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    • 专利摘要:
    To provide a lubricant having excellent practicability with excellent compatibility with ammonia and good stability and lubricity; And a lubricant for a refrigerating machine using ammonia as a refrigerant, which comprises a polyether compound represented by the following formula (1) or (2) and an additive selected from antioxidants, abrasion inhibitors and metal deactivators. [Chemical Formula 1] X {-O- (AO) n- H} p (2) X {-O- (AO 1) a - (AO 2) b -H} p (AO) n represents a polyoxyalkylene chain constituted by copolymerization of EO and an alkylene oxide having 3 or more carbon atoms, and in the terminal hydroxyl group, a secondary hydroxyl group The number is at least 50% of the total hydroxyl number. (AO 1 ) a represents a polyoxyalkylene chain constituted by copolymerization of EO with PO and / or BO, and AO 2 represents an oxyalkylene group having 3 or more carbon atoms]
    公开号:KR20020067064A
    申请号:KR1020027008707
    申请日:2001-01-19
    公开日:2002-08-21
    发明作者:가이마이다까시；다까하시히또시；야마모또고로；나미와기미요시；사네요시아야꼬
    申请人:가부시키가이샤 저펜에너지；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a lubricant for refrigerating machine using ammonia refrigerant,
    [2] The compression type freezer is a device for cooling by using a property of taking out evaporation heat from the surroundings when a refrigerant having high volatility is evaporated, such as a compressor, a condenser, an expansion mechanism (for example, an expansion valve, a capillary tube, Freezers, air conditioning equipment, show cases, automatic vending machines for soft drinks and ice cream. In addition, in an air conditioner or a vending machine, it is used for heating by using heat generated at the time of condensation, or for heating and holding drinks and foods.
    [3] As the refrigerant, fluorinated hydrocarbons (CFCs or HCFCs) containing chlorine are conventionally used, and recently, fluorine-containing hydrocarbons (HFC) containing no chlorine have been converted. However, these fluorinated hydrocarbons have a problem that the ozone layer is destroyed by electrons, and the latter has a high global warming ability. Therefore, refrigerants that do not adversely affect the environment that is substituted for them from the viewpoint of protecting the global environment are required. Therefore, refrigerants such as low molecular weight hydrocarbons and ammonia do not destroy the ozone layer, and the global warming performance is much smaller than that of fluorinated hydrocarbons, and thus they are reviewed as environmentally friendly refrigerants. In particular, ammonia has a high coefficient of performance.
    [4] Mineral oil or alkylbenzene has been used as a base oil of a refrigerator lubricant using an ammonia refrigerant, but recently, a polyether compound having compatibility with ammonia has been proposed. For example, European Patent No. 490810 discloses a lubricant comprising a polyalkylene glycol having a EO / PO ratio of 4/1 as a copolymer of ethylene oxide and propylene oxide. No. 585934 discloses a lubricant comprising a mono- or di-functional polyalkylene glycol having an EO / PO of 2/1 to 1/2. DE-A 4404804 discloses a polyether-based compound represented by the formula RO- (EO) x- (PO) y -H wherein R is an alkyl group of C1-C8 and x and y are numbers of 5 to 55 Lubricants are present. In addition, International Patent Publication No. WO94 / 12594 discloses refrigerating machine oil excellent in compatibility and stability with ammonia composed of polyalkylene glycol diether.
    [5] The use of a polyether compound having compatibility with ammonia is advantageous in that it is not necessary to equip a lubricant circulating device for separating and recovering the lubricant at the discharge side of the refrigeration compressor and returning it to the compressor again.
    [6] However, since ammonia, which is a refrigerant, is a highly active compound, it reacts with a base oil, an additive, or a heat load of the refrigerant lubricant to generate a precipitate (reaction product), causing clogging of the expansion valve or the tubular portion, There is a risk of accelerating deterioration of the lubricant. In addition, ammonia is highly corrosive to metal materials, particularly in the presence of water, and corrosion and deterioration of metal materials such as rust generation is accelerated by combination with a highly hygroscopic polyether compound. Further, since ammonia refrigerant requires higher-pressure operation than refrigerant refrigerant, refrigerant and lubricant are exposed under more severe conditions such as high temperature and high pressure, and slid sliding conditions become severe. As a result, there is concern that the generation of precipitates, the deterioration of the lubricant (base oil and additives), the increase of friction, and the abrasion may occur. Therefore, there is a demand for a lubricant that is stable and lubricous even under severe conditions using ammonia refrigerant.
    [7] As for the polyether compound, a derivative of a polyether compound (hereinafter referred to as a polyether compound including this derivative) having improved stability and hygroscopicity has been proposed by replacing its terminal hydroxyl group with an alkyl group or an acyl group. However, a manufacturing process for obtaining the derivative is added, and the compatibility with ammonia is deteriorated. On the other hand, the degree of improvement in stability and hygroscopicity is not sufficiently satisfied, and there is a limit in coping with only the base oil made of such a polyether compound. Therefore, it is required to select and use an appropriate additive in the combination of ammonia and base oil. In most cases, the additive is more active than base oil, easily reacts with ammonia, accelerates deterioration of additive, Not many.
    [8] It is an object of the present invention to provide a lubricant for refrigerator using an ammonia refrigerant, which has excellent compatibility with ammonia and has good stability and lubricity and excellent practical performance.
    [1] The present invention relates to a refrigerant lubricant using an ammonia refrigerant.
    [9] DISCLOSURE OF INVENTION
    [10] As a result of intensive studies, the present inventors have found that, as a base oil of a lubricant, a polyether compound having a high proportion of a secondary hydroxyl group among the hydroxyl groups located at the structural end is used, and further, an additive selected from an antioxidant, The above problems can be solved.
    [11] Based on this point, the present invention provides the following invention.
    [12] 1. A refrigerating machine lubricant using ammonia as a refrigerant, characterized by comprising at least one polyether compound represented by the following formula (1) or (2) and at least one additive selected from an antioxidant, an abrasion inhibitor and a metal deactivator Freezer lubricant.
    [13] X {-O- (AO) n- H} p
    [14] (AO) n represents a polyoxyalkylene chain constituted by copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, and n represents a number of 2 or more P represents a valence of X, and the number of the secondary hydroxyl groups in the hydroxyl groups located at the structural ends is 50% or more of the total hydroxyl groups.
    [15] X {-O- (AO 1) a - (AO 2) b -H} p
    [16] (AO 1 ) a represents a polyoxyalkylene chain constituted by copolymerization of ethylene oxide and propylene oxide and / or butylene oxide, and AO 2 represents a polyoxyalkylene chain constituted by copolymerization of propylene oxide and / or butylene oxide, wherein X represents a moiety excluding a hydroxyl group in the monool or polyol A represents an integer of 2 or more, b represents a number of 1 or more, and p represents a valence of X. [
    [17] 2. The refrigerator lubricant according to the above 1, wherein the antioxidant is an aromatic amine compound or a phenothiazine compound.
    [18] 3. The refrigerator lubricant according to 1 or 2, wherein the metal deactivator is a benzotriazole-based compound.
    [19] 4. The refrigerator lubricant according to any one of 1 to 3 above, wherein the abrasion preventing agent contains at least one compound selected from the group consisting of aliphatic higher alcohols having a carbon number of 10 or more, polyhydric alcohol partial esters, and polyhydric alcohol partial ethers.
    [20] (AO) n in formula ( 1 ) or (AO 1 ) a in formula (2) is a random copolymer, block copolymer or random copolymer of ethylene oxide and propylene oxide and / or butylene oxide The lubricant for a refrigerator according to any one of the above-mentioned 1 to 4, wherein the lubricant is a polyoxyalkylene group constituted by any one of the copolymers.
    [21] 6. The refrigerator lubricant according to any one of 1 to 5 above, wherein the polyether compound represented by the formula (1) or (2) has a kinematic viscosity at 40 DEG C of 15 to 200 mm2 / s.
    [22] 7. The refrigerator lubricant according to any one of 1 to 6 above, wherein the proportion of oxyethylene groups in the (AO) n in formula ( 1 ) or (AO 1 ) a in formula (2) is 10 to 50% by weight.
    [23] 8. The refrigerator lubricant according to any one of 1 to 7 above, wherein the polyether compound represented by the general formula (1) or (2) has an unsaturation degree of 0.05 meq / g or less.
    [24] BEST MODE FOR CARRYING OUT THE INVENTION
    [25] The polyether compound used in the present invention is used as a so-called base oil which is a main component of a lubricant,
    [26] [Chemical Formula 1]
    [27] X {-O- (AO) n- H} p
    [28] (AO) n represents a polyoxyalkylene group constituted by copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, and n represents a number of 2 or more, and X represents a residue other than a hydroxyl group in the monool or polyol, P represents a valence of X, and the number of the secondary hydroxyl groups in the hydroxyl groups located at the structural ends is 50% or more of the total hydroxyl groups.
    [29] Alternatively,
    [30] (2)
    [31] X {-O- (AO 1) a - (AO 2) b -H} p
    [32] (AO 1 ) a represents a polyoxyalkylene group constituted by copolymerization of ethylene oxide and propylene oxide and / or butylene oxide, and AO 2 represents a polyoxyalkylene group constituted by copolymerization of propylene oxide and / or butylene oxide, wherein A represents a residue other than a hydroxyl group in the monool or polyol A represents an integer of 2 or more, b represents a number of 1 or more, and p represents a valence of X. [
    [33] Lt; / RTI >
    [34] In the general formula (1) or (2), X represents a moiety excluding a hydroxyl group in the monool or the polyol. Examples of the monool include alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, pentanol, 2-pentanol, 3-pentanol, isopentyl alcohol, But are not limited to, hexane, heptane, octane, sec-hexanol, heptane, heptanol, sec-heptanol, octanol, 2-ethylhexanol, sec-octanol, isooctanol, , Secondary decanol, undecanol, secondary undecanol, 2-methyl decanol, lauryl alcohol, secondary dodecanol, 1-tridecanol, isotridecyl alcohol, secondary tridecanol, myristyl alcohol, But are not limited to, secondary tetradecanol, secondary pentadecanol, secondary pentadecanol, cetyl alcohol, palmityl alcohol, secondary hexadecanol, heptadecanol, secondary heptadecanol, stearyl alcohol, isostearyl alcohol, Octadecyl alcohol, oleyl alcohol, behenyl alcohol, eicosanol, dococanol, tetracosanol, hexacosanol, octacosanol, myrcyl alcohol, rasserol, tetraliacontanol, allyl alcohol, cyclopentane Octyldecanol, 2-octyldecanol, 2-octyldodecanol, 2-octyldodecanol, 2-hexyldecanol, 2-hexyldecanol, 2- 2-octyldodecanol, 2-octyltetradecanol, 2-decyldodecanol, 2-decyltetradecanol, 2-decylhexadecanol, 2-dodecyltetradecanol, 2-dodecylhexadecanol, Alcohols such as 2-tetradecyl octadecanol, 2-tetradecyl isosanol, 2-hexadecyl octadecanol and 2-hexadecyl isosanol; But are not limited to, phenol, cresol, ethylphenol, t-butylphenol, hexylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, phenylphenol, and phenol such as p-cumylphenol.
    [35] Examples of the polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, Diols such as 3-methyl-1,5-pentanediol, sorbite, caticol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol; Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl- Butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, Triol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, Trivalent alcohols such as trimethylolpropane; Pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5 - tetra-alcohols such as hexanetetrol, diglycerin and sorbitan; Pentanol such as adonitol, arabitol, xylitol and triglycerin; Hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dol- isthol, talos, and aloses; Octyl alcohol such as sucrose, polyglycerin, dehydrated condensates thereof and the like. p is a valence of X, and a number of 1 to 8 is preferable.
    [36] Also, X may be a residue of the compound derived from the monool or the polyol. Examples of the compound derived from such a monool or polyol include sodium alcoholate and potassium alcoholate of the monool or polyol.
    [37] Among them, when the p number of excess p is excessively large, the molecular weight of the polyether compound to be obtained becomes excessively high, the viscosity becomes too high, or the compatibility with the ammonia refrigerant deteriorates, so that the number p of X is more preferably 1 to 3. In particular, it is most preferable that p is 1, that is, X is a moiety other than a hydroxyl group in the monool. Even monol, if the carbon number is excessively large, the compatibility with the ammonia refrigerant may be lowered. Therefore, the carbon number of X is preferably 1 to 8, more preferably 1 to 4, and most preferably, X is Methyl group.
    [38] In formula (1), (AO) n represents a polyoxyalkylene group constituted by copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms. Examples of the alkylene oxide having 3 or more carbon atoms include propylene oxide, butylene oxide, -olefin oxide, styrene oxide and the like. The polymerization ratio of ethylene oxide and alkylene oxide having 3 or more carbon atoms is not particularly limited, but ethylene oxide is required in order to give excellent compatibility with ammonia to the polyether compound as a polymerization product.
    [39] In formula (2), (AO 1 ) a represents a polyoxyalkylene group constituted by copolymerization of ethylene oxide with propylene oxide and / or butylene oxide. The polymerization ratio of ethylene oxide to propylene oxide and / or butylene oxide is not particularly limited, but at least ethylene oxide is required in order to impart excellent compatibility with ammonia to the polyether compound as a polymerization product.
    [40] However, too, if the ratio of the ethylene oxide increases, the moisture absorption and, since a case or low-temperature properties such as pour point deterioration, the solids of the powder-like precipitated, or precipitated, which occupies the (AO) n or (AO 1) a The proportion of oxyethylene groups is preferably 50% by weight or less, more preferably 50 to 5% by weight, and most preferably 30 to 5% by weight. For the same reason, the proportion of the oxyethylene group in the molecule of the polyether compound represented by the above formula (1) or (2) used in the present invention is preferably 40% or less, more preferably 30% or less with respect to the molecular weight of the polyether compound , And most preferably 20% or less.
    [41] The form of copolymerization may be block polymerization, random phase polymerization, or a combination of block polymerization and random phase polymerization, but it is preferable that the part of (AO) n or (AO 1 ) a is a polyoxyalkylene chain (AO) n or (AO 1 ) a is a polyoxyalkylene chain constituted by random phase polymerization or a polyoxyalkylene chain containing a random phase polymerization in a part thereof because the fluidity at low temperatures may deteriorate Particularly preferred. n and a each represent a number of at least 2, preferably 2 to 150, more preferably 5 to 100.
    [42] AO 2 represents an alkylene group having 3 or more oxy in the formula (2). Examples of the oxyalkylene group having 3 or more carbon atoms include an oxypropylene group, an oxybutylene group, and an oxyalkylene group having about 5 to 24 carbon atoms. Of these, an oxypropylene group or an oxybutylene group is preferable. b represents 1 or more, preferably 1 to 10; (AO 2 ) b is a (poly) oxyalkylene group comprising one or more of the above-mentioned oxyalkylene groups having 3 or more carbon atoms.
    [43] The lubricant of the present invention is a polyether compound represented by the general formula (1) satisfying the above-mentioned condition, wherein the structural end on the opposite side of X is a hydroxyl group. In the polyether compound represented by the formula (1) used in the present invention, the secondary hydroxyl group should be at least 50% of the total hydroxyl groups with respect to the hydroxyl group located at the end of the structure. Further, it is more preferably 70% or more, and most preferably 80% or more. This is because, when the secondary hydroxyl group accounts for 50% or more of the hydroxyl groups located at the structural end, it exhibits excellent stability to the ammonia refrigerant. However, if the secondary hydroxyl group content is less than 50%, the stability deteriorates. Here, the secondary hydroxyl group is a hydroxyl group bonded to a secondary carbon atom, and the ratio of this secondary hydroxyl group can be measured by 1 H-NMR.
    [44] In the polyether compound represented by the formula (1) used in the present invention, more than 50% of the total hydroxyl groups located at the structural end is a secondary hydroxyl group, and thus exhibits excellent stability to ammonia refrigerant. Further, the polyether compound represented by the formula (2) used in the present invention has a group represented by (AO 2 ) b -H at the structural end, and thus exhibits excellent stability in the presence of ammonia refrigerant.
    [45] Generally, a hydroxyl group bonded to a primary carbon atom is converted to a carboxylic acid via aldehyde when oxidized, and the carboxylic acid generates an acid amide in the presence of ammonia, which may be precipitated. On the other hand, the hydroxyl group bonded to the secondary carbon atom is converted into the ketone even when it is oxidized, and in the presence of ammonia, the ketone is more stable than the carboxylic acid. Therefore, the reason why the polyether compound used in the present invention can exhibit excellent stability even in the presence of ammonia is that in the case of the polyether compound represented by the general formula (1), at least 50% In the case of the polyether compound represented by the general formula (2), a polyether compound obtained by finally adding an alkylene oxide having 3 or more carbon atoms is used. In the case of a polyether compound having a hydroxyl group at the structure end bonded to a secondary carbon atom As shown in Fig. That is, the lubricant of the present invention is solved by selecting a lubricant having a specific structure as described above, peculiar to a lubricant of a refrigerator using ammonia refrigerant.
    [46] In the refrigerating machine lubricant using the ammonia refrigerant of the present invention, any of the polyether compounds represented by the above formula (1) or (2) can be used, but among the hydroxyl groups located at the structural end, the secondary hydroxyl group accounts for at least 50% , And more preferably a polyether compound having a structure represented by the above formula (2).
    [47] The molecular weight of the polyether compound represented by the general formula (1) or (2) used in the present invention is not particularly limited, but the molecular weight and the kinematic viscosity tend to be proportional. Therefore, in order to set the kinematic viscosity to a preferable range described below, To about 3,000 is preferable.
    [48] The kinematic viscosity of the polyether compound represented by the formula (1) or (2) used in the present invention is not particularly limited. However, if the viscosity is too low, the sealability is poor and the lubrication performance is lowered. When the viscosity is too high, And the energy efficiency is deteriorated. Therefore, the kinematic viscosity at 40 占 폚 is preferably 15 to 200 mm2 / s, and more preferably 20 to 150 mm2 / s.
    [49] The refrigerant ammonia and the polyether lubricant represented by the formula (1) or (2) of the present invention are preferably used in the range of 99/1 to 1/99 in terms of the cooling capacity of the refrigerant and the sealing property of the lubricant, To 30/70. ≪ / RTI >
    [50] Since the polyether compound represented by the formula (1) or (2) used in the present invention is a lubricant used in a refrigerating machine for ammonia refrigerant, impurities such as moisture and chlorine are preferably as small as possible. Since moisture promotes deterioration of the lubricant and additives, the water content is preferably as small as possible, preferably 500 ppm or less, more preferably 300 ppm or less, and most preferably 100 ppm or less. Generally, the polyether compound is hygroscopic, so care must be taken when storing or charging the refrigerator, but it can be removed by passing the distillation under reduced pressure or the dryer filled with the desiccant.
    [51] In addition, chlorine forms an ammonium salt in the presence of ammonia and causes clogging of the capillary. Therefore, the chlorine content is preferably as small as possible, preferably 100 ppm or less, and more preferably 50 ppm or less.
    [52] Further, when producing lubricant for refrigerators of the present invention containing an oxypropylene group, propylene oxide may generate a side reaction to generate an allyl group having a carbon-carbon double bond. When the allyl group is produced, first, the thermal stability of the lubricant itself is lowered. In addition, it generates sludge as a result of the formation of a polymer, or it is easily oxidized, which is a cause of generation of peroxide. When peroxide is formed, it decomposes to form a carbonyl group, which reacts with ammonia refrigerant to form acid amide, which ultimately causes clogging of the capillary. Therefore, the degree of unsaturation derived from an allyl group or the like is preferably as small as possible. Specifically, the degree of unsaturation is preferably 0.05 meq / g or less, more preferably 0.03 meq / g or less, and most preferably 0.02 meq / g or less.
    [53] The peroxide value is preferably 10.0 meq / kg or less, more preferably 5.0 meq / kg or less, and most preferably 1.0 meq / kg or less. The carbonyl content is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and most preferably 20 ppm by weight or less.
    [54] In order to produce such a polyether compound of the general formula (1) or (2) having a low degree of unsaturation, the reaction temperature at the time of reacting propylene oxide is preferably 120 ° C or lower, more preferably 110 ° C or lower. If an alkali catalyst is used during the production, the degree of unsaturation can be reduced by using an inorganic adsorbent such as activated carbon, activated clay, bentonite, dolomite, aluminosilicate or the like in order to remove it. In addition, when the lubricant of the present invention is produced or used, contact with oxygen can be avoided positively or an increase in peroxide value or carbonyl value can be prevented even by using an antioxidant in combination.
    [55] The degree of unsaturation, peroxide value and carbonyl value are values measured by the following methods according to the standard maintenance analysis test method established by the Nippon Yucca Institute. The outline of the measurement method is shown below.
    [56] ≪ Measurement method of unsaturation (meq / g)
    [57] The IC1-acetic acid solution was allowed to react with the sample and allowed to stand in a dark place. Thereafter, the excess IC1 was reduced to urea, and the urea was titrated with sodium thiosulfate to give urea, Convert it to unsaturation.
    [58] ≪ Measurement method of peroxide value (meq / kg) >
    [59] The free element produced by adding potassium iodide to the sample is titrated with sodium thiosulfate, and the free element is converted to peroxide value in terms of the milliequivalent number per 1 kg of the sample.
    [60] ≪ Measurement method of carbonyl value (weight ppm)
    [61] 2,4-dinitrophenylhydrazine is added to the sample to generate color-forming alkynoid ions. The absorbance of this sample is measured at 480 nm and converted into the amount of carbolonyl based on the calibration curve obtained beforehand as cinnamaldehyde as a standard substance .
    [62] The method for producing the polyether compound represented by the general formula (1) used in the present invention is not particularly limited, but it may be a conventional method for producing a polyether compound. For example, a mixed alkylene oxide of ethylene oxide and an alkylene oxide having 3 or more carbon atoms (for example, propylene oxide) in an alcohol such as methanol as the starting material in the presence of an alkali catalyst such as sodium hydroxide or potassium hydroxide is heated at a temperature of 100 to 150 ° C , And a pressure of about 0 to 10 kg / cm 2.
    [63] In the case of the polyether compound represented by the general formula (2), a mixed alkylene oxide of ethylene oxide and propylene oxide (or butylene oxide) is reacted with an alcohol such as methanol as a starting material under the same conditions, May be reacted with an alkylene oxide having 3 or more carbon atoms. The method for producing the polyether compound represented by the general formula (2) is not particularly limited, and a mixed alkylene oxide of ethylene oxide and propylene oxide (or butylene oxide) is reacted under the same conditions and then alkylene oxide Oxides can be reacted.
    [64] The lubricant of the present invention also contains at least one additive selected from antioxidants, abrasion inhibitors and metal deactivators.
    [65] As the antioxidant to be used in the present invention, an antioxidant of aromatic amine type, phenothiazine type, phenol type, sulfur type, thiophosphoric acid type can be added.
    [66] Of these, aromatic amine compounds or phenothiazine compounds are particularly preferred because they are compounds chemically close to ammonia in the refrigerant, and thus have high affinity with ammonia and good compatibility.
    [67] Specific examples of the aromatic amine compound or phenothiazine compound include dipyridylamine, phenothiazine, phenothiazine derivatives such as an alkyl group added to the phenylene group, dialkyldiphenylamine diphenyl-p-phenylenediamine A diphenyl-p-phenylenediamine derivative in which a phenyl group is substituted with a naphthyl group or an alkyl group, and dialkylphenyl-p-phenylenediamine. Among them, preferred are dipyridylamine, p, p'-dialkyldiphenylamine having an alkyl group of 4 to 20 carbon atoms (more preferably 4 to 12 carbon atoms, particularly preferably 8 carbon atoms) N, N'-dialkylphenyl-p-phenylenediamine having an alkyl group having 1 to 4 carbon atoms (preferably having 4 to 12 carbon atoms) is preferable.
    [68] The amount of the antioxidant added is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total amount of the lubricant for refrigerator of the present invention. If the addition amount is too small, the effect as an antioxidant can not be obtained, and even if it is added in an amount exceeding 5.0 mass%, an effect corresponding to the addition amount can not be obtained. In addition, excessive additions should also be avoided in this regard, since a large amount of oil tends to be colored.
    [69] Typical examples of the metal deactivator used in the present invention include a benzotriazole-based compound and / or a derivative thereof.
    [70] Here, the benzotriazole derivative is represented by the following general formula
    [71]
    [72] [Wherein R 1 , R 2 and R 3 are hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 1 to 20 carbon atoms, which may be the same or different]. These compounds are supposed to have a function of covering the metal surface and protecting the metal material from corrosive substances such as ammonia refrigerant.
    [73] In the refrigerating machine lubricant of the present invention, the addition amount of the metal deactivating agent is not particularly limited and may be appropriately selected according to the circumstances, but is preferably 1 to 200 mass ppm, particularly preferably 5 to 50 mass ppm, relative to the whole lubricant .
    [74] Examples of the abrasion preventing agent used in the present invention include phosphate compounds such as tricresyl phosphate and triphenyl phosphate, alcohol compounds such as aliphatic higher alcohols, polyhydric alcohol esters and polyhydric alcohol ethers, and N-hydrocarbyl alkanolamine Of an anti-wear agent can be used. Particularly, it is preferable to contain at least one compound selected from the group consisting of aliphatic higher alcohols having 10 or more carbon atoms, polyhydric alcohol partial esters and polyhydric alcohol partial ethers.
    [75] Examples of the aliphatic higher alcohols having 10 or more carbon atoms include aliphatic alcohols such as 1-decanol, isodecyl alcohol, secondary decanol, undecanol, secondary undecanol, 2-methyl decanol, lauryl alcohol, But are not limited to, trimethylolpropane, 1-tridecanol, isotridecyl alcohol, secondary tridecanol, myristyl alcohol, secondary tetradecanol, pentadecanol, secondary pentadecanol, cetyl alcohol, Octadecanol, octadecyl alcohol, oleyl alcohol, behenyl alcohol, eicosanol, dococanol, tetracosanol, hexacosanol, octacosanol, octacosanol, octadecanol, Butanol, 2-hexyldecanol, 2-hexyldecanol, 2-hexyldecanol, 2-hexyldecanol, 2-hexyldecanol, 2-hexyldecanol, 2-hexyldecanol, Examples of the organic solvent include decanol, 2-octyldecanol, 2-octyldodecanol, 2-octyltetradecanol, 2-decyldodecanol, 2-decyltetradecanol, , 2-dodecyltetradecanol, 2-dodecylhexadecanol, 2-dodecyloctadecanol, 2-tetradecyloctadecanol, 2-tetradecylcosenol, 2-hexadecyloctadecanol, 2 - hexadecyl is an aliphatic alcohol such as casonol.
    [76] The polyhydric alcohol moiety ester is represented by the following formula
    [77] R 4 (OH) h {OC (O) R 5 } k
    [78] Wherein R 4 represents a linear or branched, saturated or unsaturated hydrocarbon group of 2 to 12 carbon atoms corresponding to the residue of the polyvalent alcohol of (h + k), R 5 represents a linear or branched K is a number of esterified acyl groups, h and k are numbers satisfying 1 H <6, 1 K <6, 2 H + k 6]
    [79] Lt; / RTI &gt; More specifically, it is a partial ester of a polyhydric alcohol such as glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitol and the like, and a linear or branched chain saturated or unsaturated fatty acid having 3 to 20 carbon atoms. Among them, partial esters of glycerin, sorbitol, sorbitol and fatty acids having 10 to 20 carbon atoms are preferable, mono fatty acid esters are preferable, and mono fatty acid esters of glycerin are particularly preferable.
    [80] The polyhydric alcohol partial ether is represented by the following general formula
    [81] R 6 (OH) r {OR 7 } s
    [82] Wherein R 6 represents a linear or branched, saturated or unsaturated hydrocarbon group of 2 to 12 carbon atoms corresponding to the residue of the polyvalent alcohol of r + s and R 7 represents a linear or branched saturated or unsaturated hydrocarbon group of 3 to 20 carbon atoms Or an unsaturated hydrocarbon group, r represents a number of hydroxyl groups remaining without being etherified, s represents etherified ether bond numbers, r and s satisfy 1 R <6, 1 S <6, r + s &lt; / = 6]
    [83] Lt; / RTI &gt; More specifically, it is a partial ether obtained by condensing a polyhydric alcohol such as glycol, glycerin, trimethylol propane, pentaerythritol, sorbitol, sorbitol and the like, and a linear or branched, saturated or unsaturated monol having 3 to 20 carbon atoms. Among them, glycerin, sorbitol, sorbitol and a partial ether of an aliphatic alcohol having 10 to 20 carbon atoms are preferable, monoalkyl or alkenyl ether is more preferable, and monoalkyl or alkenyl ether of glycerin is particularly preferable.
    [84] Examples of the N-hydrocarbyl alkanolamine include N-butyl monoethanol amine, N-hexyl monoethanol amine, N-cyclohexyl monoethanol amine, N-octyl monoethanol amine, N-decyl monoethanol amine, N- Derived alkyl monoethanol amine, N-wozy alkyl monoethanol amine, N-soybean oil-derived alkyl monoethanol amine, N-oleyl monoethanol amine, N-stearyl monoethanol amine, N-butyl diethanol amine, N-octyldiethanolamine, N-decyldiethanolamine, N-coconut oil-derived alkyldiethanolamine, N-wursted alkyldiethanolamine, N-soybean oil-derived alkyl Diethanolamine, N-stearyldiethanolamine, N, N-dibutylmonoethanolamine, N, N-dihexylmonoethanolamine, N, N-dicyclohexyl monoethanolamine, N, N-dioctyl monoethanolamine, N, N-decyl monoethanolamine, N, N-bis (Alkyl derived from soybean oil) monoethanolamine, N, N-diol rail monoethanolamine, N, N-diisopropylamine, Long-chain alkylalkanolamines such as tetraarylmethanolamine and tealylmonoethanolamine, and alkylene oxide adducts thereof.
    [85] The amount of the abrasion-preventing agent to be added to the refrigerating machine lubricant of the present invention is not particularly limited and may be suitably selected according to circumstances, and is preferably 0.1 to 2.0 mass%, particularly preferably 0.2 to 1.0 mass% with respect to the total amount of the lubricant.
    [86] The refrigerating machine lubricant of the present invention contains at least one additive selected from the above antioxidants, abrasion inhibitors and metal deactivators. It is a matter of course that the antioxidant, the abrasion preventing agent and the metal deactivating agent are also used in combination in the present invention. Further, it is more preferable that the refrigerating machine lubricant of the present invention contains an additive composed of at least one compound selected from the above-mentioned antioxidants, abrasion inhibitors and metal deactivators.
    [87] Further, the refrigerating machine lubricant of the present invention can be suitably used for a refrigerating machine lubricant machine such as naphthenic mineral oil, alkylbenzene oil, ether oil, ester oil, Can be compounded.
    [88] Other known additives include stabilizers such as phenyl glycidyl ether and alkyl glycidyl ether, antifoaming agents or defoamers such as polydimethylsiloxane and polymethacryl acrylate, and the like. Other defoaming agents and defoaming agents, a clean dispersant, a viscosity index improver, a corrosion inhibitor, a pour point depressant, and the like may also be added as needed. These additives are usually compounded in an amount of about 10 mass ppm to 10 mass% in the lubricant of the present invention.
    [89] The refrigerant used with the refrigerator lubricant of the present invention is an ammonia refrigerant, but it must be dissolved with a refrigerant containing ammonia. That is, not only a refrigerant composed of only ammonia but also a mixed refrigerant of ammonia, a low molecular weight hydrocarbon compound or ammonia and the above-mentioned fluorinated hydrocarbon, and a mixed refrigerant of ammonia, a low molecular weight hydrocarbon compound, and three kinds of the above-mentioned fluorinated hydrocarbons The mixed refrigerant also corresponds to the ammonia refrigerant used in the present invention.
    [90] The refrigerator lubricant and the ammonia refrigerant of the present invention may be charged at a suitable ratio in accordance with the specifications of the refrigeration system to which the refrigerant system is applied. Concretely, the mass ratio of the ammonia refrigerant / refrigerant lubricant is preferably in the range of 99/1 to 1/99, more preferably 95/5 to 30/70.
    [91] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples,% represents mass% and ratio represents mass ratio.
    [92] 1 to 12 and Comparative Examples 1 to 10:
    [93] The following five types of polyether compounds were used as base oils for refrigerating machine lubricants and the following antioxidants (two types), metal deactivators (one type) and abrasion inhibitors (three types) 1 to prepare lubricant compositions of the sample oil of the comparative examples used in the evaluation test. Then, these sample oils were subjected to an evaluation test of the stability by the sealed tube test, the evaluation test of lubricity by the melt load of parex and the compatibility test with the ammonia refrigerant.
    [94] <Base oil>
    [95] PAG1: CH 3 O (PO) m / (EO) n H
    [96] m / n = 8/2, kinematic viscosity (40 DEG C) = 46 mm2 / s
    [97] Terminal secondary hydroxyl group ratio: 90%, molecular weight: 1,000
    [98] PAG2: CH 3 O (PO) m / (EO) n H
    [99] m / n = 7/3, kinematic viscosity (40 ° C) = 46 mm 2 / s
    [100] Terminal secondary hydroxyl group ratio: 60%, molecular weight: 1,040
    [101] PAG3: CH 3 O (PO) m / (EO) n H
    [102] m / n = 6/4, kinematic viscosity (40 ° C) = 46 mm 2 / s
    [103] Terminal secondary hydroxyl group content: 40%, molecular weight: 1,060
    [104] PAG4: CH 3 O (PO) m / (EO) n CH 3
    [105] m / n = 8/2, kinematic viscosity (40 DEG C) = 46 mm2 / s
    [106] Molecular weight: 1,000
    [107] PAG5: CH 3 O (PO) m H
    [108] Kinematic viscosity (40 DEG C) = 50 mm2 / s, Molecular weight: 950
    [109] PAG6: CH 3 O (PO) m / (EO) n - (PO) 2 -H
    [110] m / n = 6/4, kinematic viscosity (40 ° C) = 54 mm 2 / s
    [111] Terminal secondary hydroxyl group ratio: 90%, molecular weight: 1,170
    [112] Wherein PO represents an oxypropylene group and EO represents an oxyethylene group. (PO) / (EO) represents a random upper part of PO and EO.
    [113] PAG1 and PAG2 are contained in the polyether compound represented by the formula (1) or (2) in the present invention, and PAG6 is contained in the polyether compound represented by the formula (2) 50% of the total number of hydroxyl groups, PAG4 has a terminal end with methyl groups, PAG5 does not contain oxyethylene groups, and is not contained in the present invention.
    [114] <Additives>
    [115] (I) Antioxidant (2 kinds)
    [116] DOPA: p, p'-di-octyl-di-phenylamine
    [117] DBPC: 2,6-di-t-butyl-p-cresol
    [118] (Ii) Metal deactivating agent (1 kind)
    [119] BTA: benzotriazole
    [120] (Iii) Abrasion resistance agent (3 kinds)
    [121] GMOE: glycerin monooleyl ether
    [122] GMO: glycerin monooleate
    [123] TCP: Tricresyl phosphate
    [124] materialsadditive AntioxidantAddition amount (% by mass)Metal deactivatorAddition amount (mass ppm)Abrasion inhibitorAddition amount (% by mass) Example 1PAG1DOPA0.05---- Example 2PAG1DOPA0.1---- Example 32PAG1DOPA0.05---- Example 4PAG1DOPA0.05BTA10-- Example 5PAG1DOPA0.05BTA20-- Example 6PAG1DOPA0.05--GMOE0.5 Example 7PAG1DOPA0.05--GMOE1.0 Example 8PAG1DOPA0.05--GMO0.5 Example 9PAG2DOPA0.05--GMOE0.5 Example 10PAG1DOPA0.05BTA10GMOE0.5 Example 11PAG2DOPA0.05BTA10GMOE0.5 Example 12PAG6DOPA0.05BTA10GMOE0.5 Comparative Example 1PAG1------ Comparative Example 2PAG2------ Comparative Example 3PAG6------ Comparative Example 4PAG3DBPC0.1---- Comparative Example 5PAG3----TCP0.5 Comparative Example 6PAG3DOPA0.05BTA10GMOE0.5 Comparative Example 7PAG4------ Comparative Example 8PAG4DOPA0.05BTA10GMOE0.5 Comparative Example 9PAG5------ Comparative Example 10PAG5DOPA0.05BTA10GMOE0.5
    [125] <Performance evaluation test of lubricant>
    [126] (I) Stability test (sealed tube test)
    [127] 8 ml of each sample oil and 2 ml of ammonia refrigerant (R717) in the examples and comparative examples shown in Table 1 were sealed in a bomb together with an iron and aluminum catalyst according to JIS K2211 to prepare a sealed tube. These sealed tubes were heated and maintained at 150 DEG C for 14 days, and then the appearance of these deteriorated sample oils and catalysts was visually observed and evaluated. The appearance of the sample oil after deterioration and the external appearance of the catalyst indicate that the same as the original one, "no change", and that precipitates are observed in the oil and that discoloration is observed in the catalyst, &Quot; and &quot; discoloration 5 &quot;.
    [128] The color of each sample oil after deterioration was measured in accordance with JIS K 2580 ASTM color test method. In other words, the color of the sample oil was compared with the color of the ASTM color standard glass and expressed as a value in the range of 0.5 to 8.0 every 0.5. When it is determined that the color of the sample oil is, for example, between 1.0 and 1.5, the color of the standard glass (1.5 in this case) is adopted, and L is given to display it as "L1.5".
    [129] (Ii) Lubrication test (Falex melt load test)
    [130] The load at the time of melt was measured by applying a block made of steel (AISI C-1137) and a pin made of steel (SAE 3135) according to ASTM D2670 at an initial temperature of 40 캜 and a rotational speed of 290 rpm.
    [131] (Iii) Compatibility test (measurement of two-layer separation temperature)
    [132] The separation temperature was measured in a sample oil / R717 (ammonia refrigerant) = 2/8 mixture according to JIS K2211 Annex 3.
    [133] The results of these evaluation tests are shown in Table 2. The term &quot; Fe discoloration &quot; as a result of evaluation of the appearance of the catalyst in the sealed tube test indicates discoloration of iron in the catalyst to the degree described in Table 2, but no discoloration was observed in aluminum.
    [134] Sealed tube testParex melt load (N)Two-layer separation temperature (℃) Color (ASTM)Sample oil appearanceCatalytic Appearance Example 1L0.5No changeFe discoloration 23825-9 Example 2L1.0No changeFe discoloration 13781-9 Example 3L1.5No changeFe discoloration 24003-16 Example 4L0.5No changeNo change3870-9 Example 5L0.5No changeNo change3914-9 Example 6L0.5No changeFe discoloration 14137-7 Example 7L1.0No changeFe discoloration 14226-6 Example 8L0.5No changeFe discoloration 24048-7 Example 9L0.5No changeFe discoloration 24359-14 Example 10L1.0No changeNo change4181-7 Example 11L1.5No changeNo change4404-13 Example 12L0.5No changeFe discoloration 14137-16 Comparative Example 1L2.5Precipitation 5Fe discoloration 53736-9 Comparative Example 2L3.0Precipitation 5Fe discoloration 43914-16 Comparative Example 3L2.0Precipitation 2Fe discoloration 44003-16 Comparative Example 4L3.5Precipitation 4Fe discoloration 44092Room temperature separation Comparative Example 5L4.5Precipitation 5Fe discoloration 54582-24 Comparative Example 6L3.0Precipitation 3Fe discoloration 24448-22 Comparative Example 7L1.5Precipitation 2Fe discoloration 4347011 Comparative Example 8L0.5No changeNo change373612 Comparative Example 9L1.0Precipitation 1Fe discoloration 43114Room temperature separation Comparative Example 10L0.5No changeNo change3336Room temperature separation
    [135] According to Table 2, in the sample oils (Examples 1 to 3) in which the aromatic amine compound or the phenothiazine compound was added as the antioxidant, discoloration was observed with respect to the appearance of the catalyst in the sealed tube test, Respectively. In addition to the aromatic amine compound or phenothiazine compound, a sample oil to which benzotriazole is added as a metal deactivator (Examples 4 and 5) and a glycerin monooleyl ether or glycerin monooleate It can be seen that all of the sample oils (Examples 6 to 9) are improved in stability and lubricity performance than the oils of Examples 1 to 3. In addition, it can be seen that the performance of the sample oils (Examples 10 to 12) to which the aromatic amine compound or the phenothiazine compound, benzotriazole and glycerin monooleylether are added is further improved. The compatibility with ammonia refrigerant was sufficiently compatible with any oil.
    [136] On the other hand, it is understood that the sample oil in which the additives are not added in the PAG1, PAG2, or PAG6 alone of Comparative Examples 1 to 3 is much inferior to the outer appearance of the sample oil and the appearance of the catalyst in the sealed tube test have.
    [137] In Comparative Examples 4 to 6, additives were added to PAG3 not contained in the present invention. As a result, the results of the sealed tube test were worse than those of Examples, indicating that there was a problem in stability.
    [138] In Comparative Examples 7 to 10, PAG4 or PAG5 alone or additives not contained in the present invention were added. However, compatibility with ammonia refrigerant was poor, and there was also a problem in lubricity.
    [139] The present invention relates to a refrigerator lubricant containing a specific polyether compound as a base oil and containing at least one additive selected from an antioxidant, an abrasion inhibitor and a metal deactivator, and has excellent stability and lubrication performance as well as compatibility with ammonia , Which is useful as a refrigerant lubricant using an ammonia refrigerant.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] 1. A refrigerating machine lubricant using ammonia as a refrigerant, characterized by containing at least one polyether compound represented by the following formula (1) or (2) and at least one additive selected from an antioxidant, Lubricants:
    [Chemical Formula 1] X {-O- (AO) n- H} p
    (AO) n represents a polyoxyalkylene chain constituted by copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, and n represents a number of 2 or more P represents a valence of X, and the number of the secondary hydroxyl groups in the hydroxyl groups located at the structural ends is 50% or more of the total hydroxyl groups.
    (2)
    X {-O- (AO 1) a - (AO 2) b -H} p
    (AO 1 ) a represents a polyoxyalkylene chain constituted by copolymerization of ethylene oxide and propylene oxide and / or butylene oxide, and AO 2 represents a polyoxyalkylene chain constituted by copolymerization of propylene oxide and / or butylene oxide, wherein X represents a moiety excluding a hydroxyl group in the monool or polyol A represents an integer of 2 or more, b represents a number of 1 or more, and p represents a valence of X. [
    [2" claim-type="Currently amended] The refrigerator lubricant according to claim 1, wherein the antioxidant is an aromatic amine compound or a phenothiazine compound.
    [3" claim-type="Currently amended] The refrigerating machine lubricant according to claim 1 or 2, wherein the metal deactivator is a benzotriazole-based compound.
    [4" claim-type="Currently amended] The anti-wear agent according to any one of claims 1 to 3, wherein the anti-wear agent contains at least one compound selected from the group consisting of aliphatic higher alcohols having 10 or more carbon atoms, polyhydric alcohol partial esters and polyhydric alcohol partial ethers Lubricating oil.
    [5" claim-type="Currently amended] The positive resist composition according to any one of claims 1 to 4, wherein (AO) n in formula ( 1 ) or (AO 1 ) a in formula (2) is a random copolymer of ethylene oxide with propylene oxide and / or butylene oxide, A lubricant for a refrigerator, which is a polyoxyalkylene group constituted by a copolymer, or a copolymer in which random copolymerization and block copolymerization are mixed.
    [6" claim-type="Currently amended] The refrigerating machine lubricant according to any one of claims 1 to 5, wherein the polyether compound represented by the general formula (1) or (2) has a kinematic viscosity at 40 DEG C of 15 to 200 mm2 / s.
    [7" claim-type="Currently amended] The refrigerating machine lubricant according to any one of claims 1 to 6, wherein the ratio of oxyethylene groups in (AO) n in formula ( 1 ) or (AO 1 ) a in formula (2) is from 5 to 50 mass%.
    [8" claim-type="Currently amended] The refrigerating machine lubricant according to any one of claims 1 to 7, wherein the polyether compound represented by the general formula (1) or (2) has an unsaturation degree of 0.05 meq / g or less.
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    同族专利:
    公开号 | 公开日
    EP1251162A4|2003-07-16|
    KR100752088B1|2007-08-27|
    EP1251162A1|2002-10-23|
    WO2001053440A1|2001-07-26|
    US6875730B2|2005-04-05|
    JP2001200285A|2001-07-24|
    US20030027729A1|2003-02-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-01-21|Priority to JP2000013248A
    2000-01-21|Priority to JPJP-P-2000-00013248
    2001-01-19|Application filed by 가부시키가이샤 저펜에너지
    2002-08-21|Publication of KR20020067064A
    2007-08-27|Application granted
    2007-08-27|Publication of KR100752088B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000013248A|JP2001200285A|2000-01-21|2000-01-21|Lubricant for refrigerator utilizing ammonia refrigerant|
    JPJP-P-2000-00013248|2000-01-21|
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