Lubricant for refrigerant

Abstract: A lubricant composition for refrigerators characterised by comprising at least 80 percent by weight of a compound having a kinematic viscosity of 6 to 500 cSt at 40 degrees centigrade and represented by the formula (1): wherein the radicals C m H 2m+1 and C n H 2n+1 may be straight or branched and wherein m represents an integer of 1 to 8, n represents an integer of 1 to 8, p represents an integer of 1 to 80, q represents an integer of 0 to 60, and r represents 0 or 1, with the proviso that the relationships: 2 ≦ m + n ≦ 9 and are both satisfied. The invention also relates to refrigerant compositions comprising the above lubricant composition and Flon 134a.

Description: The present invention relates to a lubricant for refrigerators. Particularly, it relates to a polyoxyalkylene glycol lubricant for refrigerators which is compatible with a flon used in a refrigerator. Flon compounds are excellent materials in respect of chemical stability, low toxicity and incombustibility, so that they have been widely used in the fields of refrigerant, aerosol, foaming, cleaning and so on. Recently, however, there is a strong movement on foot for the reduction in the production and consumption of specific kinds of flons, because the flons emitted into the open air not only destroy the ozonosphere but also cause the warming of the earth's surface, the so-called "greenhouse effect". Accordingly, the development of a flon which is free from the danger of causing the destruction of the ozonosphere or the greenhouse effect, i.e., a flon which does not contain any chlorine atom and is relatively easily decomposable is in progress. Under these circumtances, Flon 134a (Trade Mark) (1,1,1,2-tetrafluoroethane) has been developed as a substitute for Flon 12 (dichlorodifluoromethane) which has been widely used as the refrigerant of domestic refrigerators for business use, automotive air conditioners and so on, because the characteristics of Flon 134a are similar to those of Flon 12. However, Flon 134a exhibits poor compatibility with refrigerator oils such as naphthenic mineral oil or alkylbenzenes which result in a lowering in the reversion in the evaporator, of seizing of a compressor in or abnormal vibration of a refrigerator. Thus, it would be advantageous if a refrigerator oil could be developed which is compatible with Flon 123a. U.S. Patent No. 4755316 proposed a difunctional or higher polyoxyalkylene glycol having a molecular weight of 2,000 or below as an oil for a refrigerator using Flon 134a as a refrigerant. However, this oil is so hygroscopic that the water absorbed by the oil causes a failure in the actuation of the expansion valve of a refrigerator or blockage (water choking) thereof or accelerates the decomposition of the flon to form hydrofluoric acid which could result in corroding the metal parts of the refrigerator. The inventors of the present invention have intensively studied various synthetic lubricants and have found that a specific kind of polyoxyalkylene glycol dialkyl ether is compatible not only with conventional flon refrigerants but also with Flon 134a, is reduced in hygroscopicity and is excellent in its inertness to flons. The present invention has been accomplished on the basis of this finding. According to the present invention a lubricant for refrigerators is characterized by containing at least 80% by weight of a compound represented by the general formula (1): wherein the radicals C m H 2m+1 and C n H 2n+1 may be straight or branched and wherein m represents an integer of 1 to 8, n represents an integer of 1 to 8, p represents an integer of 1 to 80, q represents an integer of 0 to 60 and r represents 0 or 1, with the proviso that the relationships: 2 ≦ n + n ≦ 9 and -8 < m + n - 20Xq p + q < 4 are both satisfied, and by exhibiting a kinematic viscosity of 6 to 500 cSt at 40°C. The invention provides a lubricant composition for refrigerators comprising at least 80 percent by weight of a compound having the formula (1), having a kinematic viscosity of 6 to 500 cSt at 40 degree centigrade. It is preferable that the composition comprises at least 80 percent by weight of the compound and up to 20 percent by weight of an additive. The invention also provides a refrigerant composition comprising the compound above and Flon 134a. EP-A- 0 377 122 published on 17.07.90 claims the priority dates of 06.12.88. 13.12.88, 06.03.89, 07,03.89, 31.03.89 and 21.04.89 and discloses a lubricating oil for compression-type refrigerators which comprises polyoxyalkyleneglycol derivatives of R'(OR2)-m-OR3)n (I), (where R'= 1-10C alkyl, 1-10C acyl or aliphatic hydrocarbon (2-6 valencies); R2 = 2-4C alkylene; R3 =1-10C, or 1-10C acyl; n = Integer of 1-6, and m = integer of 1-8C). Examples 7 and 8 of EP-O-A 0 377 122 disclose dimethyl ether derivatives of polyoxypropyleneglycol and the compatability of these derivatives with Flon 134a is disclosed in Table 1 of that reference. EP-A- 0 377 122 is relevant to this application under Article 54(3) in respect of designated states which are common to EP-A- 0 377 122 and the present application namely AT, BE, CH, DE, ES, FR, GB, GR, IT, LI, LU, NL and SE but is not relevant to the present application under Article 54(3) in respect of the designated state DK which is also designated in the present application but not in EP-A- 0 377 122. As a consequence in the appendent claims for the designated state DK the compounds of Formula I are as defined above, but in the appendent claims for the said common designated states "q" in Formula 1 is defined as being a positive integer up to 60, i.e. q = 0 being excluded ; and r represents 1. The present invention also provides for the said common designated states a lubricant composition as claimed in claim 2 of the set of claims for the said designated states. In the above general formula (1), each of the (CH 2 CH 2 O) and (CH 2 0) units may be arranged in block or at random. Examples of the alkyl group represented by the formula: C m H 2m+1 or C n H 2n+1 include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1- butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 1-hexyl, 4-methyl-2-pentyl, 2-ethyl-1-butyl, 1-heptyl, 2-heptyl, 3 heptyl, 1-octyl, 2-octyl and 2-ethylhexyl groups. Among these groups, methyl, ethyl, 1-propyl. 1-butyl, 2-methyl-1-propyl and 2-ethylhexyl groups are preferred from the standpoint of the availability of the raw material. Compounds represented by the above general formula wherein m or n is 0 are too hygroscopic to be used as a lubricant for refrigerators, while those represented by the general formula wherein m or n is 9 or above are unsuitable as a lubricant for refrigerators, because they cause problems in that they separate from Flon 134a at a temperature of from -50 to 60°C which corresponds to the practical service temperature of a lubricant for refrigerators. Further, compounds represented by the above general formula wherein either of the relationships: 2 ≦ m + n ≦ 9 or -8 < m + n - 20 X q p + q < 4 is not satisfied also cause the same problems in that they also separate from Flon 134a at a temperature of -50 to 60°C. The polyoxyalkylene glycol dialkyl ether according to the present invention can be prepared from raw materials such as alcohols and alkylene oxides by suitably combining ordinary addition, etherification and other reactions. The lubricant for refrigerators according to the present invention must contain at least 80% by weight of a polyoxyalkylene glycol dialkyl ether represented by the above general formula (1) based on the whole composition in order to make the lubricant exhibit satisfactory performances. Further, the lubricant for refrigerators according to the present invention must exhibit a kinematic viscosity of 6 to 500 cSt at 40°C. If the kinematic viscosity of the lubricant at 40°C is less than 6 cSt, insufficient lubricity will be attained, while if it exceeds 500 cSt, the load of the compressor will increase to bring about excessive energy consumption and the reversion in the oil-separating pipe of the refrigerator will become lower. Although the lubricant for refrigerators according to the present invention may be composed solely of a polyoxyalkylene glycol dialkyl ether represented by the above general formula (1), the lubricant can further contain additives which have been found useful as lubricants for refrigerators using a flon as a refrigerant in an amount as described above. The additives include phosphates such as tricresyl phosphate; phosphites such as triethyl phosphite; epoxy compounds such as epoxidized soybean oil and bisphenol A diglycidyl ether; organotin compounds such as dibutyltin laurate; and antioxidants such as α-naphthylbenzylamine, phenothiazine and BHT. The lubricant for refrigerators according to the present invention and Flon 134a can be completely dissolved in each other at substantially any ratio (1 : 99 to 99 : 1) in the practical service temperature range of a refrigerator oil, i.e., in a temperature range of -50 to 60°C. The lubricant for refrigerators according to the present invention is well compatible with flons, particularly with Flon 134a, used in a refrigerator, so that the utilization thereof in a wide field of uses is expected. The present invention will now be described in more detail by referring to the following Examples, though the present invention is not limited to them. In the Examples 1 to 3 and 5 to 8 are within the scope of the present invention but Samples 4 and 9-17 are not. Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 (random polymer) Sample 6 (block polymer) Sample 7 (random polymer) Sample 8 (random polymer) Sample 9 Sample 10 (random polymer) Sample 11 (random polymer) Sample 12 (random polymer) Sample 13 Sample 14 Sample 15 Sample 16 Sample 17 Example 1 In a series of tests 15 parts by weight of each of the samples listed in Table 1 and 85 parts by weight of each of the flons listed in Table 1 (case 1) or 60 parts by weight of each of the samples listed in Table 1 and 40 parts by weight of each of the flons listed in Table 1 (case 2) were fed into a 1-ℓ autoclave made of glass to determine the compatibility at a temperature of -50 to 60°C. The results which were the same in case 1 and case 2 are given in Table 1. Comparative Example 1 The samples listed in Table 2 were examined for compatibility in a similar manner to that of case 1 of Example 1. The results are given in Table 2. Example 2 10 g of each of the samples listed in Table 3 was put in a 100-ml beaker and the beaker was placed in a thermo-hygrostat to determine the weight change after 24 hours. The results are given in Table 3. Sample No. Wt. before test (g) Wt. after test (g) Wt. increase (mg) 1 10.0000 10.0156 15.6 2 10.0003 10.0136 13.4 4 10.0001 10.0123 12.2 Comparative Example 2 The samples listed in Table 4 were examined for hygroscopicity in a similar manner to that of Example 2. The results are given in Table 4. As shown in Table 4, the samples exhibit weight increases larger than those of the samples of Example 2, i.e., the samples are more hygroscopic than those of Example 2. Sample No. Wt. before test (g) Wt. after test (g) Wt. increase (mg) 13 10.0000 10.6091 609.1 14 10.0002 10.2239 223.7 15 10.0002 10.1614 161.2 16 10.0000 10.1278 127.8 17 10.0001 10.1214 121.3 Example 3 14 parts by weight of a sample (No. 1, 2 or 4) listed in Table 5, 0.7 part by weight of dibutyltin laurate (Mark BT-11, a product of Adeka Argus) and 0.3 part by weight of an epoxidized soybean oil (Adekacizer 0-130P, a product of Adeka Argus) were put in a 100-ml autoclave made of stainless steel (SUS-316) to prepare a lubricant for refrigerators. This lubricant was examined for viscosity and appearance before the test. Then, 75 parts by weight of Flon 22 was introduced into the autoclave and three metal pieces (50 x 25 x 1.5 mm) respectively made of steel, copper or aluminum were placed in the autoclave. After hermetically sealing the autoclave, the contents were kept at 150°C by heating for 14 days (336 hours) to carry out a heat test. After the completion of the heat test, the autoclave was subjected to vacuum deaeration to remove the Flon 22 and the resulting lubricant was examined for viscosity and appearance after the test. Further, the metal pieces were washed with toluene and ethanol to determine the weight change thereof. It is apparent from the test results that the lubricants for refrigerators according to the present invention each exhibit a viscosity change of -10 to -22%, each have only a small influence upon the metals and are excellent in chemical stability in the presence of a flon. The results are given in Table 5. Comparative Example 3 The same procedure as that of Example 3 was repeated except that samples (No. 13 to 17) listed in Table 5 were each used to determine the stability. It is apparent that these samples each exhibit a larger viscosity change and each have a greater influence upon the metals than those of Example 3. The results are given in Table 5.

Claims: Claims for the following Contracting State : DK A lubricant composition for refrigerators, characterised by comprising at least 80 percent by weight of a compound having a kinematic viscosity of 6 to 500 cSt at 40 degrees centigrade and represented by the formula (1): wherein the radicals C m H 2m+1 and C n H 2n+1 may be straight or branched and wherein m represents an integer of 1 to 8, n represents an integer of 1 to 8, p represents an integer of 1 to 80, q represents an integer of 0 to 60, and r represents 0 or 1, with the proviso that the relationships: 2 ≦ m + n ≦ 9 and -8 < m + n - 20 x q p + q < 4 are both satisfied. A composition as claimed in claim 1, characterised in that it comprises at least 80 percent by weight of the compound of formula (1) and up to 20 percent by weight of an additive. A refrigerant composition characterised by comprising a composition as claimed in claim 1 or 2 and 1,1,1,2- tetrafluoroethane. Claims for the following Contracting States : AT, BE, CH, DE, ES, FR, GB, GR, IT, LI, LU, NL, SE A lubricant composition for refrigerators, characterised by comprising at least 80 percent by weight of a compound having a kinematic viscosity of 6 to 500 cSt at 40 degrees centigrade and represented by the formula (1): wherein the radicals C m H 2m+1 and C n H 2n+1 may be straight or branched and wherein m represents an integer of 1 to 8, n represents an integer of 1 to 8, p represents an integer of 1 to 80, q represents an integer of up to 60, and r represents 1, with the proviso that the relationships: 2 ≤ m + n ≤ 9 and -8 < m + n - 20 x q p + q < 4 are both satisfied. A lubricant composition for refrigerators, characterised by comprising at least 80 percent by weight of a compound having a kinematic viscosity of 6 to 500 cSt at 40 degrees centigrade and represented by the formula (2), (3), (4) or (5) : A composition as claimed in claim 1 or 2, characterised in that it comprises at least 80 percent by weight of the compound of formula (1), (2), (3), (4) or (5) and up to 20 percent by weight of an additive. A refrigerant composition characterised by comprising a composition as claimed in claim 1, 2 or 3 and 1,1,1,2- tetrafluoroethane.

Inventors: BABA YUZI, KAMAKURA TAMIJI, NAMIWA KIMIYOSHI, BABA, YUZI, KAMAKURA, TAMIJI, NAMIWA, KIMIYOSHI
Applicants: ASAHI DENKA KOGYO KK, ASAHI DENKA KOGYO KABUSHIKI KAISHA
Application year: 1990
Main classification: C10M107
IPC codes: C10M171, C10M105, C10N30, C10N40, C10N20, C10M107, C10M169, C10M111