CN101544925A - Refrigerator oil for refrigerant - Google Patents
Refrigerator oil for refrigerant Download PDFInfo
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- CN101544925A CN101544925A CN 200910132449 CN200910132449A CN101544925A CN 101544925 A CN101544925 A CN 101544925A CN 200910132449 CN200910132449 CN 200910132449 CN 200910132449 A CN200910132449 A CN 200910132449A CN 101544925 A CN101544925 A CN 101544925A
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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, R[1] represents an alkyl group with 5-9 carbons, R[2] represents an alkyl group with 8-10 carbons, R[1] and R[2] being in branched chain or direct chain, and total carbon number being 13-17.
Description
Technical field
The present invention relates to be used to well use the refrigerator oil for refrigerant of the cooling agent compression freezing cycle device of the little cooling agent of depletion of the ozone layer coefficients such as not chloride hydrogeneous freon refrigerant and hydro carbons cooling agent and global warming coefficient.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, used cooling agent compression freezing cycle device such as refrigerator for example uses the R-11 (Trichloromonofluoromethane) as Chlorofluorocarbons (CFCs) (CFC) always, R12 (Refrigerant 12) and as the R-22 (monochlorodifluoromethane) of Hydrochlorofluorocarbons (HCFC) etc. with fluorine and chlorine as the freonll-11 that constitutes element as cooling agent, but involve nearest depletion of the ozone layer problem, its production and use are restricted in the world, turn to for example methylene fluoride (R-32) at present just gradually, hydrogeneous freon refrigerant that Tetrafluoroethane (R-134 or R-134a) etc. are not chloride and ethane for example, propane, butane, little and hydro carbons cooling agent not halogen atom-containing of Trimethylmethane isothermal chamber effect etc.
As the refrigerator oil for refrigerant that is used for these cooling agent, the ester that the contriver has proposed with polyvalent alcohols such as employing polyols is the refrigerator oil for refrigerant (patent documentation 1) of base oil.By this, rudimentary hydro carbons cooling agent is used under the situation of working fluid, can obtains to prevent the effect of the generation of oligopolymer (polymer substance).But refrigerator, air-conditioning, refrigerator etc. are required further energy-conservationization 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 the 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 descends.
In addition, in the patent documentation 3,, proposed to comprise the refrigerator oil of saturated chain carboxylic acid of at least a kind of aliphatics mono alkyl ester, also disclosed the mixture of this ester and polyol esters of fatty acids as low viscosity and the good refrigerator oil of stability to hydrolysis.Yet the enormous amount of the combination of aliphatics saturated chain carboxylic acid mono alkyl ester and polyol esters of fatty acids will find that low viscosity and oilness are good, flash-point is high and security combination also good, that can also satisfy stability to hydrolysis is unusual difficulty.
Patent documentation 1: the Japanese Patent spy opens the 2007-254713 communique
Patent documentation 2: the Japanese Patent spy opens the 2007-248020 communique
Patent documentation 3: the public again table patent of Japanese Patent WO00/68345 communique
Summary of the invention
As mentioned above, use in the refrigerator of hydro carbons cooling agent of the littler not halogen atom-containing of not chloride hydrogeneous freon refrigerant or Greenhouse effect, for energy saving is improved, using the low lubricating oil of viscosity is effective as refrigerator oil, but adopting with paraffin Dormant oils or naphthenic hydrocarbon Dormant oils is under the refrigerator oil condition of so-called Dormant oils class of base material, exists flash-point to reduce and the dangerous problem that raises when handling.On the other hand, be under the situation of base oil with the ester that adopts polyvalent alcohol such as polyol, must use the few lipid acid of carbon number, this stability of structure significantly descends, the corrosion that the lipid acid that produces 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 hydro carbons cooling agent to use low viscosity and security, the refrigerator oil for refrigerant that has good stability with the littler not halogen atom-containing of not chloride hydrogeneous freon refrigerant or Greenhouse effect.
The present invention studies the back to achieve these goals and conscientiously and finds, base oil is that main component or the refrigerator oil that mixes polyol ester again are low at not chloride hydrogeneous freon refrigerant or hydro carbons cooling agent medium viscosity with specific monoesters, also have good lubricity, energy saving, and stability to hydrolysis is also high, as cooling agent compression freezing cycle device with lubricating oil, 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) a kind of refrigerator oil for refrigerant wherein, contains monoesters with following general formula (1) expression as main component, the not enough 7mm of the kinematic viscosity in the time of 40 ℃
2/ s;
In the formula, R
1The alkyl of expression carbon number 5～9, R
2The alkyl of expression 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), wherein, also contain polyol ester as (1) described refrigerator oil for refrigerant.
(3) as (2) described refrigerator oil for refrigerant, wherein, monoesters is the monoesters of the unary fatty acid of the aliphatic monobasic alcohol of carbon number 8 and carbon number 8, and polyol ester is 2 ethyl hexanoic acid and/or 3,5, in the polyol ester of the amyl-based polyol of 5-tri-methyl hexanoic acid and carbon number 5～10 at least a kind.
(4), wherein, comprise at least a kind in 75～95 quality % monoesters and 5～25 quality % polyol esters as (3) described refrigerator oil for refrigerant.
(5) as (4) described refrigerator oil, wherein, the kinematic viscosity in the time of 40 ℃ is 2～4mm
2/ s, flash-point are more than 130 ℃, and acid number is below 0.1mg KOH/g, and the volume specific resistance in the time of 25 ℃ is more than 10G Ω m.
(6), wherein, comprise at least a kind in 25～40 quality % monoesters and 60～75 quality % polyol esters as (3) described refrigerator oil for refrigerant.
(7) as (6) described refrigerator oil, wherein, the kinematic viscosity in the time of 40 ℃ is 4～7mm
2/ s, flash-point are more than 130 ℃, and acid number is below 0.1mg KOH/g, and the volume specific resistance in the time of 25 ℃ is more than 10G Ω m.
(8) as each the described refrigerator oil in (4)～(7), wherein, described monoesters is the ester of n-Octanol and 2 ethyl hexanoic acid.
(9) as each the described refrigerator oil in (4)～(7), wherein, described polyol ester is neopentyl glycol two-2-ethylhexanoate or tetramethylolmethane four-2-ethylhexanoate.
(10) as (8) described refrigerator oil, wherein, described polyol ester is neopentyl glycol two-2-ethylhexanoate or tetramethylolmethane four-2-ethylhexanoate.
(11), wherein, be added with the acid scavenger that 0.01～1 quality % is formed by compound with oxirane ring or carbodiimide compound as (10) described refrigerator oil.
(12), wherein, be added with the metal passivator that 1～100 quality ppm has the benzotriazole structure as (10) described refrigerator oil.
(13), wherein, be added with the oiliness improver that 0.01～1 quality % intramolecularly has the hydroxyl more than 2 as (10) described refrigerator oil.
(14) as (10) described refrigerator oil, wherein, be added with 1～100 quality ppm be selected from silicone oil, terminal with polyalkylene glycol or ester modified and silicone oil or the defoamer of fluorinated silicone oil at least a kind.
(15) a kind of used for refrigerator working fluid wherein, contains (4)～each described refrigerator oil in (7), (10)～(14) and be selected from a kind of hydro carbons cooling agent of ethane, propane, butane or Trimethylmethane at least.
(16) a kind of 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 kind of 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 (15) described used for refrigerator working fluid, compress this fluidic hermetic compressor, make the cooling agent condenser condensing, make cooling agent expansible expansion mechanism, the vaporizer of cooling agent evaporation is constituted, described hermetic compressor comprises the electric motor with rotor and stator, comprise polyethylene terephthalate in the described electric motor, polybutylene terephthalate, polyamidoimide lining polyester, any a kind insulating film in polyphenylene sulfide and the polyether-ether-ketone comprises in the described stator with the winding of second-order transition temperature in the lining of the enamel paint material more than 120 ℃.
(19) a kind of refrigerator, wherein, by (16) or (17) described used for refrigerator working fluid, compress this fluidic hermetic compressor, make the cooling agent condenser condensing, make cooling agent expansible expansion mechanism, the vaporizer of cooling agent evaporation is constituted, described hermetic compressor comprises the electric motor with rotor and stator, comprise polyethylene terephthalate in the described electric motor, polybutylene terephthalate, polyamidoimide lining polyester, any a kind insulating film in polyphenylene sulfide and the polyether-ether-ketone comprises in the described stator with the winding of second-order transition temperature in the lining of the enamel paint material more than 120 ℃.
(20) as (18) described refrigerator, wherein, described hermetic compressor is reciprocating type.
(21) as (19) described refrigerator, wherein, described hermetic compressor is reciprocating type.
By the present invention, can be provided for the hydro carbons cooling agent of the littler not halogen atom-containing of not chloride hydrogeneous freon refrigerant or Greenhouse effect, low viscosity and the refrigerator oil for refrigerant that has good stability.Therefore, play following effect: the greenhouseization of the earth etc. are little to the influence of environment, and low viscosity, and energy saving is good, and oilness is good, flash-point height and security might as well, can also satisfy 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, play 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 with following general formula (1) expression as main component, the not enough 7mm of the kinematic viscosity in the time of 40 ℃
2/ s;
In the general formula (1), R
1The alkyl of expression carbon number 5～9, R
2The alkyl of expression 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 use well with not chloride cooling agent and not halogen-containing cooling agent.Promptly, refrigerator oil for refrigerant of the present invention can be well with the refrigerator oil that acts on following cooling agent: for example methylene fluoride (R-32), the Tetrafluoroethane not chloride little hydrogeneous freon refrigerants of depletion of the ozone layer coefficient such as (R-134 or R-134a), particularly the hydro carbons cooling agent that for example not halogen-containing depletion of the ozone layer coefficient such as ethane (R170), propane (R290), butane (R600), Trimethylmethane (R600a) and global warming coefficient are all little etc.
Among the present invention, the monoesters that is used as the main component of refrigerator oil for refrigerant is represented with general formula (1).
In the formula, R
1The alkyl of expression carbon number 5～9.Alkyl can have unsaturated link(age), but from the angle of chemical stability, better is saturated hydrocarbyl.In addition, R
1Can be the alkyl of form of alkyl and aromatic nucleus or naphthalene nucleus combination, but good especially be the alkyl of straight or branched.R
2The alkyl of expression carbon number 8～10.R
2With R
1Equally, can have unsaturated link(age), also can be the alkyl of the form of alkyl and aromatic nucleus or naphthalene nucleus combination, and good especially is the alkyl of straight or branched.R
2Carbon number be lower than under 8 the situation, the viscosity that produces the ester of gained is crossed low and oilness deficiency and flash-point descend and problems such as danger increase on handling, is higher than under 10 the situation, can't 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 that produces the ester of gained is crossed low and oilness deficiency and flash-point descend and problems such as danger increase on handling, so be unfavorable.In addition, if the summation of carbon number surpasses 17, then viscosity raises, and produces the insufficient problem of energy-saving effect in the compressor.In addition, R
1The situation of carbon number less than 5 under, carbon number is more little after the hydrolysis, the strength of acid of the unary fatty acid of generation (carboxylic acid) is strong more, causes the harm such as equipment and materials around the corrosion, so be unfavorable.
By the chemical formula of general formula (1) as can be known, the such monoesters that uses among the present invention can be by synthesizing the unary fatty acid (carboxylic acid) of carbon number 6～10 and the monohydroxy-alcohol esterification of carbon number 8～10.Do not limit the manufacture method of monoesters among the present invention; as the compound that is equivalent to unary fatty acid; can adopt the acyl chlorides of unary fatty acid and carboxylic acid anhydride to wait synthetic, can also utilize the alkoxyl group that alkoxyl group or acyl group with monoesters be exchanged for other or the transesterification reaction of acyl group to synthesize.
Among the present invention, synthetic unary fatty acid as the monoesters that can be used for general formula (1) well, can exemplify caproic acid, enanthic acid, n-caprylic acid, isocaprylic acid, 2 ethyl hexanoic acid, 1-methyl enanthic acid, 2-methyl enanthic acid, 2-Valproic acid, dimethyl cyclohexylenedinitrilotetraacetic acid, n-nonanoic acid, 3,5,5-tri-methyl hexanoic acid, capric acid, wherein good especially is the sad or 2 ethyl hexanoic acid of carbon number 8.
Among the present invention, synthetic monohydroxy-alcohol as the monoesters that can be used for general formula (1) well, can exemplify n-Octanol, isooctyl alcohol, 1-isoocanol, 2-isoocanol, 2-propyl group amylalcohol, dimethyl cyclohexanol, 2-Ethylhexyl Alcohol, decyl alcohol, wherein better be the octanol or the 2-Ethylhexyl Alcohol of carbon number 8.
Also have, can realize low viscosity by the monoesters that the monohydroxy-alcohol of the unary fatty acid of carbon number 8 and carbon number 8 obtains, can improve flash-point, hydrolysis stability is good especially.
The monoesters that uses among the present invention constitutes the main component of refrigerator oil for refrigerant, thus same with refrigerator oil for refrigerant, the not enough 7mm of the kinematic viscosity in the time of preferred 40 ℃
2/ s better is not enough 6mm
2/ s is more preferably 2～5mm
2/ s surpasses 7mm
2Under the situation of/s, can't obtain energy-saving effect.Kinematic viscosity and flash-point not necessarily are directly proportional, if but kinematic viscosity is low usually, and then flash-point is low.Refrigerator oil uses in enclosed system mostly, and flash-point not too becomes problem, but the angle of the security the processing before guaranteeing to be filled in refrigerator, flash-point better is arranged on more than 120 ℃, is more preferably more than 130 ℃, and good especially is 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 in the above-mentioned monoesters of specified amount, mixing this polyol ester of specified amount, can transfer to required kinematic viscosity, and can improve stability to hydrolysis.
Amyl-based polyol is meant the above alcohol of binary with neopentane structure, uses the amyl-based polyol of carbon number 5～10 among the present invention.Carbon number surpasses 10 amyl-based polyol and is difficult for adjusting kinematic viscosity, and worsens with the consistency of cooling agent.As this amyl-based polyol, can use neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, especially preferably use neopentyl glycol and tetramethylolmethane.
The ester that uses among the present invention can by above-mentioned specific alcohol or polyvalent alcohol and specific lipid acid based on the esterification of dehydration reaction or via obtaining as the general esterification of the acid anhydrides of derivative of fatty acid, acyl chlorides etc. or the transesterification reaction of each derivative.
Also have, when modulating the refrigerator oil that comprises monoesters and polyol ester of the present invention, can be earlier with monoesters and polyol ester synthetic respectively after, with both with the regulation mixed, also can be earlier with 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, synthesize by aforesaid method.Also have, under this situation, polyol ester can be a kind, also can mix use more than 2 kinds.
The ester that obtains by aforesaid method is not specially limited unreacted and remaining acid and pure, but better is not remaining carboxyl as far as possible.If the remaining quantity of carboxyl is many, then generate metallic soap etc. by reaction with the inner employed metal of refrigerator, also produce precipitation and wait and do not wish the phenomenon that takes place, therefore the acid number of refrigerator oil of the present invention better is below 0.1mgKOH/g.This acid number obtains by the method for regulation among the JIS K2501 " petroleum product and lubricating oil-neutralization value test method, indicator titration method ".
Kinematic viscosity during when mixing in order to make 40 ℃ is not too high, the not enough 10mm of the kinematic viscosity the when mixing of monoesters and polyol ester better is 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 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 height, security and stability to hydrolysis, consistency are good.
Also have, for the refrigerator oil of the viscosity of making the VG3 level, the kinematic viscosity in the time of 40 ℃ better is 2～4mm
2/ s.
As another preferred proportioning, can exemplify the proportioning that comprises 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 height, security and stability to hydrolysis, consistency are good.
Also have, for the refrigerator oil of the viscosity of making the VG5 level, the kinematic viscosity in the time of 40 ℃ better is 4～7mm
2/ s.
For refrigerator oil of the present invention, in order to ensure the security on handling, better be flash-point more than 130 ℃, the angle on the safety such as anti-electrostatic, the volume specific resistance when better being 25 ℃ is more than 10G Ω m.
Kinematic viscosity in the time of 40 ℃ is measured by the method for regulation among the JIS K2283 " crude oil and petroleum product-kinematic viscosity test method and viscosity index method of calculation ", flash-point is measured by the method for regulation among the JIS K2265-4 " flash-point ask method-the 4th one: agar diffusion method is opened in the Cleveland ", volume specific resistance in the time of 25 ℃ is measured under 25 ℃ specimen temperature according to the method for regulation among the JIS C 2101 " electric insulation oil test method, the test of 24. volume specific resistances ".
If above-mentioned monoesters use n-Octanol and 2 ethyl hexanoic acid ester, be the 2 ethyl hexanoic acid n-octyl, then the viscosity adjustment of VG3 level or VG5 level becomes easily, so is preferred.
Similarly, as polyol ester, better be to use as the neopentyl glycol two-2-ethylhexanoate of the ester of 2 ethyl hexanoic acid and neopentyl glycol 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 that are used for refrigerator oil.For example, improving in order to make stability to hydrolysis, better is to add to have the compound of oxirane ring or the acid scavenger that carbodiimide compound forms in the machine oil that is formed by above-mentioned ester again.Compound with oxirane ring can exemplify the compound that contains glycidyl ether, the compound that contains the Racemic glycidol ester group, epoxidized fatty acid monoesters class, epoxidation grease, contain the compound of oxirane ring alkyl etc.Wherein, good especially be the compound that contains glycidyl ether, the compound that contains the Racemic glycidol ester group, epoxidized fatty acid monoesters class, epoxidation grease, contain the compound of oxirane ring alkyl.
The addition of this acid scavenger is that benchmark better is 0.01～1 quality % with refrigerator oil integral body, is more preferably 0.2～0.7 quality %.
As the phosphorated extreme-pressure additive, can exemplify phosphoric acid hydroxyl more than one esterified and phosphoric acid ester.Phosphoric acid ester can be three esters, diester or monoesters, but three esters preferably.Specifically, can exemplify 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 base 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, good especially be tricresyl phosphate (toluene ester) (TCP).Incorporation better is 0.1～2.0 quality %, is more preferably 0.2～1.5 quality %.
In addition, for stability to hydrolysis is improved, better be the compound that adds as metal passivator equally with benzotriazole structure.Compound with benzotriazole structure is meant the compound of representing with following general formula (2).
In the formula, R
1Expression hydrogen atom or methyl, R
2The group of the carbon number 0～20 of expression hydrogen atom or nitrogen atom and/or Sauerstoffatom.Addition is that benchmark better is 1～100 quality ppm with refrigerator oil integral body, is more preferably 10～80 quality ppm.
In addition, improving in order to make oilness, better is to add the oiliness improver that intramolecularly has the hydroxyl more than 2.Have the oiliness improver of the hydroxyl more than 2 as this intramolecularly, can exemplify glyceryl monooleate, glycerine list oleyl ether, glycerine list lauryl ether etc., good especially is glyceryl monooleate or glycerine list oleyl ether.Addition is that benchmark better is 0.01～1 quality % with refrigerator oil integral body, is more preferably 0.1～0.5 quality %.
In addition, for freezing-inhibiting machine oil bubbles in refrigeration system, better be add be selected from silicone oil, terminal with polyalkylene glycol or ester modified and silicone oil or the defoamer of fluorinated silicone oil at least a kind.Addition is that benchmark better is 1～100ppm with refrigerator oil integral body, is more preferably 10～80ppm.
Can suitably mix the additive except that above-mentioned in the refrigerator oil of the present invention as required again.As such additive, for example can also suitably mix 2 as required, 6-DI-tert-butylphenol compounds, 2,6-ditertbutylparacresol, 4,4-methylene radical-two (2, the 6-ditertbutylparacresol), p, additive such as depressant prescription under the antioxidant of phenols such as p '-dioctyl diphenylamine or amine and known purification dispersion agent, viscosity index rising agent, rust-preventive agent, sanitas, the yield point.These additives add with the condition that contains in refrigerator oil of the present invention about 1 quality ppm～2 quality % usually.Particularly the antioxidant of phenols or amine can significantly improve stability, the weather resistance of lubricant by adding about 0.01～0.5 quality %.
Refrigerator oil of the present invention can use well with not chloride cooling agent and not halogen-containing cooling agent.Promptly, refrigerator oil of the present invention can be used to use the refrigerator of following cooling agent well: for example methylene fluoride (R-32), the Tetrafluoroethane not chloride little hydrogeneous freon refrigerants of depletion of the ozone layer coefficient such as (R-134 or R-134a), particularly for example ethane (R170), propane (R290), butane (R600), Trimethylmethane not halogen-containing depletion of the ozone layer coefficient and all little hydro carbons cooling agent of global warming coefficient such as (R600a), perhaps mixed cooling medium more than their 2 kinds etc.
Refrigerator oil of the present invention is working fluid by mixing with these cooling agent, is responsible for the lubricated of freezing plant.By with refrigerator oil of the present invention and cooling agent with the mixed of 5:95～80:20, can be used as working fluid.Outside this scope, under oily few situation, have the danger that causes insufficient lubrication, under the oily too much situation, therefore inefficiency is unfavorable.
In addition, used for refrigerator working fluid of the present invention can be used as the working fluid that for example refrigerator, air-conditioning, refrigerator etc. have the cooling agent compression freezing plant of compressor, condenser, expansion mechanism and vaporizer at least, 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, adopt the crystalline plastic film or the composite membrane of the resin layer that the lining second-order transition temperature is high on the low film of second-order transition temperature etc. more than 50 ℃ of second-order transition temperatures such as polyethylene terephthalate, polybutylene terephthalate, polyamidoimide lining polyester, polyphenylene sulfide, polyether-ether-ketone for example as the insulating film of the electrical insulation system material of the motor part of these coolant compressors.
The magnetic wire that is used for motor part equally also adopts following film: the unitary film of the enamel paint lining of second-order transition temperatures such as polyester-imide, polymeric amide, polyamidoimide more than 120 ℃ for example perhaps is lower floor, is upper strata and the compound enamel paint tunicle that obtains etc. with the high film of second-order transition temperature with the low film of second-order transition temperature.
Also have, the viscosity of used for refrigerator working fluid of the present invention is low, therefore is suitable for the high shuttle hermetic compressor of stopping property.
Embodiment
Below, the present invention will be described in more detail based on embodiment and comparative example, but the present invention is not subjected to the qualification of embodiment.
In order to estimate the present invention, prepared the refrigerator oil for refrigerant (for formation testing) of embodiment and comparative example.Be used for for base oil, the additive of formation testing as follows.
Base oil
Monoesters 1～8: the monoesters shown in the 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,, obtain the refrigerator oil of embodiment and comparative example with the modulation of the ratio (quality %) shown in the top of table 2, table 3 and table 4.The refrigerator oil of table 2 expression embodiment 1～8, the refrigerator oil of table 3 expression embodiment 9～13, the refrigerator oil of table 4 expression comparative example 1～9.
Table 3
For the refrigerator oil of these embodiment and comparative example, measure its rerum natura and performances such as consistency, stability, estimate.It 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 following to be carried out.
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, open the determination of test method of cup type (COC) by the Cleveland.
Acid number:
According to JIS K 2501, measure total acid value by indicator titration method.
Consistency:
According to the appendix 3 of JIS K 2211, measure two layers of separation temperature.Also have, as cooling agent, use Trimethylmethane (R600a), propane (R290) and 1,1,2,2-Tetrafluoroethane (R-134a) is 2/8 condition mensuration than (weight) for formation testing/cooling agent.
Stability:
Implement so-called autoclave test, form and aspect, the acid number of the refrigerator oil after the test deterioration.That is, add 30g for formation testing and 10g cooling agent and as Fe, the Cu of catalyzer, the wire of Al in the stainless steel pressure vessel (autoclave) of inner capacities 100ml, sealing was placed 14 days in 175 ℃ thermostatic bath.Sample after the taking-up deterioration is confirmed color, acid number.Cooling agent uses R600a and R-134a, estimates 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, the determination test sheet produces the loading of burning when gluing.
Use the R of monoesters
1And R
2Summation to be 13～17 ME-2～6 be not only low viscosity oil with PE-3 as the embodiment 9～13 of another base oil as the embodiment 1～8 of base oil with ME-4 in the lump as base oil, and flash-point height, also good with consistency, the stability of cooling agent, oilness is good.
With ME-1 as the comparative example 1 of base oil because R
1And R
2Summation be low to moderate 11, so viscosity and flash-point are low excessively, are difficult to actual use.Also poor with the stability of cooling agent, the acid number after the test rises.
With ME-7 and ME-8 as the comparative example 2 of base oil and 3 because poor with the matching of cooling agent, particularly consistency, therefore be difficult to actual use.
With PE-1 and PE-2 poor stability as the comparative example 4,5 of base oil.In addition, be difficult to make kinematic viscosity to reach in the scope of target as the comparative example 6 of base oil PE-3.
MO-1 is also same with comparative example 6 as the comparative example 7 of base oil, and kinematic viscosity does not reach in the scope of target.With MO-2 and 3 low, poor stability as the flash-point of the comparative example 9 of base oil.
In order to estimate 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.
Be used for for base oil, the additive of formation testing as follows.
(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 (1000mPas@25 ℃) [silicone oil]
Use above-mentioned base oil and additive,, obtain the confession formation testing (refrigerator oil) of embodiment and comparative example with the modulation of the ratio (quality %) shown in the top of table 5.
Table 5
| The proportioning of base oil (quality %) | Additive formula | |
| Embodiment 14 | ME-10；85、PE-5；15 | Do not have |
| Embodiment 15 | ME-10；87、PE-5；10、PE-6；3 | Do not have |
| Embodiment 16 | ME-10；88、PE-5；10、PE-7；2 | Do not have |
| 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 | Do not have |
| Embodiment 22 | ME-10；33、PE-5；62、PE-6；5 | Do not have |
| Embodiment 23 | ME-10；35、PE-5；62、PE-7；3 | Do not have |
| 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 | Do not have |
| Comparative example 11 | ME-11；100 | Do not have |
| Comparative example 12 | PE-4；100 | Do not have |
| Comparative example 13 | PE-5；100 | Do not have |
| Comparative example 14 | ME-9；75、PE-5；25 | Do not have |
| Comparative example 15 | ME-9；75、PE-6；25 | Do not have |
| Comparative example 16 | ME-11；90、PE-5；10 | Do not have |
| 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 its rerum natura and performances such as consistency, stability, estimate.It the results are shown in table 6.
Also have, the physical property measurement except aforesaid measuring method and the test of performance evaluation are following to be carried out.
Bubble:
By the method for regulation among the JIS K2518 " petroleum product-oil whip test method(s) ", foaminess when 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,, use Trimethylmethane (R600a), and than (weight) be 2/8 condition mensuration for formation testing/cooling agent as cooling agent.
Stability to hydrolysis:
The method of regulation in the appendix 2 by JIS K2211 " with the test method (sealed tube test) of the chemical stability of cooling agent ", 7ml was 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 (the method lux is burnt sticking):
Carry out method lux (Falex) test (290rpm, room temperature) based on ASTM D3233, the determination test sheet produces the loading of burning when 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 60 ℃ of loading 100N, frequency 50Hz, amplitude 1mm, temperature, determination test is through the friction marks after 25 minutes.
Compressor test:
With adding 220ml in the compressor, use the 30g Trimethylmethane to refrigerator, carried out durable test with following condition as cooling agent for formation testing.
＜condition〉outlet pressure: 10kg/cm
2G, suction pressure: 0kg/cm
2G, compressor surface temperature (top): 100 ℃, runtime: 1000 hours
Behind the durable test, disassemble compressor, carried out the dirt of outlet valve and the wear evaluation of sliding part.
Use is as the n-Octanol of the aliphatic monobasic alcohol of carbon number 8 with 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 mixture of the ester PE-4～PE-7 of the neopentyl glycol of the neo-pentyl alcohol of carbon number 5～10 or tetramethylolmethane, and flash-point height, also good with consistency, stability to hydrolysis, the volume specific resistance of cooling agent, and oilness is good.
On the other hand, use the ester PE-4 of monoesters ME-9～ME-11 and amyl-based polyol poor separately, and the SRV friction marks of the oilness of comparative example 10～12 is also poor as the stability to hydrolysis of the comparative example 10～12 of base oil.Particularly comparative example 10, and the method lux of flash-point, volume specific resistance, oilness is burnt sticking also poor.Also have, use the viscosity height of the comparative example 13 of PE-5 separately, can't fully realize energy-conservation.In addition, even the sample of the ester of the pure and mild acid of use carbon number 6 or carbon number 10 mixes (comparative example 14～16) with the ester of amyl-based polyol, stability to hydrolysis is also poor, and the volume specific resistance of comparative example 14～15 is also low.Even using the goods of these base oils to add additive (comparative example 17～19) also can't improve.
The possibility of utilizing on the industry
By the present invention, can be provided for the hydro carbons refrigerant of the less not halogen atom-containing of not chloride hydrogeneous freon refrigerant or greenhouse effects, low viscosity and the refrigerator oil for refrigerant that has 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, be used for utilizing the refrigerator, air-conditioning, refrigerator etc. of refrigerant compression freezing cycle device well.
Claims (21)
1. a refrigerator oil for refrigerant is characterized in that, contains monoesters with following general formula (1) expression as main component, the not enough 7mm of the kinematic viscosity in the time of 40 ℃
2/ s;
In the formula, R
1The alkyl of expression carbon number 5～9, R
2The alkyl of expression 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 claimed in claim 1 is characterized in that, also contains polyol ester.
3. refrigerator oil for refrigerant as claimed in claim 2, it is characterized in that, monoesters is the monoesters of the unary fatty acid of the aliphatic monobasic alcohol of carbon number 8 and carbon number 8, polyol ester is 2 ethyl hexanoic acid and/or 3,5, in the polyol ester of the amyl-based polyol of 5-tri-methyl hexanoic acid and carbon number 5～10 at least a kind.
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 are 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 are 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. as each the described refrigerator oil in the claim 4～7, it is characterized in that described monoesters is the ester of n-Octanol and 2 ethyl hexanoic acid.
9. as each the described refrigerator oil in the claim 4～7, it 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 oil as claimed in claim 10 is characterized in that, is added with the acid scavenger that 0.01～1 quality % is formed by compound with oxirane ring or carbodiimide compound.
12. refrigerator oil as claimed in claim 10 is characterized in that, is added with the metal passivator that 1～100 quality ppm has the benzotriazole structure.
13. refrigerator oil as claimed in claim 10 is characterized in that, is added with the oiliness improver that 0.01～1 quality % intramolecularly has the hydroxyl more than 2.
14. refrigerator oil as claimed in claim 10 is characterized in that, be added with 1～100 quality ppm be selected from silicone oil, terminal 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 is characterized in that, contains each the described refrigerator oil in the claim 4～7,10～14 and is selected from least a kind of hydro carbons cooling agent of ethane, propane, butane or Trimethylmethane.
16. a used for refrigerator working fluid is characterized in that, contains described refrigerator oil of claim 8 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 is characterized in that, contains described refrigerator oil of claim 9 and at least a kind of hydro carbons cooling agent that is selected from ethane, propane, butane or Trimethylmethane.
18. refrigerator, it is characterized in that, by the described used for refrigerator working fluid of claim 15, compress described fluidic hermetic compressor, make the cooling agent condenser condensing, make cooling agent expansible expansion mechanism, the vaporizer of cooling agent evaporation is constituted, described hermetic compressor comprises the electric motor with rotor and stator, comprise polyethylene terephthalate in the described electric motor, polybutylene terephthalate, polyamidoimide lining polyester, any a kind insulating film in polyphenylene sulfide and the polyether-ether-ketone comprises in the described stator with the winding of second-order transition temperature in the lining of the enamel paint material more than 120 ℃.
19. refrigerator, it is characterized in that, by claim 16 or 17 described used for refrigerator working fluids, compress described fluidic hermetic compressor, make the cooling agent condenser condensing, make cooling agent expansible expansion mechanism, the vaporizer of cooling agent evaporation is constituted, described hermetic compressor comprises the electric motor with rotor and stator, comprise polyethylene terephthalate in the described electric motor, polybutylene terephthalate, polyamidoimide lining polyester, any a kind insulating film in polyphenylene sulfide and the polyether-ether-ketone comprises in the described stator with the winding of second-order transition temperature in the lining of the enamel paint material more than 120 ℃.
20. refrigerator as claimed in claim 18 is characterized in that, described hermetic compressor is reciprocating type.
21. refrigerator as claimed in claim 19 is characterized in that, described hermetic compressor is reciprocating type.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347636.3A CN104119998B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
| CN201410045869.8A CN103789070B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
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|---|---|---|---|
| JP2008080885A JP5231060B2 (en) | 2008-03-26 | 2008-03-26 | Refrigerating machine oil for refrigerant |
| JP2008-080885 | 2008-03-26 | ||
| JP2008080885 | 2008-03-26 | ||
| JP2008234962A JP5248959B2 (en) | 2008-09-12 | 2008-09-12 | Refrigerator oil, working fluid for refrigerator, and refrigerator |
| JP2008234963 | 2008-09-12 | ||
| JP2008-234963 | 2008-09-12 | ||
| JP2008234962 | 2008-09-12 | ||
| JP2008234963A JP5248960B2 (en) | 2008-09-12 | 2008-09-12 | Refrigerator oil, working fluid for refrigerator, and refrigerator |
| JP2008-234962 | 2008-09-12 |
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| CN201410045869.8A Division CN103789070B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
| CN201410347636.3A Division CN104119998B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5231060B2 (en) | 2013-07-10 |
| JP2009235179A (en) | 2009-10-15 |
| CN101544925B (en) | 2014-08-13 |
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