preferably have a kinematic viscosity of 3 to 20 cSt at 100 ° C., and 40 ° C. At a kinematic viscosity of 32 to 68 c
It is preferable to have St. The pour point of these polyether compounds of the present invention is preferably -15 ° C or lower,
It is more preferably −20 ° C. or lower. Therefore, the polyether compound of the present invention preferably has a molecular weight of about 700 to 1800.

In the general formulas (1) and (2), TFP
O, PO, EO, and BO may be random copolymerized with each other or block copolymerized with each other. However, T
FPO is difficult to randomly copolymerize with PO, EO, and BO. Therefore, PO, EO, BO random copolymers, block copolymers, or compounds to which these are added are first prepared, and then TFPO is added to these, and if desired, the hydrogen atom of the terminal hydroxyl group is substituted with an alkyl group. By doing so, the polyether compounds of the general formulas (1) and (2) can be obtained.

As an example of producing the compound of the general formula (1),
Add caustic soda or the like to the aliphatic hydrocarbon Z (OH) x + y having a hydroxyl group, and add PO in an amount depending on the degree of polymerization or a mixture of PO and EO to allow sufficient polymerization reaction and then perform polymerization. Add the amount of TFPO according to the degree,
Allow the polymerization reaction to occur. After the reaction, a specified amount of a terminating agent (such as methyl iodide) is reacted to obtain a polyether compound having an alkyl end. When an acid is added after the polymerization reaction, a polyether compound having a hydroxyl group at the terminal can be obtained. Purify by sufficiently removing water, acid, alkaline components and the like.

As an example of producing the compound of the general formula (2),
PO polymers (polyoxypropylene glycol, polyoxypropylene glycol monomethyl ether, etc.)
Or a polymer of PO, BO, and EO (polyoxypropylene-polyoxyethylene glycol, polyoxypropylene-polyoxyethylene glycol monomethyl ether, etc.) is added with an amount of TFPO and an alkali compound according to the degree of polymerization, Let the polymerize. After the reaction, a specified amount of a terminating agent (such as alkyl iodide) is reacted to obtain a polyether compound having an end alkylated. When an acid is added after the reaction, a polyether compound having a hydroxyl group at the terminal can be obtained. Purify by sufficiently removing water, alkaline components, unreacted substances and the like.

The working fluid for the refrigerator according to the present invention is
(A) 5 to 45 parts by weight of one or more polyether compounds selected from the group of polyether compounds represented by the general formula (1) or the general formula (2), and (b) a carbon number of 1 to
The refrigerant containing the fluorohydrocarbon and / or chlorofluorohydrocarbon of No. 2 is 95 to 55 parts by weight (the total weight of the polyether compound and the refrigerant is 100 parts by weight). In (a), even if the polyether compound selected from the compound group represented by the general formula (1) and the polyether compound selected from the compound group represented by the general formula (2) are mixed. Good. In the working fluid for room air conditioners and car air conditioners, the above-mentioned refrigerant 9 is added to 10 to 30 parts by weight of the polyether compound of the present invention.
Add 0 to 70 parts by weight.

Examples of the above-mentioned refrigerant include fluorohydrocarbons having 1 to 2 carbon atoms (non-chlorine type Freon: HFC, such as HFC32, HFC134a, HFC125) and
Chlorofluorohydrocarbons having 1 to 2 carbon atoms (hydrogen chlorine fluorocarbon CFC: HCFC, such as HCFC22,
HCFC123, HCFC124, HCFC142b,
HCFC 141b), each of which is a single refrigerant, or a mixed refrigerant in which two or more of these are mixed at an appropriate ratio. From the viewpoint of preventing ozone layer depletion, a mixed refrigerant of the above-mentioned fluorohydrocarbon and hydrogen-chlorine fluorine-based fluorocarbon is preferable, and a fluorohydrocarbon alone refrigerant is more preferable.

Known additives may be added to the lubricating oil for a refrigerator of the present invention in a usual amount. Examples of such additives include antioxidants such as di-tert-butyl-p-cresol and phenyl-α-naphthylamine, ZnDT.
There are antiwear agents such as P and phosphoric acid esters, extreme pressure agents, defoaming agents such as silicone oil, metal deactivators such as benzotriazole and chelate compounds.

[0036]

The lubricating oil for refrigerator of the present invention is HFC32, HF.
C134a, non-chlorine CFC refrigerant such as HFC125, or HCFC22, HCFC123, HCFC12
4, HCFC142b, HCFC141b and other hydrogen-chlorine-fluorine-based CFC refrigerants, or mixed refrigerants thereof, show excellent solubility from a high temperature to a low temperature, and more excellent lubricity than ordinary PAG. Therefore, it is extremely suitable as a lubricating oil for a CFC compressor such as a room air conditioner, a car air conditioner, a refrigerator, a dehumidifier, a showcase, a building air conditioner, a chemical plant refrigerator, a frozen warehouse, and the like.

[0037]

EXAMPLES Hereinafter, description will be given based on specific examples. First, a polyether compound was produced according to the following production examples.

(Production Example 1) In a dry three-necked flask,
23 ml of dried 1,2-dimethoxyethane (DME)
And dried polyoxypropylene glycol (molecular weight 725) H [OCH (CH ₃ ) CH ₂ ] _m OH (average value of degree of polymerization m = 12.5) of 21.75 g (30 mmo)
1) and 1.95 g (30 mmol) of powdered KOH are added, and the mixture is stirred at room temperature for 30 minutes. Dried TFP
O5.1 ml (60 mmol) is gradually added, and the mixture is stirred at room temperature. As the temperature of the reactants increases with stirring, 4
Keep at 0 ° C. Twenty-four hours after the addition of TFPO, 3.7 ml (59 mmol) of methyl iodide, which is a terminating agent, is added.

The reaction mass is dissolved in ether and washed with water. Then, sodium sulfate is added and dried. Evaporate the solvent and dry under vacuum. 26.14 g of liquid is obtained (yield 91%). ¹ H-NMR, 13 C
-NMR, 19F-NMR and infrared absorption spectrum are analyzed. The presence of CH, CH ₂ , OCH ₃ , CH ₃ , CF _{3 and} the presence of OH, F, ether are confirmed. The structural formula of the polyether compound according to this Production Example is shown below.

[0040]

[Chemical 6]

Methine group C obtained by ¹ H-NMR
The ratio between the average degree of polymerization of PO and the average degree of polymerization of TFPO is calculated from the peak integral ratio of H, the methylene group CH ₂ , the methoxy group OCH ₃ , and the total hydroxyl groups and the methyl group. Since this ratio and the average value of the polymerization degree m of the polyoxypropylene glycol used are 12.5, the average value of the polymerization degree 1 of TFPO is 1.7. Further, the kinematic viscosity of the polyether compound according to the present production example at 100 ° C. is 7.
It is 5 cSt.

(Production Example 2) In the same manner as in Production Example 1, the polyether compound of the present invention is produced. However, 1, 2
The amount of dimethoxyethane (DME) is 22 ml. The molecular weight of polyoxypropylene glycol is 725,
The average value of the degree of polymerization m is 12.5, and the addition amount is 16.9 g.
(23 mmol). The amount of powdered KOH added is 1.5
It is set to 2 g (23 mmol). The amount of TFPO added is 8.
The amount of methyl iodide as a terminating agent is 0 ml (93 mmol), and the amount of methyl iodide added is 2.9 ml (47 mmol). In this way, the reaction is performed to obtain 24.18 g of a liquid material (yield 88%). Then, analysis is performed in the same manner as in Production Example 1, and it is confirmed that the polyether compound has the same structural formula as in Production Example 1. In the same manner as in Production Example 1, the average value 4.2 of the polymerization degree 1 of TFPO is calculated. The kinematic viscosity at 100 ° C. of the polyether compound according to this production example is 9.8.
It is cSt.

(Production Example 3) In a dry three-necked flask,
25 ml of dried 1,2-dimethoxyethane (DME)
And 17.00 g (40 mmol) of dried polyoxypropylene glycol (molecular weight 425) H [OCH (CH ₃ ) CH ₂ ] _m OH (average value of degree of polymerization m = 6.8).
And 2.60 g (40 mmol) of powder KOH,
Stir for 30 minutes at room temperature. Add this to dried TFPO1
0.3 ml (120 mmol) is gradually added and stirred at room temperature. As the temperature of the reactants increases with stirring, 4
Keep at 0 ° C. 24 hours after the addition of TFPO, 8.5 ml (42.5 mmol) of 5N hydrochloric acid is added.

The reaction is dissolved in ether and washed with water. Then, sodium sulfate is added and dried. Evaporate the solvent and dry under vacuum. 22.65 g of liquid is obtained (74% yield). ¹ H-NMR, 13 C
-NMR, 19F-NMR and infrared absorption spectrum are analyzed. The presence of CH, CH ₂ , CH ₃ , CF ₃ , OH,
Presence of F and ether is confirmed. The structural formula of the polyether compound according to this Production Example is shown below.

[0045]

[Chemical 7]

A methine group obtained by ¹ H-NMR,
The ratio between the average degree of polymerization of PO and the average degree of polymerization of TFPO is calculated from the peak integration ratio of the sum of methylene groups and hydroxyl groups and the methyl group. Since the average value of this ratio and the polymerization degree m of the polyoxypropylene glycol used is 6.8, the average value of the polymerization degree l of TFPO is calculated as follows:
It is 4.8. 1 of the polyether compound according to this production example
The kinematic viscosity at 00 ° C. is 8.8 cSt.

(Production Example 4) In a dry three-necked flask,
23 ml of dried 1,2-dimethoxyethane (DME)
And dried polyoxyethylene polyoxypropylene glycol monomethyl ether (molecular weight 816) CH ₃
O [CH (CH ₃₎ CH ₂ O] _{m (CH 2 CH 2 O)} n
H (average of polymerization degree m = 12, average of polymerization degree n = 2)
24.50 g (30 mmol) and powder KOH 1.9
Add 5 g (30 mmol) and stir at room temperature for 30 minutes. To this, 5.1 ml of dry TFPO (6.0 mm
ol) is gradually added and the mixture is stirred at room temperature. Since the temperature of the reaction product rises with stirring, it is maintained at 40 ° C. TFP
24 hours after the addition of O, the terminator methyl iodide 3.7 was added.
Add ml (60 mmol).

The reaction is dissolved in ether and washed with water. Then, sodium sulfate is added and dried. Evaporate the solvent and dry under vacuum. 28.00 g of liquid is obtained (yield 90%). ¹ H-NMR, 13 C
-NMR, 19F-NMR and infrared absorption spectrum are analyzed. The presence of CH, CH ₂ , OCH ₃ , CH ₃ , CF _{3 and} the presence of OH, F, ether are confirmed. The structural formula of the polyether compound according to this Production Example is shown below.

[0049]

[Chemical 8]

The average value of the degree of polymerization 1 of TFPO was calculated by the same method as in Production Examples 1 to 3, and was 2.0. The kinematic viscosity at 100 ° C. of the polyether compound according to this Production Example is 8.8 cSt.

(Production Example 5) In the same manner as in Production Example 1, the polyether compound of the present invention is produced. However, 5.8 ml of propyl iodide was used as a terminator for the polymerization reaction of TFPO.
(59 mmol) is added. Then, analysis is performed in the same manner as in Production Example 1, and a polyether compound having the following structural formula is confirmed. The average value of the degree of polymerization 1 of TFPO was calculated in the same manner as in Production Example 1 to be 1.7. The kinematic viscosity at 100 ° C. of the polyether compound according to this production example is 9.2 cSt.

[0052]

[Chemical 9]

(Production Example 6) In a dry three-necked flask,
20 ml of dried 1,2-dimethoxyethane (DME)
And dried polyoxypropylene glycol monomethyl ether (molecular weight 960) H [OCH (CH ₃ ) CH
₂ ] _m OCH ₃ (average value of degree of polymerization m = 18.3) is 2
2.40 g (23 mmol) and powder KOH 1.52 g
(23 mmol) is added and the mixture is stirred at room temperature for 30 minutes.
To this, 4.0 ml of dried TFPO (47 mmol)
Is gradually added and stirred at room temperature. Since the temperature of the reaction product rises with stirring, it is maintained at 40 ° C. 24 hours after the addition of TFPO, 2.9 ml of methyl iodide as a terminator
(46 mmol) is added.

The reaction product was purified in the same manner as in Production Example 1 to obtain 23.54 g of a liquid product (yield 85%).
The liquid substance was subjected to ¹ H-NMR, 13 C-NMR, 19 F-N
Analyze by MR and out-of-seat absorption spectrum. CH, CH ₂ ,
The presence of OCH ₃ , CH ₃ and CF ₃ , and the presence of F and ether are confirmed. The structural formula of the polyether compound according to this Production Example is shown below.

[0055]

[Chemical 10]

A methine group obtained by ¹ H-NMR,
The ratio between the average degree of polymerization of PO and the average degree of polymerization of TFPO is calculated from the peak integration ratio of the sum of methylene groups and methoxy groups and the methyl group. Since the average value of this ratio and the degree of polymerization m of the polyoxypropylene glycol monomethyl ether used was 18.3.
The average value of is calculated to be 3.5. The kinematic viscosity of the polyether compound according to this production example at 100 ° C. is 9.5.
It is cSt.

(Production Example 7) In a dry three-necked flask,
Dry 1,2-dimethoxyethane (DME) ml,
Dried neopentyloxypolyoxypropylene glycol

[Chemical 11](Average value of degree of polymerization e = 7) is 18.32 g (20 mmo
1) and powder KOH 2.64 g (40 mmol)
And stir at room temperature for 30 minutes. Dried TFPO
6.9 ml (80 mmol) was gradually added to 40 ° C or less.
Stir at room temperature. 24 hours after adding TFPO,
Add 5.0 ml (80 mmol) of certain methyl iodide
It The reaction is dissolved in ether and washed with water. That
Then, sodium sulfate is added and dried. Evaporate the solvent
And vacuum dry. 23.74 g of liquid is obtained
(Yield 87%). Liquid matter,¹H-NMR,¹³C-NM
R,¹⁹Analyze by F-NMR and infrared absorption spectrum. C
H, CH₂, OCH₃, CH₃, CF ₃The presence of OH,
Presence of F and ether is confirmed. Poly according to this manufacturing example
The structural formula of the ether compound is shown below.

[0058]

[Chemical 12]

The ratio between the average degree of polymerization of PO and the average degree of polymerization of TFPO is calculated from the peak integral ratio of the sum of methine, methylene and methoxy groups and the sum of methyl groups obtained by ¹ H-NMR. Since this ratio and the average value of the degree of polymerization e of neopentyloxypolyoxypropylene glycol used are 7, the average value of the degree of polymerization d of TFPO is calculated to be 2.0. The kinematic viscosity of the polyether compound according to this production example at 100 ° C. is 10.2 cS.
t.

Next, the polyether compound of each of Production Examples 1, 3, 5, and 6 (hereinafter abbreviated as PAG 1, 3, 5, and 6) is compatible with the non-chlorine-based CFC refrigerant and lubricity. To test. Further, the following compounds are prepared as the polyether compounds of Comparative Examples 1 and 2. Comparative Example _{1: C 4 H 9 ─ (} PO) p─OH ( NOF Corporation, "Yunirubu MB─11"). Comparative Example _{2: C 4 H 9 ─ (} PO) p─ (EO) e─OH
("Unilub 50MB11" manufactured by Nippon Oil & Fats Co., Ltd.).

(Compatibility with mixed refrigerant of HFC32 and HFC134a) 0.6 g of each of the polyether compounds of PAG1, 3, 5, 6 and Comparative Examples 1 and 2 was sampled in a glass tube, and HFC32 and HFC134a were further collected. 30 parts by weight /
2.4 g of a mixed refrigerant mixed at a ratio of 70 parts by weight is collected and a glass tube is sealed. The glass tube is cooled and heated to observe whether the polyether compound and the refrigerant are mutually dissolved or separated.

As a result, the polyether compound P of the present invention was obtained.
Comparing the compatibility of AG1, 3, 5, and 6 with the mixed refrigerant, all of the above-mentioned four polyether compounds are polyethers at a temperature lower than −50 ° C. on the low temperature side and a temperature higher than + 70 ° C. on the high temperature side. The compound and the refrigerant are mutually dissolved. On the other hand, in the case of the polyether compounds of Comparative Examples 1 and 2, both the polyether compound and the refrigerant are mutually dissolved at a temperature lower than -50 ° C on the low temperature side.
On the high temperature side, the polyether compound and the refrigerant are separated at + 19 ° C. Therefore, the polyether compound of the present invention is
The melting temperature on the high temperature side with the chlorine-free CFC refrigerant is higher than the conventional temperature by 50 ° C. or more.

(Compatibility with HFC125 Refrigerant) Further, HFC125 refrigerant is used in place of the above mixed refrigerant,
The compatibility of the polyether compounds of PAG 1, 3, 5, 6 and Comparative Examples 1 and 2 with the HFC125 refrigerant is tested according to the method described above.

In the case of PAGs 1, 3, 5, and 6 of the present invention, all are temperatures below -50 ° C on the low temperature side and +70 on the high temperature side.
At temperatures exceeding ° C, the polyether compound and the refrigerant are stably dissolved in each other. In the case of the polyether compound of Comparative Example 1, on the low temperature side, the polyether compound and the refrigerant are mutually dissolved at a temperature of less than -50 ° C.
On the high temperature side, the polyether compound and the refrigerant separate at + 47 ° C. In the case of the polyether compound of Comparative Example 2, the polyether compound and the refrigerant are mutually dissolved at a temperature lower than -50 ° C on the low temperature side, but + 50 ° C on the high temperature side.
The polyether compound and the refrigerant are separated by.

Therefore, the polyether compound of the present invention is
The melting temperature on the high temperature side with the chlorine-free CFC refrigerant is higher than the conventional temperature by 20 ° C or more. Further, the polyether compound and the refrigerant are stably dissolved in a wide temperature range from low temperature to high temperature.

(Lubricity Test) For the polyether compounds of PAG 1, 3, 5, 6 and Comparative Examples 1 and 2, ASTM
In accordance with D-3223-7, Falex (Fale
x) Measure the seizure load. The test conditions and test results are as follows.

[0067]

[Table 1] Test conditions: Rotational speed 290 rpm Test temperature 30 ° C HFC134a blowing amount 70 ml / min Test piece pin Steel (SAE 313
5) V-Block Steel (AISI C-113
7)

[0068]

Table 2 Test Results: Falex Baking Load (lbs) PAG1 920 PAG3 970 PAG5 940 PAG6 910 Comparative Example 1 700 Comparative Example 2 760

As can be seen from the above results, the PAGs 1, 3, 5, 6 of the present invention were compared with the polyether compounds of Comparative Examples.
Has a load capacity of 150 to 2 under a chlorine-free fluorocarbon refrigerant.
It's over £ 100.

[0070]

As described above, according to the present invention, it exhibits excellent solubility in a chlorine-free fluorocarbon refrigerant or a hydrogen-chlorine fluorine-based fluorocarbon refrigerant from a high temperature to a low temperature, and more than in a normal PAG. Has excellent lubricity, and can provide a refrigerator lubricating oil suitable for air conditioners, car air conditioners, refrigerators, dehumidifiers, commercial / industrial refrigerators, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Takahashi 3-17-35, Niizominami, Toda City, Saitama Prefecture

Claims (6)

[Claims] 1. A refrigerating machine lubricating oil containing, as a main component, one or more polyether compounds selected from the group of polyether compounds represented by the general formula (1). [Chemical 1] In the general formula (1), Z is an aliphatic hydrocarbon residue obtained by removing a hydroxyl group from a compound having a hydroxyl group of 2 to 6, and R ¹ is an alkyl group having a carbon number of 1 to 8 and a carbon number of 1 to 8 Is an alkenyl group or a fluorine-substituted alkyl group having 1 to 8 carbon atoms, A is at least one oxyalkylene group selected from the group consisting of oxyethylene groups and oxybutylene groups, and a is 1 to 5 B is an integer of 2-10, c is an integer of 0-5, d is an integer of 1-5, e is an integer of 2-10, f Is an integer of 0 to 5, x is 0 to 6, y is 0 to 6, and x + y is equal to the number of hydroxyl groups. 2. In the general formula (1), a is an integer of 1 to 4, b is an integer of 3 to 7, c is an integer of 0 to 3, and d is 1 Is an integer of 4 to 4, e is an integer of 3 to 7, f is an integer of 0 to 3, and the polyether compound has a kinematic viscosity at 100 ° C. of 3 to 20 cSt. Item 1. A refrigerating machine lubricating oil according to item 1. 3. (a) 5 to 45 parts by weight of one or more polyether compounds selected from the group of polyether compounds represented by the general formula (1) according to claim 1, and (b) 1 carbon atom. 2 to 95, and a refrigerant containing fluorohydrocarbon and / or chlorofluorohydrocarbon.
A working fluid for a refrigerator, which comprises 100 parts by weight (the total weight of the polyether compound and the refrigerant is 100 parts by weight). 4. A refrigerating machine lubricating oil containing one or more polyether compounds selected from the group of polyether compounds represented by the general formula (2). [Chemical 2] In the general formula (2), R ² and R ³ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or 1 carbon atom.
To 8 are fluorine-substituted alkyl groups, A is one or more oxyalkylene groups selected from the group consisting of oxyethylene groups and oxybutylene groups, l is an integer from 1 to 6, and m is Is an integer of 4 to 20, and n is an integer of 0 to 5. 5. In the general formula (2), l is an integer of 2 to 5, m is an integer of 6 to 20, n is an integer of 0 to 3, and the polyether is The refrigerator lubricating oil according to claim 4, wherein the compound has a kinematic viscosity at 100 ° C of 3 to 20 cSt. 6. (C) 5 to 45 parts by weight of one or more polyether compounds selected from the group of polyether compounds represented by the general formula (2) according to claim 4, and (D) 1 carbon atom. 2 to 95, and a refrigerant containing fluorohydrocarbon and / or chlorofluorohydrocarbon.
A working fluid for a refrigerator, which comprises 100 parts by weight (the total weight of the polyether compound and the refrigerant is 100 parts by weight).