Refrigeration oil composition

Abstract: The refrigeration oil composition comprises (1) a hydrogenated fluoroethane and (2) an ester compound obtained from (2-a) an aliphatic polyhydric alcohol having 1 to 6 primary hydroxyl groups, (2-b) a saturated aliphatic monocarboxylic acid having 2 to 9 carbon atoms, straight or branched, or a derivative thereof and (2-c) a saturated aliphatic dicarboxylic acid having 2 to 10 carbon atoms, straight or branched, or a derivative thereof, said ester compound having a kinematic viscosity at 100 degree C of 1 to 100 cst.

Description: The invention relates to a refrigeration oil. composition, and particularly to a lubricating oil for a refrigerator or a refrigerator oil, comprising a hydrogenated fluoroethane. The use of dichlorodifluoromethane (R-12) in refrigerators and automotive air conditioners has recently been restricted and will be prohibited in future, in order to protect the ozone layer. Therefore, various fluoroethane refrigerants which do not destroy the ozone layer have been developed as a substitute for R-12. Since these fluoroethane refrigerants have higher polarity than that of R-12, they have a low compatibility with lubricating oils that have been used conventionally as a refrigerator oil, such as naphthenic mineral oil, poly-α-olefin or alkylbenzenes. This causes phase separation at lower temperatures. If this phenomenon occurs, oil return deterioriates and a thick oil film adheres around a condenser or an evaporator as a heat-exchanger, which prevents heat transfer and results in major defects such as poor lubrication, bubbling at the start, and so forth. Accordingly, the conventional refrigerator oils cannot be used as a refrigerator oil in an atmosphere of these new refrigerants. As to the lubricating property, R-12 is effective in that it is partially decomposed to generate hydrogen chloride which reacts with the friction surface to form a chloride film, which improves its lubricating property. Because fluoroethane refrigerants which do not contain chlorine atom(s), such as pentafluoroethane, 1,1,1-trifluoroethane or 1,1-difluoroethane, cannot be expected to provide such an effect, a refrigerator oil used in combination with them must have a higher lubricating property than that of conventional refrigerator oils. Furthermore, the refrigerator oil must have a high stability in a refrigerant atmosphere, and not produce any adverse effects on organic materials such as an insulating material used for a refrigerator or a hose used for an automative air conditioner. To solve the problem of poor compatibility of the lubricating oils with the fluoroethane refrigerants, a polyether lubricating oil has been proposed. Since this type of lubricating oil has higher polarity than that of a naphthenic mineral oil, it has a good compatibility with these refrigerants at low temperatures. As described in U.S. Patent No. 4,755,316, however, the polyether lubricating oil is disadvantageous in that when the temperature rises, it is likely to cause phase separation, so that it cannot be used reliably as a refrigerator oil. There are some other problems with the polyether lubricating oil. One of them is that since it has high polarity, it interacts with the insulating material used in the refrigerator, such as a PET film, producing adverse effects. Another problem is its high hygroscopicity. The moisture in this lubricating oil reduces its thermal stability in a refrigerant atmosphere and causes hydrolysis of the organic material, for example, PET film. Furthermore, the polyether lubricating oil does not possess entirely satisfactory lubricating properties. In comparison with the conventional R-12 - naphthenic mineral oil system, the fluoroethane refrigerant - polyether lubricating oil system has poor lubricating property. Several methods of using esters in combination with fluoromethane have been proposed and are disclosed in, for example, Japanese Patent Laid-Open Nos. 131548/1981, 133241/1981, 181895/1986, and 592/1987. The use of esters mixed with other lubricating oil is disclosed in Japanese Patent Laid-Open Nos. 125494/1981, 125495/1981 and 62596/1986. Furthermore, the use of esters together with additives is disclosed in Japanese Patent Laid-Open Nos. 155093/1980, 36570/1981, 125494/1981, 15592/1983, 103594/1983, 171799/1986, and 292895/1987. However, all of these prior art methods are directed to the systems used in combination with dichlorodifluoromethane (R- 12) or monochlorodifluoromethane (R- 22) refrigerant but do not mention the fluoroethane refrigerant. Moreover, the object of these methods is to improve the thermal stability in R-12 or R-22 atmosphere. Japanese Patent Laid-Open Nos. 143609/1978 and 164393/1984 mention the compatibility with R-12 or R-22 in addition to the improvement of the thermal stability in F-12 or R-22 atmosphere. However, the former is directed to the prevention of excessive dissolution in R-12 and the latter in R-22. In other words, they do not at all mention an improvement in compatibility with the fluoroethane refrigerant. As described above, the prior art technique is not one directed to the development of a refrigerator oil having excellent compatibility, thermal stability and lubricating properties in a fluoroethane refrigerant atmosphere. Accordingly, it is an object of the present invention to provide a refrigerator oil which has sufficient viscosity and high compatibility with the fluoroethane refrigerant at both low and high temperatures, and has excellent thermal stability and lubricating properties in this refrigerant atmosphere. As a result of intensive studies, the inventor of this invention has discovered that certain kinds of ester compounds can fulfil the above objectives. The refrigeration oil composition of the invention comprises (1) a hydrogenated fluoroethane and (2) an ester compound obtained only from: (2-a) an aliphatic dihydric alcohol having 1 to 2 primary hydroxyl groups; (2-b) a branched saturated aliphatic monocarboxylic acid having 2 to 9 carbon atoms, or a derivative thereof; and (2-c) a saturated aliphatic dicarboxylic acid having 2 to 8 carbon atoms, straight or branched, or a derivative thereof, said ester compound having a kinematic viscosity at 100°C in the range of 1 to 100 x 10 -6 m 2 /S(cst). It is preferable that a weight ratio of (1) the hydrogenated fluoroethane to (2) the ester compound ranges from 10/1 to 1/5, and more preferably from 5/1 to 1/2. The above composition may further comprise another lubricant at a weight ratio to the ester compound of up to 95 wt.%. The ester compound may have a kinematic viscosity at 100 degree C in the range of 1 to 20 10 -6 m 2 /s (cst) or 20 to 100 10 -6 m 2 /s (cst). The ester compound may be obtained from 1 mole of (2-a), 4 moles or less of (2-b) and 0.9 mole or less of (2-c). The ester compound may have a saponification value of 330 mg KOH/g or larger. The hydrogenated fluoroethane may be 1,1,1,2- tetrafluoroethane. The carboxylic acid or its derivative used for the preparation of the ester used in the present invention includes branched saturated monocarboxylic acids and their derivatives, as the component (2-b), and straight-chain and branched saturated aliphatic dicarboxylic acids and their derivatives as the component (2-c). The number of carbon atoms of the monocarboxylic acid as the component (2-b) ranges from 2 to 9, preferably from 5 to 8. If the number of carbon atoms is greater than 9, the compatibility with the fluoroethane refrigerant decreases. Particular examples of these monocarboxylic acids and their derivatives include isobutyric acid, isovaleric acid, pivalic acid, 2-methylbutyric acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, 2,2-dimethylbutyric acid, 2-ethylbutyric acid, tert-butylacetic acid, 2,2-dimethyl-pentanoic acid, 2-ethylpentanoic acid, 3-ethyl-pentanoic acid, 2-methylhexanoic acid (isoheptanoic acid), 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-ethylhexanoic acid, 3,5-dimethylhexanoic acid, 2,2-dimethylhexanoic acid, 2-methylheptanoic acid (isooctanoic acid), 3-methylheptanoic acid, 4-methylheptanoic acid, 2-propylpentanoic acid, , 2,2-dimethylheptanoicacid, 3,5,5-trimethylhexanoic acid, 2-methyloctanoic acid, 2-ethylheptanoic acid, 3-methyloctanoic acid, and their methyl esters, ethyl esters and acid anhydrides. The esters used in the present invention are obtained by reacting the components (2-a) to (2-c) together. The compatibility of the ester used in the present invention with the fluoroethane refrigerant at low temperatures, generally decreases with increasing viscosity. Accordingly, the kinematic viscosity of the ester at 100°C is preferably not smaller than 1 10 -6 m 2 /s (cst) and not greater than 20 10 -6 m 2 /s (cst), more preferably, it is not smaller than 1 cst and not greater than 15 10 -6 m 2 /s (cst). If the kinematic viscosity at 100°C is greater than 20 10 -6 m 2 /s (cst), the,compatibility with the fluoroethane refrigerant at low temperatures decreases. As to the lubricating property in an atmosphere of the fluoroethane refrigerant, on the other hand, the ester used in the present invention is superior to the polyether lubricating oil. Among the esters used in the present invention, those having a higher viscosity have better lubricating properties. Those esters having a kinematic viscosity of higher than 20 10 -6 m 2 /s (cst) at 100°C are particularly preferred. In consideration of the compatibility, those esters whose kinematic viscosity at 100°C is not greater than 100 10 -6 m 2 /s (cst) are preferred. The ester used in the present invention, having a kinematic viscosity of higher than 20 10 -6 m 2 /s (cst) at 100°C, can be used as a base oil and also in a mixture with the esters used in the invention whose kinematic viscosity at 100°C is not greater than 20 10 -6 m 2 /s (cst), and esters other than those used in the present invention, or with synthetic oils such as polyether. When the esters used in the invention are mixed in this manner, the lubricating property of the esters used in the present invention, whose kinematic viscosity at 100°C is not greater than 20 10 -6 m 2 /s (cst); the esters other than those used in the present invention; or the synthetic oils such as polyether, can be improved. As to the esters used in the present invention whose kinematic viscosity at 100°C is greater than 20 10 -6 m 2 /s (cst), and whose compatibility with the fluoroethane refrigerant at low temperatures is poor, their compatability with the fluoroethane refrigerant at low temperatures can be improved by mixing them with the esters used in the present invention whose kinematic viscosity at 100°C is not greater than 20 10 -6 m 2 /s (cst), as described above. The esters used in the present invention, exhibit excellent compatibility with the fluoroethane refrigerant at low temperatures and excellent lubricating properties. Particular example of the dihydric alcohols (2-a) are ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, and 2-ethyl-1,3-hexanediol; and hindered alcohols represented by the following formula (I). The number of carbon atoms of the aliphatic dihydric alcohol ranges from 2 to 30, preferably from 2 to 20, and more preferably from 2 to 10. The hindered alcohol represented by the following formula (I) exhibits excellent heat stability. where R 1 and R 2 are each a C 1 to C 6 alkyl group. Particular examples of the component (2-c) described above include oxalic acid, malonic acid, methylmalonic acid, succinic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, glutaric acid, adipic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, butylmalonic acid, diethylmalonic acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2-ethyl-2-methylsuccinic acid, 3-methyladipic acid, pimelic acid, suberic acid, and 2,2-dimethyladipic acid. The esters used in the present invention exhibit excellent compatibility with the fluoroethane refrigerant at low temperatures when the kinematic viscosity is high. Even when the kinematic viscosity at 100°C is greater than 20 10 -6 m 2 /s (cst), the compatibility is excellent. As to the lubricating property, this ester is better than those obtained from the trior higher-hydric alcohols of the same viscosity grade among the esters used in the present invention. In the ester used in the present invention, any of the alcohol, monocarboxylic acid and dicarboxylic acid as the starting materials preferably has a branched structure from the aspect of corrosion resistance to metals and hydrolysis stability. From the aspect of the compatibility with the fluoroethane refrigerant, the saponification value of the ester of the present invention is preferably at least 330 mgKOH/g and more preferably at least 350 mgKOH/g. If the saponification value is smaller than this value, the compatibility with the fluoroethane refrigerant decreases. The esters used in the present invention can be obtained by an ordinary esterification or transesterification reaction. In this case, up to 0.9 mol of the dicarboxylic acid or its derivative is reacted with 1 mol of the polyhydric alcohol. If the amount of the acid is greater than 0.9 mol, the viscosity becomes high. The acid value of the resulting ester is preferably as low as possible and is not more than 5 mgKOH/g, preferably not more than 1 mgKOH/g and more preferably not more than 0.2 mgKOH/g. The refrigerator oil used in the present invention contains the ester described above as the base oil, and may further contain mineral oil and synthetic oil such as poly-α-olefin, alkylbenzene, esters other than those described above, polyethers, perfluoropolyethers, phosphoric esters or their mixture. However, the synthetic oil is not limited to those described above. The weight ratio in the mixture of the ester of this invention to other lubricating oil may be arbitrary so long as the performance such as the compatibility with the hydrogenated fluoroethane refrigerant is not lowered. Generally, the weight ratio ranges from 100/0 to 5/95, preferably 100/0 to 10/90, and more preferably 100/0 to 30/70. The ester used in the present invention exhibits excellent performance with respect to the fluoroethane refrigerant and can provide a refrigerator oil exhibiting excellent compatibility, thermal stability and lubricating properties, particularly when used in a hydrogenated fluoroethane refrigerant atmosphere. Examples of the hydrogenated fluoroethane refrigerant include 1,1,1,2-tetrafluoroethane (R-134a), 1,1,1,2-tetrafluoro-2-chloroethane (R-124), pentafluoroethane (R-125), 1,1-difluoro-1-chloroethane (R-142b), 1,1,1-trifluoroethane (R-143a), and 1,1-difluoroethane (R-152). It is possible to add ordinary lubricant additives such as an antioxidant, an extreme-pressure additive, an oiliness improving agent, a defoaming agent, a metal deactivator, and the like, to the refrigerator oil of the present invention, whenever necessary. Examples of the antioxidants that can be used include phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol and 4,4'-methylenebis(2,6-di-t-butylphenol); amine antioxidants such as p,p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylphenyl-1-naphthylamine, and alkylphenyl-2-naphthylamine; sulfur-containing antioxidants such as alkyl disulfide, thiodipropionic acid esters and benzothiazole; and zinc dialkyl dithiophosphate and zinc diaryl dithiophosphate. Examples of the extreme-pressure additive and oiliness improving agents that can be used include zinc compounds such as zinc dialkyl dithiophosphate and zinc diaryl dithiophosphate; sulfur compounds such as thiodipropinoic acid esters, dialkyl sulfide, dibenzyl sulfide, dialkyl polysulfide, alkylmercaptan, dibenzothiophene and 2,2'-dithiobis(benzothiazole); phosphorus compounds such as triaryl phosphates such as tricresyl phosphate and trialkyl phosphates; dialkyl or diaryl phosphates; trialkyl or triaryl phosphites; dialkyl or diaryl phosphites; monoalkyl or monoaryl phosphites; fluorine compounds such as perfluoroalkyl polyethers, trifluorochloroethylene polymers and graphite fluoride; silicon compounds such as a fatty acid-modified silicone; molybdenum disulfide, graphite, and the like. Examples of the defoaming agents that can be used include a silicone oil such as dimethylpolysiloxane and organosilicates such as diethyl silicate. Examples of the metal deactivators that can be used include alizarin, quinizarin and mercaptobenzothiazole. Furthermore, epoxy compounds such as phenyl glycidyl ethers, alkyl glycidyl ethers, epoxystearic acid esters and epoxidized vegetable oil, organotin compounds and boron compounds may be added as the additive for stabilizing refrigerants. The refrigeration oil used in accordance with the present invention has sufficient viscosity, high compatibility with the hydrogenated fluoroethane refrigerants, and excellent thermal stability and lubricating property in this refrigerant atmosphere The present invention will now be described more specifically with reference to Examples thereof, though it is not limited to these Examples. Preparation Example A stirrer, a thermometer, a nitrogen blow pipe and a dehydration tube equipped with a cooler were fitted to a 1-ℓ four-necked flask. Then, 104g (1.0 mol) of neopentyl glycol, 116g (1.0 mol) of caproic acid and 66g (0.5 mol) of glutaric acid were put into the flask to conduct esterification at 240°C for 10 hours in a nitrogen stream to thereby obtain an ester. Similar reactions were carried out by use of the alcohols and carboxylic acids listed in Table 1 and the esters Nos. 1-5 used in the present invention and the esters Nos. 1 to 7 of the Comparative Products were obtained. The esters Nos. 1-5 used in the invention, the comparative products Nos. 1 to 13 were tested to determine a kinematic viscosity at 40°c, at 100 °c and a viscosity index according to JIS K2283, and then a pour point according to JIS K2269. Results are shown in Table 1. Example 1: In order to examine the compatibility of each of the products Nos. 1 to 5 and the Comparative Products Nos. 1 to 13 obtained in the preparation Example with 1,1,1,2-tetrafluoroethane (R-134a), the phase separation temperatures at both low and high temperatures of each sample in the concentration of 10 vol% for 1,1,1,2-tetrafluoroethane were measured. As to the Comparative Products having an insufficient low temperature phase separation temperature, the measurement of the high temperature phase separation temperature was omitted. The results are given in Table 2. As can be understood clearly from Table 2, the esters used in the present invention had excellent compatibility with 1,1,1,2-tetrafluoroethane at the low temperature and the compatibility did not decrease even when the temperature increased. (Esters Nos. 1, 2, and 3 of this invention) had sufficiently high compatibility even when the viscosity was high. Low-temperature separation temperature (°C) High-temperature separation temperature (°C) Product of this invention 1 -60> 70< 2 -60> 70< 3 -60> 70< 4 -28 70< 5 -60> 70< Comparative product 1 30< measurement omitted 2 30< " 3 30< " 4 -13 " 5 30< " 6 30< " 7 30< " 8 30< " 9 30< " 10 -60> 70< 11 -60> 70< 12 -60> 58 13 30< measurement omitted Example 2: The load resistance of each of the products Nos. 3 and 4 in this invention and Comparative Products Nos. 8 to 11 was examined by carrying out the Falex test. More specifically, while blowing 1,1,1,2,-tetrafluoroethane (Flon 134a) at a rate of 150cc/min, non-load rotation was effected for 10 minutes and then, after preliminary rotation was effected at 200 lb for 5 minutes, the load was increased by 50-lb load every two minutes to examine a seizure load. The results are given in Table 3. As can be understood clearly from Table 3, the naphthene oil (Comparative Product No.8) has a lower load resistance when 1,1,1,2-tetrafluoroethane was blown (450 lb) than when dichlorodifluoromethane (R-12) was blown (Reference Example 1: 600 lb). The load resistance of poly-α-olefin (Comparative Product No. 9) and polyethers (Comparative Products Nos. 10 and 11) was not greater than 550 lb when 1,1,1,2-tetrafluoroethane was blown, so that they had inferior load resistance. On the other hand, the load resistance of each of the esters used in the present invention was not smaller than 600 lb when 1,1,1,2-tetrafluoroethane was blown, demonstrating that they had superior load resistance. The esters having a kinematic viscosity of higher than 20 cst at 100°C (Products Nos. 3 and of 4 this invention) exhibited a particularly high load resistance. Seizure load (1b) Product of this invention 3 1400< 4 1400< Comparative Products 8 450 9 450 10 550 11 550 Reference Example 1 600 Example 3: The wear resistance of products Nos. 1 and 3 of this invention and Comparative Products Nos. 8 to 11 obtained in the preparation Example, the Product. No. 6 of this invention as the mixture of the product No. 1 of this invention (70 wt%) and the product No. 3 of this invention (30 wt%). More specifically, non-load rotation was effected for 10 minutes while blowing 1,1,1,2-tetrafluoroethane (R-134a) at a rate of 150cc/min and then preliminary rotation was effected at 200 lb for 5 minutes. Thereafter the rotation was effected at 350 lb for 60 minutes and the quantity of wear of the V block and pins after the operation was examined. The results are given in Table 4. As can be understood clearly from Table 4, the esters used in the present invention exhibited a higher wear resistance than that of the naphthene oil (Comparative Product No.8), the poly-α-olefin (Comparative Product No. 9) and the polyethers (Comparative Products Nos. 10 and 11) and the wear resistance was equal or superior to that when dichlorodifluoromethane (R-12) was blown into the naphthene oil (Reference Example 1). Among the esters used in the present invention, those having a kinematic viscosity of greater than 20 10 -6 m 2 /s (cst) at 100°C (the product No. 3 of this invention) showed a particularly high wear resistance. The wear resistance could be improved by mixing esters having a kinematic viscosity of higher than 20 10 -6 m 2 /s (cst) with the esters of the present invention having a kinematic viscosity of not greater than 20 10 -6 m 2 /s (cst) (the product Nos 6 of this invention). Quantity of wear Product of this invention 1 13.9 6 8.0 Comparative Product 8 seizure 9 " 10 40.2 11 46.3 Reference Example 1 *3 14.9 Example 4: The sealed tube test (175°C x 14 days) was carried out by use of iron, copper and aluminum as the catalyst in order to examine the thermal stability of each of the products Nos. 3 and 5 of this invention obtained in the preparation Example in an atmosphere of 1,1,1,2-tetrafluoroethane. The results are given in Table 5. As can be understood clearly from Table 5, each of the esters used in the present invention had good appearance but did not give any precipitate, and had good thermal stability. Appearance Precipitate Product of this invention 3 Good nil 5 " "

Claims: A refrigeration oil composition comprising: (1) a hydrogenated fluoroethane and (2) an ester compound obtained only from: (2-a) an aliphatic dihydric alcohol having 1 to 2 primary hydroxyl groups; (2-b) a branched saturated aliphatic monocarboxylic acid having 2 to 9 carbon atoms, or a derivative thereof; and (2-c) a saturated aliphatic dicarboxylic acid having 2 to 8 carbon atoms, straight or branched, or a derivative thereof, said ester compound having a kinematic viscosity at 100°C in the range of 1 to 100 x 10 -6 m 2 /S(cst). The composition as claimed in Claim 1, in which the ester compound is obtained from 1 mole of (2-a), 4 moles or less of (2-b) and 0.9 mole or less of (2-c). The composition as claimed in Claim 1, in which the ester compound has a saponification value of at least 330 mg KOH/g. The composition as claimed in Claim 1, in which the hydrogenated fluoroethane is 1,1,1,2-tetrafluoroethane.

Inventors: HAGIHARA TOSHIYA, SAKAI AKIMITSU, HAGIHARA, TOSHIYA, SAKAI, AKIMITSU
Applicants: KAO CORP, KAO CORPORATION
Application year: 1990
Main classification: C10M105
IPC codes: C09K5, C10M171, C10M111, C10M105, C10N20, C10N40