CN103733003B - Cooling air conditioner compressor and refrigerating air conditioning device - Google Patents
Cooling air conditioner compressor and refrigerating air conditioning device Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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- C09K2205/24—Only one single fluoro component present
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
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- C10N2020/101—Containing Hydrofluorocarbons
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Abstract
The invention provides the wearability improving and use difluoromethane (HFC32) as the cooling air conditioner compressor of cold-producing medium, improve long-term reliability, realize the high efficiency of the refrigeration air-conditioner using this compressor simultaneously.The invention provides a kind of cooling air conditioner compressor, it possesses the refrigerant compression portion with sliding part, is sealed with the difluoromethane as cold-producing medium and refrigerator oil, and wherein, described refrigerator oil is 40 ~ 100mm the kinematic viscosity of 40 DEG C
2/ s, described refrigerator oil is cyclic ketal compound or cyclic acetal compounds, and the low temperature side critical solution temperature of cold-producing medium and refrigerator oil is less than-10 DEG C.
Description
Technical field
The present invention relates to the cooling air conditioner compressor and refrigerating air conditioning device that adopt heat pump cycle.
Background technology
In refrigeration air-conditioner field; in order to environment of preserving our planet, the CFC(CFC just always used in the cold-producing medium or insulation material of active research ozone-layer depleting substance) or HCFC(HCFC) substitute and as the HFC(hydrofluoroalkane used in the high efficiency of global warming countermeasure and cold-producing medium always) substitute.
As the substituting of CFC or HCFC of the material damaged the ozone layer, not damage the ozone layer, toxicity and combustibility is low and can guarantee that efficiency is for the starting point, carry out selection and the equipment development of cold-producing medium and insulation material.Its result, in the insulation material of refrigerator, as blowing agent, according to HCFC141b, pentamethylene order replace CFC11, at present to vacuum thermal insulating material and use transition.
As cold-producing medium, in refrigerator and air conditioning for automobiles, CFC12 is replaced according to the order of HFC134a [GWP(global warming potential)=1430], in indoor air conditioner and combined type air conditioner, replace HCFC22 with R410A [HFC32/HFC125(50/50 % by weight) mixture: GWP=2088].
But, within 1997, in climatic fluctuation framework treaty the 3rd Meeting of States Parties (COP3) of Kyoto, Japan, HFC discharge capacity (is scaled CO as greenhouse effect gas
2) limit, therefore, promote the reduction of HFC.
Therefore, in household electric refrigerator, the enclosed volume of cold-producing medium is few, and judgement can use combustible refrigerant, with flammable R600a(iso-butane: GWP=3 in manufacture) replace HFC134a.In addition, surging due to public opinion, at present, is also being conceived to HFC134a used for automobile air conditioning and indoor air conditioner and combined type air conditioner R410A.In addition, in commercial refrigerator, the enclosed volume of cold-producing medium is many, from risk during inclosure combustible refrigerant, still uses HFC134a at present.
In reality, the household electrical appliances absorption method (particular home electrical appliance commercialization method again) that calendar year 2001 implements and the automobile absorption method (law about the renewable resources etc. of abandoned car) implemented for 2003 make the recovery of equipment become voluntary, reclaim and process the HFC etc. used as cold-producing medium, therefore, decrease HFC etc. and be directly discharged into discharge capacity in air.But, EU(European Union) and in 2006 instruction (Directive, 2006/40/EC), from January, 2011 listing, the agent of auto Not Permitted air-conditioning refrigeration uses the cold-producing medium of GWP > 150.Affect by this, air conditioning for automobiles industry has made various reaction, worries that in indoor air conditioner, also early party restriction uses R410A.According to above-mentioned EU instruction, within 2011, also likely make the adjustment listed in by fixed air-conditioning in limited field, just replace the research of cold-producing medium in acceleration.
As such substituted type cold-producing medium, from having the thermal physical characteristic equal with HFC134a, the reasons such as low GWP, hypotoxicity, low combustible are considered, candidate have 2,3,3,3-tetrafluoeopropene (HFO1234yf(HF hydrocarbon) (GWP=4), 1, the independent cold-producing medium of 3,3,3-tetrafluoeopropene (HFO1234ze) (GWP=10) or difluoromethane (HFC32) or the cold-producing medium of their mixing.As the cold-producing medium mixed with 2,3,3,3-tetrafluoeopropene, be mainly difluoromethane (HFC32).
In addition, according to the GWP that low combustible allows, also can consider to mix HFC134a and HFC125.
As other cold-producing medium, the hydrofluoroalkane of the hydrocarbon such as propane, propylene and the low GWP such as fluoroethane (HFC161), Difluoroethane (HFC152a) can be enumerated.In the cold-producing medium of these candidates, consider the change (exploitation) etc. of device efficiency decline that combustibility, cooling and warming ability, non-azeotropic refrigerant thermograde cause, ease for operation, cold-producing medium cost and the equipment based on described physical properties, most preferably difluoromethane (HFC32), the task of top priority is indoor air conditioner, the combined type air conditioner of this cold-producing medium of application.
As difluoromethane cold-producing medium refrigerator oil, patent document 1 and patent document 2 disclose polyalcohol ester oil difluoromethane being demonstrated to intermiscibility.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-235960 publication
Patent document 2: Japanese Unexamined Patent Publication 2002-129178 publication
Summary of the invention
The problem that invention will solve
In combined type air conditioner and multi-connected air conditioner, the pipe arrangement forming circulation is long, and the enclosed volume of the cold-producing medium of every platform air-conditioning is many, therefore, is difficult to use high flammable cold-producing medium.In addition, because pipe arrangement is long, therefore, need to use the refrigerator oil good with the intermiscibility of cold-producing medium.
In addition, refrigerator oil is used for sealed electrical compressor, play its sliding part lubricated, seal, the effect of cooling etc.The most important characteristic of cooling air conditioner refrigerator oil is the intermiscibility with cold-producing medium, if the interior two separate that liquid refrigerant and refrigerator oil occur of the compressor being configured at off-premises station, the liquid refrigerant be then separated supplies to each sliding part, may cause insufficient lubrication.In addition, in compressor operation, due to mechanism, refrigerator oil becomes vaporific, discharges to circulation side, and when intermiscibility difference, refrigerator oil is trapped in the low-temp. portion of circulation, and the recirculating oil quantity to compressor reduces.Particularly, in combined type air conditioner and multi-connected air conditioner, the pipe arrangement forming circulation is long, therefore needs to use the refrigerator oil good with the intermiscibility of cold-producing medium.
In patent document 1,2, as refrigerator oil, propose polyalcohol ester oil difluoromethane being demonstrated to intermiscibility, but in order to ensure long-term reliability and the oil return characteristic of cooling air conditioner compressor, still abundant not with the intermiscibility of difluoromethane, require to use the better refrigerator oil of intermiscibility.
Like this, because the intermiscibility of existing refrigerator oil and difluoromethane is insufficient, may insufficient lubrication be caused, particularly not be suitable for combined type air conditioner and the multi-connected air conditioner of the pipe arrangement length forming circulation.
The object of the invention is to, improve the wearability using difluoromethane (HFC32) as the cooling air conditioner compressor of cold-producing medium, improve long-term reliability, realize the high efficiency of the refrigeration air-conditioner using this compressor simultaneously.
Solve the means of problem
The present invention is a kind of cooling air conditioner compressor, and it possesses the refrigerant compression portion with sliding part, is sealed with the difluoromethane as cold-producing medium and refrigerator oil, it is characterized in that,
The kinematic viscosity that described refrigerator oil contains 40 DEG C is 40 ~ 100mm
2/ s(second), the compound that represented by following chemical formula (1) (in formula, R
1~ R
2represent the alkyl of hydrogen or carbon number 1 ~ 3) based on oil.
[changing 1]
The present invention is a kind of cooling air conditioner compressor, and it possesses the refrigerant compression portion with sliding part, is sealed with the difluoromethane as cold-producing medium and refrigerator oil, it is characterized in that,
Described refrigerator oil contains: the kinematic viscosity of 40 DEG C represented by following chemical formula (1) is 40 ~ 100mm
2the compound of/s (in formula, R
1~ R
2represent the alkyl of hydrogen or carbon number 1 ~ 3) base oil that forms and represented by following chemical formula (2) additional polyols ester oil (in formula, R
3represent the alkyl of carbon number 7 ~ 9), described additional polyols ester oil (that is, the polyalcohol ester oil added) consist of 1 ~ 10 % by weight.
[changing 2]
[changing 3]
In addition, in cooling air conditioner compressor as above, it is characterized in that, the low temperature side critical solution temperature of described cold-producing medium and refrigerator oil is less than-10 DEG C.
The present invention is a kind of cooling air conditioner compressor, and it possesses the refrigerant compression portion with sliding part, is sealed with the difluoromethane as cold-producing medium and refrigerator oil, it is characterized in that, described refrigerator oil is 40 ~ 100mm the kinematic viscosity of 40 DEG C
2/ s, described refrigerator oil is cyclic ketal compound or cyclic acetal compounds, and the low temperature side critical solution temperature of cold-producing medium and refrigerator oil is less than-10 DEG C.
Invention effect
According to the present invention, can obtain guaranteeing using difluoromethane as the long-term reliability of the cooling air conditioner compressor of cold-producing medium and oil return characteristic and the refrigerating air conditioning device considering environment.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram of the formation representing indoor air conditioner.
Fig. 2 is the profile representing indoor air conditioner vortex hermetic type compressor.
Detailed description of the invention
Below, the cooling air conditioner compressor of an embodiment of the present invention is described and uses the refrigerating air conditioning device of this cooling air conditioner compressor.
Above-mentioned cooling air conditioner compressor possesses the refrigerant compression portion with sliding part, is sealed with the difluoromethane as cold-producing medium and refrigerator oil.At this, refrigerator oil is 40 ~ 100mm the kinematic viscosity of 40 DEG C
2/ s, the low temperature side critical solution temperature of cold-producing medium and refrigerator oil is less than-10 DEG C.Be explained, in the evaporimeter of use in refrigeration system GM Refrigerator Working, require that cryogenic temperature is less than-10 DEG C.
In above-mentioned cooling air conditioner compressor, refrigerator oil is cyclic ketal compound or cyclic acetal compounds.
In above-mentioned cooling air conditioner compressor, refrigerator oil contain be selected from following chemical formula (1) and represent compound (in formula, R
1~ R
2represent the alkyl of hydrogen or carbon number 1 ~ 3) at least one based on oil.
[changing 4]
Above-mentioned refrigerating air conditioning device uses above-mentioned cooling air conditioner compressor.Above-mentioned cooling air conditioner compressor is the vortex or the rotary closed type compressor that are built-in with engine, and refrigerator oil is 40 ~ 100mm the kinematic viscosity of 40 DEG C
2/ below s.
Below, embodiment is used to be described in detail.
Embodiment discloses the compressor using difluoromethane and the refrigerating air conditioning device using this compressor.
The cold-producing medium of embodiment is difluoromethane, and refrigerator oil is cyclic ketal compound or cyclic acetal compounds, and they are obtained by the condensation reaction of polyalcohol and ketone or aldehyde.As the polyalcohol of raw material and ketone or aldehyde preferably by the kinematic viscosity obtained as product, flash-point, boiling point, purity, the decision such as intermiscibility, electrical insulating property with cold-producing medium.Polyalcohol is preferably 4 ~ 8 yuan, and carbon number is about 4 ~ 10.Specifically antierythrite can be enumerated, diglycerol, arabinose, ribose, D-sorbite, mannitol, galactitol, iditol, talitol, allitol, 4, 7-dioxadecane-1, 2, 9, 10-tetrol, 5-methyl-4, 7-dioxadecane-1, 2, 9, 10-tetrol, 4, 7, 10-trioxatridecane-1, 2, 12, 13-tetrol, 1, 6-dimethoxy hexane-2, 3, 4, 5-tetrol, 3, 4-diethoxy hexane-1, 2, 5, the polyalcohols such as 6-tetrol, or pentaerythrite, two trimethylolethane, double trimethylolpropane, dipentaerythritol, tripentaerythritol, 2, 9-diethyl-2, 9-dihydroxymethyl-4, 7-dioxadecane-1, 10-glycol, 2, 12-diethyl-2, 12-dihydroxymethyl-5, 8-dimethyl-4, 7, 10-trioxatridecane-1, the hindered alcohols such as 13-glycol, preferred radical of saturated aliphatic alcohol.
The carbon number of ketone or aldehyde is 2 ~ 6, specifically can enumerate: acetone, MEK, methyl propyl ketone, methyl isopropyl Ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), acetaldehyde, propionic aldehyde, butyraldehyde, isobutylaldehyde, 2 methyl butyraldehyde etc.
Then, additional polyols ester oil be following chemical formula (2) represent compound (in formula, R
3represent the alkyl of carbon number 7 ~ 9), be subject to resistance type preferably by the good thermal stability making the condensation reaction of polyalcohol and unary fatty acid obtain.
[changing 5]
The preferred dipentaerythritol of polyalcohol as raw material.In dipentaerythritol, as impurity, containing a large amount of pentaerythrite or tripentaerythritol.
In addition, the unary fatty acid as raw material has 2 ethyl hexanoic acid, 3,5,5-tri-methyl hexanoic acids etc., and they can be used alone or mix two or more use.
As additional polyols ester oil, can be compound polyalcohol ester oil (compound ester oil), it be by the ester compounds of polyalcohol, binary of fatty acids and unary fatty acid bonding.
At this, as the polyalcohol preference of raw material as neopentyl glycol, trimethylolpropane and pentaerythrite.In addition, unary fatty acid as raw material has positive valeric acid, n-caproic acid, positive enanthic acid, caprylic acid, 2-Methyl Butyric Acid, 2 methyl valeric acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, isooctyl acid, 3,5,5-tri-methyl hexanoic acids etc., they can be used alone or mix two or more use.In addition, the binary of fatty acids as raw material has malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid etc., and they can be used alone or mix two or more use.
Viscosity grade for the aircondition of embodiment and the refrigerator oil of refrigeration machine is different because of the kind of compressor, and in scroll compressor, preferably the kinematic viscosity of 40 DEG C is 40 ~ 100mm
2the scope of/s.In addition, in rotary compressor, preferably the kinematic viscosity of 40 DEG C is 40 ~ 70mm
2the scope of/s.Be explained, when the viscosity of 40 DEG C are 40mm
2during/below s, oil film formative and sealing are deteriorated, when viscosity is greater than 100mm
2during/s, the mechanical loss caused by viscous drag, frictional resistance etc. increases, and compressor resistance reduces.Therefore, as long as the kinematic viscosity of 40 DEG C is at 40 ~ 100mm
2refrigerator oil within the scope of/s, just can meet above-mentioned each condition.
The heat-resisting rank of electric insulation is electrically learned electrical specification by the heat-resisting rank of electric insulation and Evaluation of Heat Tolerance JEC-6147(and is investigated standard specification) regulation, the insulating materials that refrigerating and air-conditioning compressor adopts also is selected according to the heat-resisting kind of above-mentioned specification.But, when refrigeration air-conditioner organic insulation, owing to using in the such particular surroundings of cold-producing medium atmosphere, therefore need to consider to suppress except by the distortion also caused by pressure except temperature and sex change, in addition, due to cold-producing medium or the such polar compound of refrigerator oil also will be contacted, therefore, also solvent resistance must be considered, resistance to extractability, heat/chemical/mechanical stability, [be full of cracks is (after giving stress to film for resistance to cold-producing medium, the fine snake abdomen shape crackle produced when impregnated in cold-producing medium), blister (bubble of the film that the cold-producing medium Yin Wendu that tunicle absorbs rises and causes)] etc.
Particularly the adiabatic exponent of HFC32 is little, and therefore, the refrigerant temperature of discharge is high.Therefore, the insulating materials using high heat-resisting rank (E type, more than 120 DEG C) is needed.
The insulating materials used at most in compressor is PET(PETG).As purposes, use membrane material with the coil insulation of the iron core of winding engine, the lashing wire of coil, the clad material of engine lead-in wire use fibrous PET.As other dielectric film, can enumerate: PPS(polyphenylene sulfide), PEN(PEN), PEEK(polyethers ether copper), PI(polyimides), PA(polyamide) etc.In addition, the major insulation clad material of coil uses THEIC modified poly ester, polyamide, polyamidoimide, polyesterimide, imide etc., preferably uses the dual coated copper cash of the bilayer coating implementing polyesterimide-amide imide.
In the present invention, lubricity improver (also containing EP agents such as tricresyl phosphates), antioxidant, sour agent for capturing, defoamer, matal deactivator etc. can also be added in above-mentioned refrigerator oil.Particularly there is deterioration because of hydrolysis down because polyalcohol ester oil coexists at moisture, therefore must coordinate antioxidant and sour agent for capturing.
As antioxidant, preferred phenolic DBPC(2,6-BHT).
As sour agent for capturing, be generally used as aliphatic epoxy based compound or the carbodiimide based compound of the compound with epoxide ring.Reactivity particularly due to carbodiimide based compound and aliphatic acid is high, catches the hydrogen ion dissociated from aliphatic acid, therefore, suppresses the effect of the hydrolysis of polyalcohol ester oil very large.As carbodiimide based compound, two (2,6-isopropyl phenyl) carbodiimide can be enumerated.The use level of acid agent for capturing is preferably 0.05 ~ 1.0 % by weight relative to refrigerator oil meter.In addition, due to wearing no resistance of cyclic ketal compound or cyclic acetal compounds, therefore, as lubricity improver, preferably coordinating with tricresyl phosphate is the phosphotriester etc. of representative.
(embodiment 1 and comparative example 1 ~ 8)
(with the intermiscibility evaluation of cold-producing medium)
The cold-producing medium enclosed in cooling air conditioner compressor and the intermiscibility of refrigerator oil described above, from kind of refrigeration cycle to the aspect guaranteeing compressor reliability to the oil return (guaranteeing the oil mass of compressor inside) of compressor or the maintenance etc. of heat exchanger effectiveness, it is one of key property.
The intermiscibility evaluation of difluoromethane and refrigerator oil measures according to JIS K 2211.
The mixture that the oil (refrigerator oil) of mixing any amount and cold-producing medium are made is sealing into withstand voltage glass container, observes the content under the state changing temperature.If content gonorrhoea, be then judged to be two separate, if transparent, be then judged to dissolve.
In general, if the temperature of said mixture is enough high, then can not there is two separate, but dissolve, but, if reduce the temperature of this mixture gradually, then there is two separate.In this intermiscibility carried out is evaluated, the temperature of mixture is reduced gradually from 20 DEG C and measures.Therefore, the data when temperature (solution temperature) that failed call dissolves is more than 20 DEG C.The oil dissolved more than 20 DEG C is not suitable as the oil for cooling air conditioner compressor.
In intermiscibility is evaluated, with the concentration of the oil mixed in cold-producing medium (oil concentration) for transverse axis, take solution temperature as the longitudinal axis, make curve map.This curve map is generally expressed as the oil concentration dependence being separated into two-layer temperature, for having the curve of maximum.This maximum is defined as low temperature side critical solution temperature.
The refrigerator oil used is as described below.At this, the viscosity of 40 DEG C refers to the kinematic viscosity of the refrigerator oil at 40 DEG C.
(A) the cyclic ketal compound obtained by 1mol D-sorbite and 3mol MEK: the viscosity 63.1mm of 40 DEG C
2/ s
(B) by resistance type polyol ester oil (H-POE) (2 ethyl hexanoic acid/3 of pentaerythrite system, the fatty acid mixed ester oil of 5,5-tri-methyl hexanoic acid): the viscosity 64.9mm of 40 DEG C
2/ s
(C) by resistance type polyol ester oil (H-POE) (the aliphatic acid ester oils of 3,5,5-tri-methyl hexanoic acids of trimethylolpropane system): the viscosity 51.6mm of 40 DEG C
2/ s
(D) polyethylene ether oil (PVE) (alkoxy vinyl based polyalcohol, alkoxyl is the copolymer ether oil of ethyoxyl and isobutoxy): the viscosity 64.9mm of 40 DEG C
2/ s
(E) polyethylene ether oil (PVE) (alkoxy vinyl based polyalcohol, alkoxyl is the ether oil of ethyoxyl): the viscosity 67.8mm of 40 DEG C
2/ s
(F) naphthene series mineral oil: the viscosity 54.1mm of 40 DEG C
2/ s
(G) by resistance type polyol ester oil (H-POE) (the aliphatic acid ester oil of the 2 ethyl hexanoic acid of neopentyl glycol system): the viscosity 7.5mm of 40 DEG C
2/ s
Table 1 represents the intermiscibility evaluation result of difluoromethane (HFC32) as cold-producing medium and refrigerator oil.In this table, in the refrigerating air conditioning device using existing cold-producing medium R410A, the intermiscibility evaluation result of the main refrigerator oil used is as shown in comparative example 7 and 8.
[table 1]
From this table, there is very big-difference as the HFC32 of cold-producing medium and the intermiscibility degree (i.e. low temperature side critical solution temperature) of refrigerator oil according to the kind of refrigerator oil.The refrigerator oil mixed with HFC32 can be selected by this table.
In the combination of the cold-producing medium shown in embodiment 1 and refrigerator oil, low temperature side critical solution temperature is less than-10 DEG C.
Use refrigerator oil (B), (D), evaluate the intermiscibility with HFC32, result is as shown in comparative example 1 and 3, and when low temperature side critical solution temperature is more than+20 DEG C, intermiscibility is deteriorated.
In addition, as shown in comparative example 2, even if the kinematic viscosity changing polyalcohol ester oil can not improve intermiscibility.
As shown in comparative example 6, also have the oil good with the intermiscibility of HFC32, but kinematic viscosity is 40mm
2/ below s, is difficult to be applied to aircondition.
And then comparative example 5 represents the evaluation result of the intermiscibility of different types of oil, low temperature side critical solution temperature is more than+20 DEG C, and therefore, intermiscibility is poor, is difficult to use.
In contrast to this, in embodiment 1, good with the intermiscibility of HFC32, and low temperature side critical solution temperature is less than-10 DEG C, therefore, can be applicable to refrigerating air conditioning device.
(embodiment 2 ~ 6)
(the adsorptivity evaluation to ferrous material)
Obtain the key property as refrigerator oil intermiscibility embodiment 1 compound in,
In order to obtain lubricity, by relative to above-claimed cpd coordinate 1 ~ 10 % by weight following chemical formula (2) represent additional polyols ester oil (in formula, R
3represent the alkyl of carbon number 7 ~ 9) significantly improve the reliability of cooling air conditioner compressor and device.
[changing 6]
The good thermal stability that additional polyols ester oil obtains preferably by the condensation reaction of polyalcohol and unary fatty acid by resistance type.
The preferred dipentaerythritol of polyalcohol as raw material.In dipentaerythritol, as impurity, containing a large amount of pentaerythrite or tripentaerythritol.
In addition, the unary fatty acid as raw material has 2 ethyl hexanoic acid, 3,5,5-tri-methyl hexanoic acids etc., and they can be used alone or mix two or more use.
As additional polyols ester oil, can be compound polyalcohol ester oil (compound ester oil), it be by the ester compounds of polyalcohol, binary of fatty acids and unary fatty acid bonding.
At this, as the polyalcohol preference of raw material as neopentyl glycol, trimethylolpropane and pentaerythrite.In addition, unary fatty acid as raw material has positive valeric acid, n-caproic acid, positive enanthic acid, caprylic acid, 2-Methyl Butyric Acid, 2 methyl valeric acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, isooctyl acid, 3,5,5-tri-methyl hexanoic acids etc., they can be used alone or mix two or more use.In addition, the binary of fatty acids as raw material has malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid etc., and they can be used alone or mix two or more use.
Kinematic viscosity preferably as the cyclic ketal compound of refrigerator oil host or 40 DEG C of cyclic acetal compounds is 40mm
2/ s ~ 100mm
2/ s, the kinematic viscosity of 40 DEG C of additional polyols ester oil is 180mm
2/ more than s.
Above-mentioned cooling air conditioner compressor comprises the sliding part formed by ferrous material, and the interface pressure of sliding part is more than 10MPa.
In above-mentioned cooling air conditioner compressor, attached polyalcohol ester oil is higher than refrigerator oil host more than 10 times to the adsorption capacity of ferrous material, when the poor lubricity of refrigerator oil host, the film strength of compressor sliding part reduces, cause wearing and tearing, the reliability of refrigerating air conditioning device also declines.Therefore, the adsorptivity of refrigerator oil composition to sliding part is important parameter.The position be made up of ferrous material in sliding part is many, and its surface forms iron oxide.Refrigerator oil in this description refers to the adsorption capacity of refrigerator oil to iron oxide substantially to the adsorption capacity of ferrous material.
Based on this viewpoint, in the present embodiment, the Fe of average grain diameter 1 μm is used
3o
4powder (the specific area 1.57m of (tri-iron tetroxide)
2/ g) evaluate the adsorption capacity of refrigerator oil.
By the concentration before and after the absorption of refrigerator oil composition of diluting in nuclear magnetic resonance spectroscopy (NMR) quantitative assay solvent, calculate the amount of croci absorption.Solvent uses hexane, regulates each refrigerator oil composition to be 0.3mol-ppm.After extraction 3g croci puts into 20ml screwed pipe, add the solution of 10g refrigerator oil composition, disperse 30 minutes in ultrasonic washer, the supernatant of placement after 48 hours is carried out
1h-NMR analyzes.
At this, mol-ppm refers to mole for the ppm(PPM of benchmark).That is, the PPM being denominator with the molal quantity of solution (mixture of solvent and solute), calculating for molecule with the molal quantity of solute is referred to.
As test compound, use (A), (B), (D), (F) and (H) by resistance type polyol ester oil (POE) (2 ethyl hexanoic acid/3 of dipentaerythritol system, the fatty acid mixed ester oil of 5,5-tri-methyl hexanoic acid) (the viscosity 217mm of 40 DEG C
2/ s) implement the evaluation of above-mentioned adsorptivity.As its evaluation result, measure compound to the adsorbance of croci, result is as shown in table 2.
[table 2]
It can thus be appreciated that each compound is different to the adsorbance (adsorption capacity) of croci, and polar compound more easily adsorbs ferrous material.In polar compound, the adsorbance in molecular structure with the compound (H) of a large amount of ester group is many.That is, (H) is higher more than 4.0 times than other refrigerator oil composition (A), (B), (D), (F) to the adsorption capacity of ferrous material (iron oxide).Particularly high more than 10 times than cyclic ketal compound (A) of the present invention.Think thus, refrigerator oil composition (A) easily forms lubricating film by adding (H) on compressor sliding part.
Think this is because following reason.
There is electronegative tendency in the oxygen of the carbonyl (C=O) contained in ester group.In contrast to this, generally there is hydration and form hydroxyl in iron oxide surface.Therefore, produce the gravitation produced by Coulomb force between the hydrogen existed in the hydroxyl of iron oxide surface and the oxygen of ester group, easily adsorb.
According to this result, use (H) as additional polyols ester oil of the present invention.
(embodiment 7 ~ 10 and comparative example 9 ~ 11)
(lubricity evaluation)
Evaluate the lubricity of the refrigerator oil being confirmed adsorptivity by embodiment.Use shell-type four-ball friction and wear test machine, evaluate the lubricity of refrigerator oil.Using 1/2 inch of SUJ2 steel ball as test film, in load: 280N, temperature: 120 DEG C, rotating speed: 1200/min, time: 10min condition under test, then measure friction marks footpath (3 values are average) and the coefficient of friction of fixation test sheet.As refrigerator oil host, use (A), coordinate (H) additional polyols ester oil wherein, it is evaluated.In addition, evaluate in (A) be combined with TCP(tricresyl phosphate) refrigerator oil.As comparative example 9 ~ 11, evaluate independent (A), in (A), coordinate the refrigerator oil being less than (H) of 1.0 % by weight and the refrigerator oil being greater than (H) of 10 % by weight to (A) middle cooperation.
The result evaluating the lubricity of each refrigerator oil is as shown in table 3.
[table 3]
As shown in comparative example 9, when testing separately with (A), friction marks footpath is large, and coefficient of friction is high.In contrast to this, the refrigerator oil being combined with (H) additional polyols ester oil of 1 ~ 10 % by weight shown in embodiment 7 ~ 9, compared with independent (A), inhibits friction marks footpath and coefficient of friction, obtains lubricity and improve effect.This is because: the adsorption capacity of additional polyols ester oil to ferrous material is greater than refrigerator oil host, and therefore, the surface energy of rubbing surface reduces, and obtains the effect reducing wearability and coefficient of friction.
In addition, as described in Example 10, when being combined with the TCP as common lubricant improver in (A), can significantly be suppressed friction marks footpath and coefficient of friction, and be improved the effect of lubricity.In additional polyols ester oil, known as shown in comparative example 10, when use level is few, can not get sufficient lubricity and improve effect.In addition, as shown in comparative example 11, when use level is many, can obtains lubricity and improve effect, but producing kinematic viscosity increases and the problem of intermiscibility reduction, therefore, preferred use level is less than 10 % by weight.
(embodiment 11,12 and comparative example 12 ~ 16)
(evaluation of air-conditioning real machine)
Fig. 1 represents the skeleton diagram of the cooling and warming dual-purpose type indoor air conditioner used in the present embodiment.
Indoor air conditioner 50 is made up of indoor set 51 and off-premises station 52.Indoor heat converter 5 is built-in with in indoor set 51.In addition, compressor 100, cross valve 2, outdoor heat converter 3 and expansion gear 4(bulge is built-in with in off-premises station 52).Compressor 100 possesses the refrigerant compression portion with sliding part.
When to indoor refrigeration, in compressor 100, the refrigerant gas of the HTHP of insulated compression uses as condensing unit at outdoor heat converter 3(after discharge pipe and cross valve 2) in cooled, become the liquid refrigerant of high pressure.This cold-producing medium by expansion gear 4(such as, capillary or temperature-type expansion valve etc.) expand, become only containing the Low temperature low pressure liquid of a small amount of gas, arrive indoor heat converter 5(to use as vaporising device), air obtains heat and again arrives compressor 1 through cross valve 2 with cryogenic gas state indoor.When to indoor heating, the flow direction being changed cold-producing medium by cross valve 2, in the other direction, realizes reaction.As compressor 100, use scroll compressor.
Fig. 2 represents the schematic configuration of above-mentioned scroll compressor.
Compressor 100 comprises: the fixed scroll member 6 with the scroll scroll 8 be vertically installed on end plate 7, the rotary vortex rotary part 9 with the scroll 10 of shape substantially the same with this fixed scroll member 6, support the framework 14 of rotary vortex rotary part 9, make the pressure vessel 15 of the bent axle 11 of rotary vortex rotary part 9 rotary motion, motor 17 and built-in above-mentioned part.Scroll scroll 8 is relative with scroll 10 to be engaged, and forms compression mechanical part.
When rotary vortex rotary part 9 is by bent axle 11 rotary motion, discharge chambe 12(12a, 12b etc. of being formed between fixed scroll member 6 and rotary vortex rotary part 9) in, being positioned at outermost discharge chambe 12 along with rotary motion volume reduces gradually, and the central part simultaneously to fixed scroll member 6 and rotary vortex rotary part 9 moves.Time near the central part that discharge chambe 12 arrives fixed scroll member 6 and rotary vortex rotary part 9, discharge chambe 12 is communicated with outlet 13, and the Compressed Gas of discharge chambe 12 inside is discharged to compressor 100 outside from discharge pipe 16.
In compressor 100, bent axle 11 rotates with constant speed or according to the rotary speed of the voltage by not shown converter Control, carries out compressed action.In addition, below motor 17, be provided with oil storage portion 20, the oil in oil storage portion 20 by pressure differential through being arranged at the oilhole 19 of bent axle 11, for the lubrication of the sliding part, sliding bearing 18 etc. of rotary vortex rotary part 9 and bent axle 11.
In embodiment 11,12 and comparative example 12 ~ 16, use the indoor air conditioner shown in Fig. 1, indoor set is arranged in thermostatic chamber (room temperature 35 DEG C, humidity 75%), operates 2160 hours, carry out real machine test.The iron core of engine and the insulation of coil use heat-resisting PET film (Type B, 130 DEG C), and the major insulation of coil uses the dual coated copper cash of the bilayer coating implementing polyesterimide-amide imide.
In the evaluation of indoor air conditioner, be conceived to the state of wear of scroll compressor, measure the gap recruitment that the wearing and tearing between the framework ~ axle before and after by real machine test cause.The gap recruitment demonstrated between framework ~ axle is larger, and wear extent is larger, and in general, vibration and noise increase along with gap recruitment and become large.
As cold-producing medium, use difluoromethane (HFC32).The advantage of difluoromethane is, the refrigeration air-conditioner circulation of existing R410A machine almost can directly use.In refrigeration air-conditioner circulation, the intermiscibility of cold-producing medium and refrigerator oil is the key property for guaranteeing the recirculating oil quantity to compressor, identical with cold-producing medium, and refrigerator oil also must circulate.When intermiscibility difference, the refrigerator oil of being discharged by mechanical component from compressor is not circulated, and particularly in the raw delay of fry dried food ingredients that low-temp. portion is separated, causes the oil mass in compressor to reduce, hinders the lubrication of sliding part.Therefore, preferably the temperature range inner refrigerant of operating condition in the circulating cycle and refrigerator oil dissolve.
In the present embodiment, propose, with difluoromethane, there is intermiscibility, and confirm lubricity and improve the embodiment 8 of effect and the refrigerator oil of embodiment 10.As comparative example, have rated (B) and (D) with the intermiscibility difference of difluoromethane.In addition, for being used as (B) and (D) of the R410A of existing cold-producing medium also to compare evaluation.
In this test, the state of preferred compressor is: the gap recruitment (the gap recruitment of sliding bearing) caused by the wearing and tearing between the framework ~ axle after testing is less than 10 μm; And ensure that the oily residual quantity of compressor.
Table 4 represents the result of embodiment 11,12 and comparative example 12 ~ 16.
[table 4]
In this table, as shown in comparative example 15 and 16, in existing R410A machine, the gap recruitment between the framework ~ axle of compressor is little, and fully ensure that the oily residual quantity of the refrigerator oil in compressor.But as shown in comparative example 12 and 13, situation about implementing under the combination of the intermiscibility difference with difluoromethane, the refrigerator oil residual quantity of compressor reduces, and can not guarantee sufficient oil film, and therefore, it is large that the gap between framework ~ axle increases quantitative change.Even if good but when such as can not get sufficient lubricity shown in comparative example 14 with the intermiscibility of difluoromethane, even if ensure that the refrigerator oil residual quantity of compressor, also can not get required oil film thickness, therefore, it is large that the gap between framework ~ axle increases quantitative change.
In contrast to this, the refrigerating air conditioning device shown in embodiment 11,12 significantly can reduce the gap recruitment between framework ~ axle, and can guarantee the residual quantity of the refrigerator oil of compressor, and therefore, the reliability of refrigerating air conditioning device is able to height.
From the result of above embodiment, refrigerating air conditioning device of the present invention can either suppress the wearing and tearing of compressor, fully can guarantee again the reliability of long-term insulation.
In addition confirm, in the oscillating compressor of rotary compressor, two-spool compressor, two-stage compressing rotating compressor and roller and blade integration, also can obtain identical effect.
Industrial applicability
The present invention is applicable to cooling air conditioner compressor and refrigerating air conditioning device.
Symbol description
100: compressor; 2: cross valve; 3: outdoor heat converter; 4: expansion gear; 5: indoor heat converter; 6: fixed scroll member; 7: end plate; 8: scroll scroll; 9: rotary vortex rotary part; 10: scroll; 11: bent axle; 12,12a, 12b: discharge chambe; 13: outlet; 14: framework; 15: pressure vessel; 16: discharge pipe; 17: motor; 18: sliding bearing; 19: oilhole; 20: oil storage portion; 50: indoor air conditioner; 51: indoor set; 52: off-premises station.
Claims (4)
1. cooling air conditioner compressor, possesses the refrigerant compression portion with sliding part, is sealed with the difluoromethane as cold-producing medium and refrigerator oil, it is characterized in that,
Described refrigerator oil contains: the kinematic viscosity of 40 DEG C represented by following chemical formula (1) is 40 ~ 100mm
2the base oil that the compound of/s is formed and the additional polyols ester oil represented by following chemical formula (2), described additional polyols ester oil consist of 1 ~ 10 % by weight,
In formula, R
1~ R
2represent the alkyl of hydrogen or carbon number 1 ~ 3,
In formula, R
3represent the alkyl of carbon number 7 ~ 9.
2. cooling air conditioner compressor according to claim 1, is characterized in that, described refrigerator oil is cyclic ketal compound or cyclic acetal compounds.
3. the cooling air conditioner compressor described in claim 1 or 2, is characterized in that, the low temperature side critical solution temperature of described cold-producing medium and refrigerator oil is less than-10 DEG C.
4. refrigerating air conditioning device, is characterized in that, uses the cooling air conditioner compressor described in any one of claim 1 ~ 3.
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| JP2011-217497 | 2011-09-30 | ||
| JP2011217497A JP5562920B2 (en) | 2011-09-30 | 2011-09-30 | Compressor for refrigeration and air-conditioning equipment |
| PCT/JP2012/065516 WO2013046822A1 (en) | 2011-09-30 | 2012-06-18 | Compressor for refrigeration and air conditioning, and refrigeration and air conditioning device |
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| KR (1) | KR101587205B1 (en) |
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| KR101469983B1 (en) * | 2008-04-22 | 2014-12-05 | 한라비스테온공조 주식회사 | Integral diffuser for evaporator |
| JP2014203141A (en) | 2013-04-02 | 2014-10-27 | キヤノン株式会社 | Management device, management system, control method and computer program |
| US20160084556A1 (en) * | 2013-06-06 | 2016-03-24 | Mitsubishi Electric Corporation | Refrigeration cycle apparatus and method of operating the same |
| JP2015017730A (en) * | 2013-07-10 | 2015-01-29 | 日立アプライアンス株式会社 | Air conditioner |
| JP2015140994A (en) * | 2014-01-30 | 2015-08-03 | 日立アプライアンス株式会社 | Air conditioner, and refrigerator oil |
| CN105680644B (en) * | 2014-11-20 | 2019-01-29 | 上海海立电器有限公司 | Improve the method and compressor electric motor insulation system of compressor electric motor insulation performance |
| EP3272838B1 (en) | 2015-03-19 | 2022-05-11 | Hitachi-Johnson Controls Air Conditioning, Inc. | Compressor for refrigeration and air conditioning, and refrigeration and air conditioning device |
| JP6838561B2 (en) * | 2015-12-25 | 2021-03-03 | 日油株式会社 | Ester for refrigerating machine oil |
| WO2017145278A1 (en) * | 2016-02-24 | 2017-08-31 | 三菱電機株式会社 | Refrigeration device |
| US11209023B2 (en) | 2017-02-10 | 2021-12-28 | Carnot Compression Inc. | Gas compressor with reduced energy loss |
| US11725672B2 (en) | 2017-02-10 | 2023-08-15 | Carnot Compression Inc. | Gas compressor with reduced energy loss |
| US10359055B2 (en) | 2017-02-10 | 2019-07-23 | Carnot Compression, Llc | Energy recovery-recycling turbine integrated with a capillary tube gas compressor |
| US11835067B2 (en) | 2017-02-10 | 2023-12-05 | Carnot Compression Inc. | Gas compressor with reduced energy loss |
| EP3865785B1 (en) * | 2018-10-09 | 2024-04-03 | Mitsubishi Electric Corporation | Compressor and refrigeration device provided with compressor |
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| WO1996006839A1 (en) * | 1994-08-29 | 1996-03-07 | Kao Corporation | Synthetic lubricating oil |
| CN1074452C (en) * | 1995-12-28 | 2001-11-07 | 大金工业株式会社 | Refrigerating machine oil and refrigerator using same |
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| KR20140039311A (en) | 2014-04-01 |
| WO2013046822A1 (en) | 2013-04-04 |
| JP5562920B2 (en) | 2014-07-30 |
| KR101587205B1 (en) | 2016-01-20 |
| CN103733003A (en) | 2014-04-16 |
| JP2013076533A (en) | 2013-04-25 |
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