CN101544925B - Refrigerator oil for refrigerant - Google Patents
Refrigerator oil for refrigerant Download PDFInfo
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- CN101544925B CN101544925B CN200910132449.2A CN200910132449A CN101544925B CN 101544925 B CN101544925 B CN 101544925B CN 200910132449 A CN200910132449 A CN 200910132449A CN 101544925 B CN101544925 B CN 101544925B
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Abstract
The invention provides a refrigerator oil for refrigerant used together with hydrogen containing Freon coolant without chlorine contained or hydrocarbon refrigerant without halogen atom and having smaller greenhouse effect, which has low viscosity, great stability. A refrigerator oil for refrigerant includes a monoester represented by a general formula (1) as a main component, has kinematic coefficient of viscosity lower than 7mm2/s under 40 DEG C. In the formula, R1 represents an alkyl group with 5-9 carbons, R2 represents an alkyl group with 8-10 carbons, R1 and R2 being in branched chain or direct chain, and total carbon number being 13-17.
Description
Technical field
The present invention relates to can be well for using the refrigerator oil for refrigerant of the cooling agent compression freezing cycle device of the cooling agent that the depletion of the ozone layer coefficients such as not chloride hydrogeneous freon refrigerant and hydro carbons cooling agent and global warming coefficient are little.In addition, the invention still further relates to the good low viscous refrigerator oil of energy saving and use this oily used for refrigerator working fluid and refrigerator.
Background technology
In the past, refrigerator, air-conditioning, the cooling agent compression freezing cycle device used such as refrigerator is for example used the R-11 (Trichloromonofluoromethane) as Chlorofluorocarbons (CFCs) (CFC) always, R12 (Refrigerant 12) and as R-22 (monochlorodifluoromethane) of Hydrochlorofluorocarbons (HCFC) etc. using fluorine and chlorine as the freonll-11 of Constitution Elements as cooling agent, but involve nearest depletion of the ozone layer problem, its production and use are restricted in the world, turn to just gradually at present for example methylene fluoride (R-32), the hydrogeneous freon refrigerant that Tetrafluoroethane (R-134 or R-134a) etc. are not chloride and for example ethane, propane, butane, Trimethylmethane isothermal chamber effect hydro carbons cooling agent little and not halogen atom-containing etc.
As the refrigerator oil for refrigerant for these cooling agent, contriver has proposed to take to adopt the refrigerator oil for refrigerant (patent documentation 1) that the ester of the polyvalent alcohols such as polyol is base oil.By this, rudimentary hydro carbons cooling agent, in the situation of working fluid, can be obtained to the effect of the generation that prevents oligopolymer (polymer substance).But refrigerator, air-conditioning, refrigerator etc. are required further energy-saving recently, for refrigerator oil, also require to realize the energy-saving refrigerator oil of lowering viscousity.
The viscosity that has disclosed a certain polyol esters of fatty acids in patent documentation 2 is low, and oilness is good, but in order to reduce viscosity by polyol esters of fatty acids, the carbon number of lipid acid must be below 5, and stability to hydrolysis significantly declines.
In addition, in patent documentation 3, as low viscosity and the good refrigerator oil of stability to hydrolysis, propose the refrigerator oil that comprises saturated chain carboxylic acid mono alkyl ester of at least a kind of aliphatics, also disclosed the mixture of this ester and polyol esters of fatty acids.Yet, the enormous amount of the combination of saturated chain carboxylic acid mono alkyl ester of aliphatics and polyol esters of fatty acids, find that low viscosity and oilness are good, flash-point is high and security also combination good, that can also meet stability to hydrolysis be very difficult.
Patent documentation 1: Japanese Patent Laid-Open 2007-254713 communique
Patent documentation 2: Japanese Patent Laid-Open 2007-248020 communique
Patent documentation 3: Japanese Patent is public table patent WO00/68345 communique again
Summary of the invention
As mentioned above, use in the refrigerator of hydro carbons cooling agent of the not halogen atom-containing that not chloride hydrogeneous freon refrigerant or Greenhouse effect are less, for energy saving is improved, using the low lubricating oil of viscosity is effective as refrigerator oil, but adopt, take under the refrigerator oil condition of the so-called Dormant oils class that paraffin Dormant oils or naphthenic hydrocarbon Dormant oils be base material, to exist flash-point to reduce and the dangerous problem raising while processing.On the other hand, take and adopt the ester of the polyvalent alcohols such as polyol under base oil condition, must use the few lipid acid of carbon number, the stability of this structure significantly declines, the corrosion that the lipid acid producing in the time of also may decomposing causes.
The present invention is the invention that solves above-mentioned problem, the object of the present invention is to provide together with the hydro carbons cooling agent with not chloride hydrogeneous freon refrigerant or the less not halogen atom-containing of Greenhouse effect and use, low viscosity and security, the refrigerator oil for refrigerant having good stability.
After studying to achieve these goals and conscientiously, the present invention finds, base oil be take specific monoesters as main component or mixes the refrigerator oil of polyol ester again low at not chloride hydrogeneous freon refrigerant or hydro carbons cooling agent medium viscosity, also there is good oilness, energy saving, and stability to hydrolysis is also high, as cooling agent compression lubricating oil for freezing cycle device, be that refrigerator oil for refrigerant is very good, thereby expected the present invention.
That is, the present invention is following refrigerator oil for refrigerant.
(1) refrigerator oil for refrigerant, wherein, contains monoesters that the general formula (1) of usining below represents as main component, the not enough 7mm of kinematic viscosity in the time of 40 ℃
2/ s;
In formula, R
1the alkyl that represents carbon number 5～9, R
2the alkyl that represents carbon number 8～10, R
1and R
2can be respectively side chain or straight chain, and R
1and R
2the summation of carbon number be 13～17.
(2) refrigerator oil for refrigerant as described in (1), wherein, also contains polyol ester.
(3) refrigerator oil for refrigerant as described in (2), wherein, monoesters is the monoesters of the aliphatic monobasic alcohol of carbon number 8 and the unary fatty acid of carbon number 8, polyol ester is 2 ethyl hexanoic acid and/or 3, in the polyol ester of the amyl-based polyol of 5,5-tri-methyl hexanoic acid and carbon number 5～10 at least a kind.
(4) refrigerator oil for refrigerant as described in (3), wherein, comprises at least a kind in 75～95 quality % monoesters and 5～25 quality % polyol esters.
(5) refrigerator oil as described in (4), wherein, the kinematic viscosity in the time of 40 ℃ is 2～4mm
2/ s, flash-point is more than 130 ℃, and acid number is below 0.1mgKOH/g, and the volume specific resistance in the time of 25 ℃ is more than 10G Ω m.
(6) refrigerator oil for refrigerant as described in (3), wherein, comprises at least a kind in 25～40 quality % monoesters and 60～75 quality % polyol esters.
(7) refrigerator oil as described in (6), wherein, the kinematic viscosity in the time of 40 ℃ is 4～7mm
2/ s, flash-point is more than 130 ℃, and acid number is below 0.1mgKOH/g, and the volume specific resistance in the time of 25 ℃ is more than 10G Ω m.
(8) refrigerator oil as described in any one in (4)～(7), wherein, described monoesters is the ester of n-Octanol and 2 ethyl hexanoic acid.
(9) refrigerator oil as described in any one in (4)～(7), wherein, described polyol ester is neopentyl glycol two-2-ethylhexanoate or tetramethylolmethane four-2-ethylhexanoate.
(10) refrigerator oil as described in (8), wherein, described polyol ester is neopentyl glycol two-2-ethylhexanoate or tetramethylolmethane four-2-ethylhexanoate.
(11) refrigerator oil as described in (10), wherein, is added with 0.01～1 quality % by having the compound of oxirane ring or the acid scavenger that carbodiimide compound forms.
(12) refrigerator oil as described in (10), wherein, is added with the metal passivator that 1～100 quality ppm has benzotriazole structure.
(13) refrigerator oil as described in (10), wherein, is added with the oiliness improver in 0.01～1 quality % molecule with 2 above hydroxyls.
(14) refrigerator oil as described in (10), wherein, be added with 1～100 quality ppm be selected from silicone oil, end with polyalkylene glycol or ester modified and silicone oil or the defoamer of fluorinated silicone oil at least a kind.
(15) a used for refrigerator working fluid, the refrigerator oil described in any one in wherein, contain (4)～(7), (10)～(14) and be selected from least a kind of hydro carbons cooling agent of ethane, propane, butane or Trimethylmethane.
(16) a used for refrigerator working fluid, wherein, contains (8) described refrigerator oil and at least a kind of hydro carbons cooling agent that is selected from ethane, propane, butane or Trimethylmethane.
(17) a used for refrigerator working fluid, wherein, contains (9) described refrigerator oil and at least a kind of hydro carbons cooling agent that is selected from ethane, propane, butane or Trimethylmethane.
(18) a kind of refrigerator, wherein, by the used for refrigerator working fluid (15) Suo Shu, compress the hermetic compressor of this fluid, make the condenser of cooling agent condensation, the expansion mechanism that cooling agent is expanded, the vaporizer of cooling agent evaporation is formed, described hermetic compressor comprises the electric motor with rotor and stator, described electric motor comprises polyethylene terephthalate, polybutylene terephthalate, polyamidoimide coating polyester, the insulating film of any a kind in polyphenylene sulfide and polyether-ether-ketone, described stator comprises the winding in more than 120 ℃ enamel paint material coatings with second-order transition temperature.
(19) a kind of refrigerator, wherein, by the used for refrigerator working fluid (16) or (17) Suo Shu, compress the hermetic compressor of this fluid, make the condenser of cooling agent condensation, the expansion mechanism that cooling agent is expanded, the vaporizer of cooling agent evaporation is formed, described hermetic compressor comprises the electric motor with rotor and stator, described electric motor comprises polyethylene terephthalate, polybutylene terephthalate, polyamidoimide coating polyester, the insulating film of any a kind in polyphenylene sulfide and polyether-ether-ketone, described stator comprises the winding in more than 120 ℃ enamel paint material coatings with second-order transition temperature.
(20) refrigerator as described in (18), wherein, described hermetic compressor is reciprocating.
(21) refrigerator as described in (19), wherein, described hermetic compressor is reciprocating.
By the present invention, can be provided for the hydro carbons cooling agent of the not halogen atom-containing that not chloride hydrogeneous freon refrigerant or Greenhouse effect are less, low viscosity and the refrigerator oil for refrigerant having good stability.Therefore, play following effect: the greenhouse of the earth etc. are little on the impact of environment, and low viscosity, and energy saving is good, and oilness is good, the high and security of flash-point might as well, can also meet stability to hydrolysis and oxidative stability etc.In addition, adopt the used for refrigerator working fluid of the present invention of described refrigerator oil to play following effect: can not damage each equipment and the parts of refrigeration system, this refrigeration system steadily in the long term can turn round.In addition, the refrigerator for adopting this refrigerator oil, plays following effect: energy-conservation, work steadily in the long term.
Embodiment
The present invention is specifically described.
The present invention is a kind of refrigerator oil for refrigerant, wherein, contains monoesters that the general formula (1) of usining below represents as main component, the not enough 7mm of kinematic viscosity in the time of 40 ℃
2/ s;
In general formula (1), R
1the alkyl that represents carbon number 5～9, R
2the alkyl that represents carbon number 8～10, R
1and R
2can be respectively side chain or straight chain, and R
1and R
2the summation of carbon number be 13～17.
Refrigerator oil for refrigerant of the present invention can be used well together with not chloride cooling agent and not halogen-containing cooling agent.; refrigerator oil for refrigerant of the present invention can be used the refrigerator oil that acts on following cooling agent well: the hydro carbons cooling agent that the not chloride little hydrogeneous freon refrigerants of depletion of the ozone layer coefficient such as methylene fluoride (R-32), Tetrafluoroethane (R-134 or R-134a), particularly not halogen-containing depletion of the ozone layer coefficients such as ethane (R170), propane (R290), butane (R600), Trimethylmethane (R600a) and global warming coefficient are all little etc.
In the present invention, the monoesters that is used as the main component of refrigerator oil for refrigerant represents with general formula (1).
In formula, R
1the alkyl that represents carbon number 5～9.Alkyl can have unsaturated link(age), but from the angle of chemical stability, is better saturated hydrocarbyl.In addition R,
1can be the alkyl of the form of alkyl and aromatic nucleus or naphthalene nucleus combination, but the alkyl of straight or branched particularly preferably.R
2the alkyl that represents carbon number 8～10.R
2with R
1equally, can have unsaturated link(age), can be also the alkyl of the form of alkyl and aromatic nucleus or naphthalene nucleus combination, the particularly preferably alkyl of straight or branched.R
2carbon number lower than in 8 situation, the viscosity of ester that produces gained is too low and oilness deficiency and flash-point decline and problems such as danger increase on processing, in 10 situation, cannot obtain energy-saving effect.
In addition R,
1and R
2the summation of carbon number be 13～17, during the summation less than 13 of carbon number, the viscosity of ester that produces gained is too low and oilness deficiency and flash-point decline and problems such as danger increase on processing, so be undesirable.In addition, if the summation of carbon number surpasses 17, viscosity raises, and produces the problem of the energy-saving effect deficiency in compressor.In addition, R
1the situation of carbon number less than 5 under, after hydrolysis, carbon number is less, the strength of acid of the unary fatty acid of generation (carboxylic acid) is stronger, causes the corrosion harm such as equipment and materials around, so be undesirable.
From the chemical formula of general formula (1), the such monoesters using in the present invention can be by synthesizing the monohydroxy-alcohol esterification of the unary fatty acid of carbon number 6～10 (carboxylic acid) and carbon number 8～10.In the present invention, do not limit the manufacture method of monoesters; as the compound that is equivalent to unary fatty acid; can adopt the acyl chlorides of unary fatty acid and carboxylic acid anhydride etc. to synthesize, can also utilize the alkoxyl group of monoesters or acyl group is exchanged for other alkoxyl group or the transesterification reaction of acyl group is synthesized.
In the present invention, as can be well for the synthetic unary fatty acid of the monoesters of general formula (1), can exemplify caproic acid, enanthic acid, n-caprylic acid, isocaprylic acid, 2 ethyl hexanoic acid, 1-methyl enanthic acid, 2-methyl enanthic acid, valproic acid, dimethyl cyclohexylenedinitrilotetraacetic acid, n-nonanoic acid, 3,5,5-tri-methyl hexanoic acid, capric acid, the wherein sad or 2 ethyl hexanoic acid of carbon number 8 particularly preferably.
In the present invention, as can be well for the synthetic monohydroxy-alcohol of the monoesters of general formula (1), can exemplify n-Octanol, isooctyl alcohol, 1-isoocanol, 2-isoocanol, 2-propyl group amylalcohol, dimethyl cyclohexanol, 2-Ethylhexyl Alcohol, decyl alcohol, be better wherein octanol or the 2-Ethylhexyl Alcohol of carbon number 8.
Also have, the monoesters being obtained by the unary fatty acid of carbon number 8 and the monohydroxy-alcohol of carbon number 8 can be realized low viscosity, can improve flash-point, and stability to hydrolysis resistance is good especially.
The monoesters that uses in the present invention forms the main component of refrigerator oil for refrigerant, thus same with refrigerator oil for refrigerant, the preferred not enough 7mm of kinematic viscosity 40 ℃ time
2/ s is better not enough 6mm
2/ s, is more preferably 2～5mm
2/ s, surpasses 7mm
2in the situation of/s, cannot obtain energy-saving effect.Kinematic viscosity and flash-point are not necessarily directly proportional, if but kinematic viscosity is low conventionally, and flash-point is low.Refrigerator oil is used mostly in enclosed system, and flash-point not too becomes problem, but from guaranteeing to be filled in the angle of the security in the processing refrigerator, flash-point is better arranged on more than 120 ℃, is more preferably more than 130 ℃, particularly preferably more than 140 ℃.
In addition,, in another embodiment of the present invention, use the polyol ester of the amyl-based polyol of 2 ethyl hexanoic acid and/or 3,5,5 Trimethylhexanoic acid and carbon number 5～10.By mix this polyol ester of specified amount in the above-mentioned monoesters of specified amount, can be adjusted to required kinematic viscosity, and can improve stability to hydrolysis.
Amyl-based polyol refers to the alcohol more than binary with neopentane structure, uses the amyl-based polyol of carbon number 5～10 in the present invention.Carbon number surpasses 10 the difficult kinematic viscosity of adjusting of amyl-based polyol, and worsens with the consistency of cooling agent.As this amyl-based polyol, can use neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, particularly preferably use neopentyl glycol and tetramethylolmethane.
The ester of using in the present invention can be by above-mentioned specific alcohol or polyvalent alcohol and specific lipid acid the esterification based on dehydration reaction or via the general esterification of the acid anhydrides as derivative of fatty acid, acyl chlorides etc. or the transesterification reaction of each derivative, obtain.
Also have, while modulating the refrigerator oil that comprises monoesters and polyol ester of the present invention, after can be first that monoesters and polyol ester is synthetic respectively, both are mixed with regulation ratio, also can be first by monohydroxy-alcohol, unary fatty acid, 2 ethyl hexanoic acid and/or 3,5,5-tri-methyl hexanoic acid and amyl-based polyol or their derivative mix with aequum, by aforesaid method, synthesize.Also have, in this situation, polyol ester can be a kind, also can two or more mix use.
The ester obtaining by aforesaid method is not specially limited unreacted and remaining acid and alcohol, but is better the not remaining carboxyl of trying one's best.If the remaining quantity of carboxyl is many, by the reacting of metal of using with refrigerator inside, generate metallic soap etc., also produce precipitation and wait the phenomenon of not wishing generation, therefore the acid number of refrigerator oil of the present invention is better below 0.1mgKOH/g.This acid number obtains by the method for regulation in JIS K2501 " petroleum product and lubricating oil-neutralization value test method, indicator titration method ".
Kinematic viscosity during in order to make to mix 40 ℃ is not too high, the not enough 10mm of kinematic viscosity when the mixing of monoesters and polyol ester is better 40 ℃ with base material
2/ s, is more preferably not enough 8mm
2/ s.
As the preferred proportioning of monoesters and polyol ester, can exemplify the proportioning that comprises the above-mentioned monoesters of 75～95 quality % and 5～25 quality % polyol esters.By adopting this proportioning, can make low viscosity, be the refrigerator oil of the viscosity of VG3 level, and oilness is good, flash-point and volume specific resistance are high, and security and stability to hydrolysis, consistency are good.
Also have, in order to make the refrigerator oil of the viscosity of VG3 level, the kinematic viscosity in the time of 40 ℃ is better 2～4mm
2/ s.
As another preferred proportioning, can exemplify the proportioning that comprises the above-mentioned monoesters of 25～40 quality % and 60～75 quality % polyol esters.By adopting this proportioning, can make low viscosity, be the refrigerator oil of the viscosity of VG5 level, and oilness is good, flash-point and volume specific resistance are high, and security and stability to hydrolysis, consistency are good.
Also have, in order to make the refrigerator oil of the viscosity of VG5 level, the kinematic viscosity in the time of 40 ℃ is better 4～7mm
2/ s.
For refrigerator oil of the present invention, in order to ensure the security on processing, be better flash-point more than 130 ℃, the angle the safety such as anti-electrostatic, the volume specific resistance while being better 25 ℃ is more than 10G Ω m.
Kinematic viscosity in the time of 40 ℃ is measured by the method for regulation in JIS K2283 " crude oil and petroleum product-movement viscosity test method and viscosity index method of calculation ", flash-point is measured by the method for regulation in JIS K2265-4 " flash-point ask 4 of Fa-: agar diffusion method is opened in Cleveland ", volume specific resistance in the time of 25 ℃ is measured under the specimen temperature of 25 ℃ according to the method for regulation in JIS C 2101 " electric insulation oil test method, 24. volume specific resistance tests ".
If above-mentioned monoesters use n-Octanol and 2 ethyl hexanoic acid ester, be 2 ethyl hexanoic acid n-octyl, the viscosity adjustment of VG3 level or VG5 level becomes easily, so is preferred.
Similarly, as polyol ester, be better used as 2 ethyl hexanoic acid and neopentyl glycol ester neopentyl glycol two-2-ethylhexanoate or as the tetramethylolmethane four-2-ethylhexanoate of the ester of 2 ethyl hexanoic acid and tetramethylolmethane.
In order further to improve the performance as refrigerator oil, refrigerator oil for refrigerant of the present invention can mix the various additives for refrigerator oil.For example, for stability to hydrolysis is improved, be better to add and there is the compound of oxirane ring or the acid scavenger that carbodiimide compound forms again in the machine oil being formed by above-mentioned ester.The compound with oxirane ring can exemplify the compound containing glycidyl ether, the compound that contains Racemic glycidol ester group, epoxidized fatty acid monoesters class, epoxidation grease, contain the compound of oxirane ring alkyl etc.Wherein, particularly preferably containing the compound of glycidyl ether, compound containing Racemic glycidol ester group, epoxidized fatty acid monoesters class, epoxidation grease, containing the compound of oxirane ring alkyl.
The addition of this acid scavenger be take refrigerator oil integral body as benchmark is better 0.01～1 quality %, is more preferably 0.2～0.7 quality %.
As phosphorous extreme-pressure additive, can exemplify of hydroxyl of phosphoric acid above esterified and phosphoric acid ester.Phosphoric acid ester can be three esters, diester or monoesters, but three esters preferably.Specifically, can exemplify the triaryl phosphates such as triphenylphosphate, tricresyl phosphate (toluene ester), tricresyl phosphate (ethylbenzene ester), tricresyl phosphate (propyl benzene ester), tricresyl phosphate (butylbenzene ester), tricresyl phosphate base diphenyl, phosphoric acid ethylbenzene diphenyl, phosphoric acid propyl phenyl diphenyl, phosphoric acid butylbenzene base diphenyl, di(2-ethylhexyl)phosphate tolyl phenylester, p diethylaminobenzoic acid phenyl ester, di(2-ethylhexyl)phosphate propyl phenyl phenylester, di(2-ethylhexyl)phosphate butylbenzene base phenylester.Wherein, particularly preferably tricresyl phosphate (toluene ester) is (TCP).Incorporation is better 0.1～2.0 quality %, is more preferably 0.2～1.5 quality %.
In addition for stability to hydrolysis is improved, be better the compound with benzotriazole structure adding as metal passivator equally.The compound with benzotriazole structure refers to the compound representing with general formula (2) below.
In formula, R
1represent hydrogen atom or methyl, R
2the group that represents the carbon number 0～20 of hydrogen atom or nitrogen atom and/or Sauerstoffatom.Addition be take refrigerator oil integral body as benchmark is better 1～100 quality ppm, is more preferably 10～80 quality ppm.
In addition, for oilness is improved, be better to add the oiliness improver in molecule with 2 above hydroxyls.Oiliness improver as having 2 above hydroxyls in this molecule, can exemplify glyceryl monooleate, glycerine list oleyl ether, glycerine list lauryl ether etc., particularly preferably glyceryl monooleate or glycerine list oleyl ether.Addition be take refrigerator oil integral body as benchmark is better 0.01～1 quality %, is more preferably 0.1～0.5 quality %.
In addition, for freezing-inhibiting machine oil bubbles in refrigeration system, be better add be selected from silicone oil, end with polyalkylene glycol or ester modified and silicone oil or the defoamer of fluorinated silicone oil at least a kind.Addition be take refrigerator oil integral body as benchmark is better 1～100ppm, is more preferably 10～80ppm.
In refrigerator oil of the present invention, can suitably mix again as required the additive except above-mentioned.As such additive, for example can also suitably mix as required 2,6-DI-tert-butylphenol compounds, 2,6-ditertbutylparacresol, 4,4-methylene radical-bis-(2,6-ditertbutylparacresol), p, the additive such as depressant prescription under the antioxidant of the phenols such as p '-dioctyl diphenylamine or amine and known purification dispersion agent, viscosity index improving agent, rust-preventive agent, sanitas, yield point.These additives add to contain the condition of 1 quality ppm～2 quality % left and right in refrigerator oil of the present invention conventionally.Particularly the antioxidant of phenols or amine, by adding 0.01～0.5 quality % left and right, can significantly improve stability, the weather resistance of lubricant.
Refrigerator oil of the present invention can be used well together with not chloride cooling agent and not halogen-containing cooling agent.; refrigerator oil of the present invention can be well for being used the refrigerator of following cooling agent: the not chloride little hydrogeneous freon refrigerants of depletion of the ozone layer coefficient such as methylene fluoride (R-32), Tetrafluoroethane (R-134 or R-134a); particularly not halogen-containing depletion of the ozone layer coefficient and all little hydro carbons cooling agent of global warming coefficient such as ethane (R170), propane (R290), butane (R600), Trimethylmethane (R600a), or their mixed cooling medium of more than two kinds etc.
Refrigerator oil of the present invention, by mixing as working fluid with these cooling agent, is responsible for the lubricated of freezing plant.By refrigerator oil of the present invention and cooling agent are mixed with the ratio of 5: 95～80: 20, can be used as working fluid.Outside this scope, in oily few situation, have the danger that causes insufficient lubrication, in oily too much situation, inefficiency, is therefore undesirable.
In addition, used for refrigerator working fluid of the present invention can be used as the working fluid that such as refrigerator, air-conditioning, refrigerator etc. at least has the cooling agent compression freezing plant of compressor, condenser, expansion mechanism and vaporizer, is particularly preferred for mainly adopting the refrigerator of hydro carbons cooling agent.
Adopt in the refrigerator of working fluid of the present invention, general use enclosed rotary or shuttle compressor, as the insulating film of the electrical insulation system material of the motor part of these coolant compressors, adopt 50 ℃ of above crystalline plastic films such as the second-order transition temperature such as polyethylene terephthalate, polybutylene terephthalate, polyamidoimide coating polyester, polyphenylene sulfide, polyether-ether-ketone or the composite membrane of the resin layer that coating second-order transition temperature is high on the low film of second-order transition temperature etc.
Equally the magnetic wire for motor part also adopts following film: the unitary film of 120 ℃ of above enamel paint coatings such as the second-order transition temperature such as polyester-imide, polymeric amide, polyamidoimide, or with the high film of the low Mo Wei lower floor of second-order transition temperature, the second-order transition temperature of take as upper strata the compound enamel paint tunicle obtaining etc.
Also have, the viscosity of used for refrigerator working fluid of the present invention is low, is therefore suitable for the shuttle hermetic compressor that stopping property is high.
Embodiment
Below, based on embodiment and comparative example, the present invention will be described in more detail, but the present invention is not subject to the restriction of embodiment.
In order to evaluate the present invention, prepared the refrigerator oil for refrigerant (for formation testing) of embodiment and comparative example.As follows for base oil, additive for formation testing.
Base oil
Monoesters 1～8: the monoesters shown in table 1
Table 1
Polyol ester 1 (PE-1): the valerate of neopentyl glycol (NPG)
Polyol ester 2 (PE-2): the capronate of NPG
Polyol ester 3 (PE-3): the 2-ethylhexanoate of NPG
Dormant oils 1 (MO-1): paraffin class lubricant base (40 ℃ of kinematic viscosity: 7.8mm
2/ s)
Dormant oils 2 (MO-2): paraffin class lubricant base (40 ℃ of kinematic viscosity: 5.2mm
2/ s)
Dormant oils 3 (MO-3): cycloalkane lubricant base (40 ℃ of kinematic viscosity: 5.0mm
2/ s)
Additive:
Acid scavenger: 2-ethylhexyl glycidyl ether
Extreme pressure agent: tricresyl phosphate (toluene ester)
Oiliness improver: glyceryl monooleate
Use above-mentioned base oil and additive, with ratio (quality %) modulation shown in the top of table 2, table 3 and table 4, obtain the refrigerator oil of embodiment and comparative example.Table 2 represents the refrigerator oil of embodiment 1～8, and table 3 represents the refrigerator oil of embodiment 9～13, and table 4 represents the refrigerator oil of comparative example 1～9.
Table 3
For the refrigerator oil of these embodiment and comparative example, measure the performances such as its physical property and consistency, stability, evaluate.The results are shown in the bottom of table 2 and table 3.
Also have, the test of physical property measurement and performance evaluation is carried out as follows.
Kinematic viscosity (40 ℃):
According to JIS K 2283, use the modified form of the Atlantic Ocean (Atlantic) viscometer to measure.
Flash-point:
According to JIS K 2265, by Cleveland, open the determination of test method of cup type (COC).
Acid number:
According to JIS K 2501, by indicator titration method, measure total acid value.
Consistency:
According to the appendix of JIS K 2,211 3, measure two layers of separation temperature.Also have, as cooling agent, use Trimethylmethane (R600a), propane (R290) and 1,1,2,2-Tetrafluoroethane (R-134a), the condition that is 2/8 than (weight) for formation testing/cooling agent is measured.
Stability:
Implement the test of so-called autoclave, test form and aspect, the acid number of the refrigerator oil after deteriorated.That is, in the stainless steel pressure vessel (autoclave) of inner capacities 100ml, add 30g confession formation testing and 10g cooling agent and as Fe, the Cu of catalyzer, the wire of Al, seal, in the thermostatic bath of 175 ℃, placing 14 days.Take out the sample after deteriorated, confirm color, acid number.Cooling agent is used R600a and R-134a, evaluates respectively.Also have, acid number is by measuring with above-mentioned same method.
Oilness:
Carry out method lux (Falex) test (290rpm, room temperature) based on ASTM D3233, determination test sheet produces the loading of burning while gluing.
Use the R of monoesters
1and R
2summation be 13～17 low viscosity oil is not only as the embodiment 1～8 of base oil and the embodiment using PE-3 as another base oil 9～13 in the lump using ME-4 as base oil in ME-2～6, and flash-point is high, also good with consistency, the stability of cooling agent, oilness is good.
Comparative example 1 using ME-1 as base oil is due to R
1and R
2summation be low to moderate 11, so viscosity and flash-point too low, be difficult to actual use.Also poor with the stability of cooling agent, the acid number after test rises.
Comparative example 2 and 3 using ME-7 and ME-8 as base oil, because the matching with cooling agent, particularly consistency are poor, is therefore difficult to actual use.
Poor stability using PE-1 and PE-2 as the comparative example 4,5 of base oil.In addition, the comparative example using PE-3 as base oil 6 is difficult to make kinematic viscosity to reach in the scope of target.
Comparative example 7 using MO-1 as base oil is also same with comparative example 6, and kinematic viscosity does not reach in the scope of target.The flash-point of MO-2 and 3 comparative examples 9 as base oil is low, poor stability.
In order to evaluate the refrigerator oil of the present invention that comprises monoesters and polyol ester, prepared the refrigerator oil for refrigerant (for formation testing) of embodiment and comparative example.
As follows for base oil, additive for formation testing.
(base oil)
ME-9: the just own ester of n-caproic acid
ME-10:2-thylhexoic acid n-octyl
ME-11: n-capric acid ester in the positive last of the ten Heavenly stems
PE-4: neopentyl glycol two n-hexoates
PE-5: neopentyl glycol two-2-ethylhexanoate
PE-6: tetramethylolmethane four-2-ethylhexanoate
The mixing acid of PE-7:2-thylhexoic acid (50 quality %) and 3,5,5 Trimethylhexanoic acid (50 quality %) and the ester of tetramethylolmethane.
(additive)
Acid scavenger: 2-ethylhexyl glycidyl ether [EPO]
Dialkyl phenyl organic carbodiimide [CDI]
Oiliness improver: glyceryl monooleate [GMO]
Metal scavenger: benzotriazole [BTA]
Defoamer: dimethyl siloxane (1000mPas25 ℃) [silicone oil]
Use above-mentioned base oil and additive, with ratio (quality %) modulation shown in the top of table 5, obtain the confession formation testing (refrigerator oil) of embodiment and comparative example.
Table 5
| The proportioning of base oil (quality %) | Additive formula | |
| Embodiment 14 | ME-10；85、PE-5；15 | Nothing |
| Embodiment 15 | ME-10；87、PE-5；10、PE-6；3 | Nothing |
| Embodiment 16 | ME-10；88、PE-5；10、PE-7；2 | Nothing |
| Embodiment 17 | ME-10；87、PE-5；10、PE-6；3 | EPO; 0.25 quality % |
| Embodiment 18 | ME-10；87、PE-5；10、PE-6；3 | EPO; 0.25 quality %, CDI; 0.05 quality % |
| Embodiment 19 | ME-10；87、PE-5；10、PE-6；3 | EPO; 0.25 quality %, CDI; 0.05 quality %BTA; 30 quality ppm, silicone oil; 40 quality ppm |
| Embodiment 20 | ?ME-10；87、PE-5；10、PE-6；3 | EPO; 0.25 quality %, CDI; 0.05 quality %GMO; 0.1 quality %, BTA; 30 quality ppm silicone oil; 40 quality ppm |
| Embodiment 21 | ME-10；30、PE-5；70 | Nothing |
| Embodiment 22 | ME-10；33、PE-5；62、PE-6；5 | Nothing |
| Embodiment 23 | ME-10；35、PE-5；62、PE-7；3 | Nothing |
| Embodiment 24 | ME-10；33、PE-5；62、PE-6；5 | EPO; 0.25 quality % |
| Embodiment 25 | ME-10；33、PE-5；62、PE-6；5 | EPO; 0.25 quality %, CDI; 0.05 quality % |
| Embodiment 26 | ME-10；33、PE-5；62、PE-6；5 | EPO; 0.25 quality %, CDI; 0.05 quality %BTA; 30 quality ppm, silicone oil; 40 quality ppm |
| Embodiment 27 | ?ME-10；33、PE-5；62、PE-6；5 | EPO; 0.25 quality %, CDI; 0.05 quality %GMO; 0.1 quality %, BTA; 30 quality ppm silicone oil; 40 quality ppm |
| Comparative example 10 | ME-9；100 | Nothing |
| Comparative example 11 | ME-11；100 | Nothing |
| Comparative example 12 | PE-4；100 | Nothing |
| Comparative example 13 | PE-5；100 | Nothing |
| Comparative example 14 | ME-9；75、PE-5；25 | Nothing |
| Comparative example 15 | ME-9；75、PE-6；25 | Nothing |
| Comparative example 16 | ME-11；90、PE-5；10 | Nothing |
| Comparative example 17 | ME-9；75、PE-5；25 | EPO; 0.25 quality %, CDI; 0.05 quality %BTA; 30 quality ppm, silicone oil; 40 quality ppm |
| Comparative example 18 | ME-11；90、PE-5；10 | EPO; 0.25 quality %, CDI; 0.05 quality %BTA; 30 quality ppm, silicone oil; 40 quality ppm |
| Comparative example 19 | ?ME-11；90、PE-5；10 | EPO; 0.25 quality %, CDI; 0.05 quality %GMO; 0.1 quality %, BTA; 30 quality ppm silicone oil; 40 quality ppm |
For the refrigerator oil of these embodiment and comparative example, measure the performances such as its physical property and consistency, stability, evaluate.The results are shown in table 6.
Also have, the physical property measurement except aforesaid measuring method and the test of performance evaluation are carried out as follows.
bubble:
By the method for regulation in JIS K2518 " petroleum product-oil whip test method(s) ", the foaminess while measuring 24 ℃ and bubble stability.
two layers of separation temperature:
By the method for regulation in the appendix 3 " with the compatibility test method of cooling agent " of JIS K 2211, measure two layers of separation temperature.Also have, as cooling agent, use Trimethylmethane (R600a), and the condition that is 2/8 than (weight) for formation testing/cooling agent is measured.
stability to hydrolysis:
The method of regulation in appendix 2 by JIS K2211 " with the test method (sealed tube test) of the chemical stability of cooling agent ", 7ml is placed 14 days under the environment of 175 ℃ of W/O component 500ppm, temperature for the mixture of formation testing and 3ml Trimethylmethane cooling agent (R600a), measure total acid value.
oilness (method lux is burnt sticky):
Carry out method lux (Falex) test (290rpm, room temperature) based on ASTM D3233, determination test sheet produces the loading of burning while gluing.
oilness (SRV friction marks):
Use ball (ball) (SUJ-2 system)/dish (disk) (SUJ-2 system) type SRV frictional testing machines, with the condition of loading 100N, frequency 50Hz, amplitude 1mm, temperature 60 C, the friction marks of determination test after 25 minutes.
compressor test:
To refrigerator, with adding 220ml for formation testing in compressor, use 30g Trimethylmethane as cooling agent, with following condition, carried out durable test.
< condition > outlet pressure: 10kg/cm
2g, suction pressure: 0kg/cm
2g, compressor surface temperature (top): 100 ℃, runtime: 1000 hours
After durable test, disassemble compressor, carried out the dirt of outlet valve and the wear evaluation of sliding part.
Be used as carbon number 8 aliphatic monobasic alcohol n-Octanol and as the ester ME-10:2 thylhexoic acid (n-octyl) and 2 ethyl hexanoic acid or 3 of the 2 ethyl hexanoic acid of the aliphatics unary fatty acid of carbon number 8,5,5-tri-methyl hexanoic acid and be not only low viscosity oil as the embodiment 14～27 of base oil as the neopentyl glycol of neo-pentyl alcohol of carbon number 5～10 or the mixture of the ester PE-4～PE-7 of tetramethylolmethane, and flash-point is high, also good with consistency, stability to hydrolysis, the volume specific resistance of cooling agent, and oilness is good.
On the other hand, use separately the ester PE-4 of monoesters ME-9～ME-11 and amyl-based polyol poor as the stability to hydrolysis of the comparative example 10～12 of base oil, and the SRV friction marks of the oilness of comparative example 10～12 is also poor.Particularly comparative example 10, and the method lux of flash-point, volume specific resistance, oilness is burnt sticky also poor.Also have, use separately the viscosity of comparative example 13 of PE-5 high, cannot fully realize energy-conservation.In addition,, even if use carbon number 6 or the alcohol of carbon number 10 and the sour sample of ester and the ester of amyl-based polyol to mix (comparative example 14～16), stability to hydrolysis is also poor, and the volume specific resistance of comparative example 14～15 is also low.Even if using the goods of these base oils to add additive (comparative example 17～19) also cannot improve.
The possibility of utilizing in industry
By the present invention, can be provided for the hydro carbons cooling agent of the not halogen atom-containing that not chloride hydrogeneous freon refrigerant or Greenhouse effect are less, low viscosity and the refrigerator oil for refrigerant having good stability.Therefore, the greenhouse of the earth etc. are little on the impact of environment, and low viscosity, can expect energy saving, so can be effectively, well for utilizing refrigerator, air-conditioning, refrigerator of cooling agent compression freezing cycle device etc.
Claims (17)
1. a refrigerator oil for refrigerant, is characterized in that, contains monoesters that the general formula (1) of usining below represents as main component, the not enough 7mm of kinematic viscosity in the time of 40 ℃
2/ s, flash-point is more than 120 ℃, also use hydro carbons cooling agent Trimethylmethane R600a or propane R290 and with two layers of separation temperature <-60 ℃ of hydro carbons cooling agent;
In formula, R
1represent amyl group, heptyl, 1-ethyl pentyl group or nonyl, R
2represent octyl group or 2-ethylhexyl, and R
1and R
2the summation of carbon number be 13～17.
2. refrigerator oil for refrigerant as claimed in claim 1, is characterized in that, also contains polyol ester.
3. refrigerator oil for refrigerant as claimed in claim 2, is characterized in that, described polyol ester is at least a kind in the polyol ester of amyl-based polyol of 2 ethyl hexanoic acid and/or 3,5,5 Trimethylhexanoic acid and carbon number 5～10.
4. refrigerator oil for refrigerant as claimed in claim 3, is characterized in that, comprises at least a kind in 75～95 quality % monoesters and 5～25 quality % polyol esters.
5. refrigerator oil as claimed in claim 4, is characterized in that, the kinematic viscosity in the time of 40 ℃ is 2～4mm
2/ s, flash-point is more than 130 ℃, and acid number is below 0.1mgKOH/g, and the volume specific resistance in the time of 25 ℃ is more than 10G Ω m.
6. refrigerator oil for refrigerant as claimed in claim 3, is characterized in that, comprises at least a kind in 25～40 quality % monoesters and 60～75 quality % polyol esters.
7. refrigerator oil as claimed in claim 6, is characterized in that, the kinematic viscosity in the time of 40 ℃ is 4～7mm
2/ s, flash-point is more than 130 ℃, and acid number is below 0.1mgKOH/g, and the volume specific resistance in the time of 25 ℃ is more than 10G Ω m.
8. the refrigerator oil as described in any one in claim 4～7, is characterized in that, described monoesters is the ester of n-Octanol and 2 ethyl hexanoic acid.
9. the refrigerator oil as described in any one in claim 4～7, is characterized in that, described polyol ester is neopentyl glycol two-2-ethylhexanoate or tetramethylolmethane four-2-ethylhexanoate.
10. refrigerator oil as claimed in claim 8, is characterized in that, described polyol ester is neopentyl glycol two-2-ethylhexanoate or tetramethylolmethane four-2-ethylhexanoate.
11. refrigerator oils as claimed in claim 10, is characterized in that, are added with 0.01～1 quality % by having the compound of oxirane ring or the acid scavenger that carbodiimide compound forms.
12. refrigerator oils as claimed in claim 10, is characterized in that, are added with the metal passivator that 1～100 quality ppm has benzotriazole structure.
13. refrigerator oils as claimed in claim 10, is characterized in that, are added with the oiliness improver in 0.01～1 quality % molecule with 2 above hydroxyls.
14. refrigerator oils as claimed in claim 10, is characterized in that, be added with 1～100 quality ppm be selected from silicone oil, end with polyalkylene glycol or ester modified and silicone oil or the defoamer of fluorinated silicone oil at least a kind.
15. 1 kinds of used for refrigerator working fluids, is characterized in that, contain the refrigerator oil described in any one in claim 4～7,10～14 and are selected from least a kind of hydro carbons cooling agent of ethane, propane, butane or Trimethylmethane.
16. 1 kinds of used for refrigerator working fluids, is characterized in that, contain refrigerator oil claimed in claim 8 and at least a kind of hydro carbons cooling agent that is selected from ethane, propane, butane or Trimethylmethane.
17. 1 kinds of used for refrigerator working fluids, is characterized in that, contain refrigerator oil claimed in claim 9 and at least a kind of hydro carbons cooling agent that is selected from ethane, propane, butane or Trimethylmethane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410045869.8A CN103789070B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
| CN201410347636.3A CN104119998B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
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| JP2008-080885 | 2008-03-26 | ||
| JP2008080885 | 2008-03-26 | ||
| JP2008080885A JP5231060B2 (en) | 2008-03-26 | 2008-03-26 | Refrigerating machine oil for refrigerant |
| JP2008234963 | 2008-09-12 | ||
| JP2008-234963 | 2008-09-12 | ||
| JP2008234962 | 2008-09-12 | ||
| JP2008-234962 | 2008-09-12 | ||
| JP2008234963A JP5248960B2 (en) | 2008-09-12 | 2008-09-12 | Refrigerator oil, working fluid for refrigerator, and refrigerator |
| JP2008234962A JP5248959B2 (en) | 2008-09-12 | 2008-09-12 | Refrigerator oil, working fluid for refrigerator, and refrigerator |
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| CN201410347636.3A Division CN104119998B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
| CN201410045869.8A Division CN103789070B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
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| JP2011106787A (en) * | 2009-11-20 | 2011-06-02 | Hitachi Appliances Inc | Refrigerant compressor and refrigerating cycle |
| JP5667362B2 (en) * | 2010-01-29 | 2015-02-12 | 日立アプライアンス株式会社 | Reciprocating compressor and refrigerator using the same |
| JP5525877B2 (en) * | 2010-03-17 | 2014-06-18 | Ｊｘ日鉱日石エネルギー株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| EP2554639A4 (en) * | 2010-03-31 | 2013-11-20 | Nippon Steel & Sumikin Chem Co | Lubricating oil composition |
| JP6195429B2 (en) * | 2012-03-29 | 2017-09-13 | Ｊｘｔｇエネルギー株式会社 | Working fluid composition for refrigerator and refrigerator oil |
| JP6384649B2 (en) * | 2012-12-19 | 2018-09-05 | 協同油脂株式会社 | Lubricating base oil |
| CN103509638A (en) * | 2013-08-01 | 2014-01-15 | 广东美芝制冷设备有限公司 | Refrigerating machine oil composition, and compressor and refrigeration equipment using the composition |
| CN105255560A (en) * | 2015-10-16 | 2016-01-20 | 中国石油化工股份有限公司 | Lubricating oil |
| EP3406693B1 (en) * | 2016-01-20 | 2020-12-23 | NOF Corporation | Freezer oil for r32 refrigerant and composition comprising same |
| TWI746720B (en) * | 2016-12-05 | 2021-11-21 | 日商日油股份有限公司 | Refrigerating machine oil composition and working fluid composition for refrigerator containing the same |
| EP3617503A1 (en) * | 2017-04-28 | 2020-03-04 | Panasonic Appliances Refrigeration Devices Singapore | Hermetically sealed refrigerant compressor and refrigeration device using same |
| KR102500507B1 (en) | 2018-02-07 | 2023-02-16 | 에네오스 가부시키가이샤 | Compositions of refrigeration oils and working fluids for refrigeration machines |
| KR102516452B1 (en) * | 2018-02-07 | 2023-03-31 | 에네오스 가부시키가이샤 | Compositions of refrigeration oils and working fluids for refrigeration machines |
| JP7198589B2 (en) * | 2018-03-13 | 2023-01-04 | Ｅｎｅｏｓ株式会社 | Refrigerator, use of refrigerating machine oil, method for suppressing oligomer elution, refrigerating machine oil, working fluid composition for refrigerating machine, and method for producing refrigerating machine oil |
| JP7016733B2 (en) * | 2018-03-13 | 2022-02-07 | 出光興産株式会社 | Lubricating oil composition, manufacturing method of lubricating oil composition and continuously variable transmission |
| JP7421287B2 (en) * | 2019-08-23 | 2024-01-24 | Ｅｎｅｏｓ株式会社 | Refrigerating machine oil, working fluid composition for refrigerating machines, and refrigerating machines |
| CN115353921B (en) * | 2022-09-16 | 2023-05-12 | 珠海格力电器股份有限公司 | Antiwear agent for refrigerator oil, and working fluid composition |
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