CN105331422A - High-performance refrigeration lubricating oil composition - Google Patents
High-performance refrigeration lubricating oil composition Download PDFInfo
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- CN105331422A CN105331422A CN201410390065.1A CN201410390065A CN105331422A CN 105331422 A CN105331422 A CN 105331422A CN 201410390065 A CN201410390065 A CN 201410390065A CN 105331422 A CN105331422 A CN 105331422A
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Abstract
The invention provides a refrigeration lubricating oil composition. The composition comprises polyol ester products obtained after reaction of tripentaerythritol, dipentaerythritol, pentaerythritol or a mixture of tripentaerythritol, dipentaerythritol and pentaerythritol with one or more straight-chain/branched-chain saturated/nonsaturated C4-20 aliphatic acid; or the composition comprises a mixture of polyol ester products obtained after reaction of tripentaerythritol with one or more straight-chain/branched-chain saturated/nonsaturated C4-20 aliphatic acid, polyol ester products obtained after reaction of dipentaerythritol with one or more straight-chain/branched-chain saturated/nonsaturated C4-20 aliphatic acid or polyol ester products obtained after reaction of pentaerythritol with one or more straight-chain/branched-chain saturated/nonsaturated C4-20 aliphatic acid. The polyol ester products have the following properties: intermiscible temperature of the polyol ester products and a refrigerant (such as a hydrofluorocarbon refrigerant and a hydrofluoroolefin refrigerant) is lower than -25 DEG C (with 20% of polyol esters in the refrigerant); the dynamic viscosity of the polyol ester products at a temperature of 40 DEG C is in a range of 46 to 460 cSt; and the polyol ester products show high operation viscosity in testing under related standard compressor conditions.
Description
Technical field
The present invention relates to a kind of refrigeration lubrication oil constituent, it comprises the saturated or unsaturated C by tripentaerythritol (TriPE), Dipentaerythritol (DiPE), tetramethylolmethane (PE) or its mixture and one or more straight or branched
4-20fatty acid response and the polyol ester class product (polyol-ester (POE)) that obtains, or by the saturated or unsaturated C of tripentaerythritol (TriPE) with one or more straight or branched
4-20fatty acid response and obtain polyol ester class product, by the saturated or unsaturated C of Dipentaerythritol (DiPE) with one or more straight or branched
4-20saturated or the unsaturated C of fatty acid response and the polyol ester class product that obtains or tetramethylolmethane (PE) and one or more straight or branched
4-20fatty acid response and the mixture of the polyol ester class product obtained, this polyol ester class product (POE) has following character: with the temperature of dissolving each other of refrigerant (such as hydrofluorocarbons (HFC) refrigerant, HF hydrocarbon (HFO) refrigerant etc.) lower than-25 DEG C (the polyol ester class of 20% is in refrigerants), and at the kinematic viscosity (kinematicviscosity) of 40 DEG C between 46 ~ 460cSt, and it is demonstrating comparatively high workload viscosity after testing under associated compressor standard conditions.
Background technology
Be the threat in response to global warming in recent years, from the Kyoto Protocol to Copenhagen agreement, what various countries set about starting carrying out being correlated with one after another subtracts carbon work, therefore carbon emission regulation increasingly stringent.In refrigeration air-conditioner industry, except must in response to except the operating specification of relevant novel environment friendly refrigerant and time-histories, each Compressors Factory comes back along with the fermentation of energy shortage subject under discussion and environmental consciousness, and the lifting also for refrigerant system efficiency has the demand grown with each passing day.
Assessment refrigerant system efficiency is mainly Energy Efficiency Ratio (COP: the electric power of every 1kW, the refrigerating capacity kW that energy output per hour is how many).The higher expression of COP value is with same refrigerating capacity, and required electric power is fewer, and running cost is also just low.
For improving the COP of refrigeration equipment, mainly can improve from both direction:
(1) compressor design is improved:
1. upconversion operation;
2. appropriate mix motor;
3. improve rotor flute profile (improve area utilization factor, reduce leakage area);
4. adopt high-precision processing units, reduce the vibration of compressor and noise, the raising compressor life-span;
5. use high-precision oil strainer, control the exhaust clearance of compressor, improve volumetric efficiency;
6. precisely control compression ratio, reduce insufficient compression or compress excessive improper wasted work;
7. improve oil separator and block oily efficiency, oil mass (oilcarryover) will be thrown and control within 2%, and can prevent excessive refrigeration oil from entering vaporizer (Evaporator), and then increase hot transfer efficiency, and improve refrigerating capacity; With
8. improve the Pressure Drop (reducing the input work needed for compressor) of compressor primary clustering and valve class; And
(2) high-effect refrigeration lubrication oil is selected:
Refrigeration lubrication oil by increasing airtight, lubricating bearings, minimizing noise, take away the heat of compression (cooling), reduce the frictional coefficient of oil film, reduce motor wasted work and clean (dissolved impurity and by product avoid obstruction) and reach high-effect.
By selecting high-effect refrigeration lubrication oil to improve COP, no matter consider with regard to cost consideration or operation ease, all comparatively improve compressor design simply more convenient.
But refrigeration lubrication oil affects the main key of the efficiency of refrigeration system from two parts:
(1) the refrigeration lubrication oil in vaporizer and the mutual solubility of refrigerant
(miscibility) and the hot transfer efficiency of refrigerant, and
(2) compressor internal lubrication and sealing effectiveness.
Select the override of refrigeration lubrication oil to be thought of as the mutual solubility (miscibility) of itself and refrigerant, it affects and is divided into two aspects: compressor oil return consideration and the hot transfer efficiency of vaporizer.Although be usually provided with oil separator (Oilseparator) at compressor outlet, cause compressor inside cold lubricating oil not enough to prevent refrigeration lubrication oil from causing too much refrigeration lubrication oil to leave compressor with refrigerant because throwing oily phenomenon (Oilcarryover), and then compressor fault occurs.But, inevitably, a little refrigeration lubrication oil will be had to leave compressor, finally enter in vaporizer with refrigerant.Under the low temperature environment of vaporizer, refrigeration lubrication oil will be deteriorated with the mutual solubility of refrigerant, if the now situation that is separated because mutual solubility is not enough, refrigeration lubrication oil will be caused to be accumulated in evaporator surface and cannot to get back in compressor, thus the hot transfer efficiency of refrigerant in vaporizer can not only be affected, more seriously by causing the quantity not sufficient of refrigeration lubrication oil in compressor, cause compressor fault.
The selection of refrigeration lubrication oil except above-mentioned in vaporizer with except the mutual solubility of refrigerant, also need to consider that refrigeration lubrication oil is in compressor internal lubrication and stopping property.But affecting the most important factor of oilness and stopping property, is the work viscosity that refrigeration lubrication oil possesses under compressor operation condition.
Consider from oilness: when high temperature operation, when work viscosity is too low, easily cause mechanical part lack of lubrication and cause the electric energy of input and mechanical work increases in the running, reduce COP; Appropriateness raising work viscosity, will improve the oilness of mechanical part, and then increase COP.
Consider from stopping property: when high temperature operation, when work viscosity is too low, refrigeration lubrication oil will be deteriorated to the sealing effectiveness of mechanical part, easily cause refrigerant to leak under High Temperature High Pressure operation, reduce refrigeration capacity, and then reduce COP; If appropriate raising work viscosity, the stopping property of mechanical part will be improved, to the lifting of COP by helpful.
Consider from running resistance (Dragforce): the prerequisite that the viscosity when high temperature operation enough lubricates, when working temperature reduces, viscosity will improve gradually, if viscosity is too high, running resistance is larger, the electric energy and mechanical work that cause input is increased, reduces COP.
Affect refrigeration lubrication oil with the factor of refrigerant mutual solubility (miscibility) be mainly with the polarity of refrigeration lubrication oil and viscosity relevant.Generally speaking, refrigeration lubrication oil viscosity is higher, and polarity is poorer, and mutual solubility is also poorer.
The factor affecting refrigeration lubrication oil work viscosity mainly comprises:
(1) the original viscosity of refrigeration lubrication oil, and
(2) refrigeration lubrication oil viscosity index (ViscosityIndex, VI): viscosity index is higher, it is less that viscosity varies with temperature degree, and
(3) under Working environment, the ratio that refrigerant dissolves in refrigeration lubrication oil just determines the viscosity dilution effect caused.When refrigerant, to dissolve in refrigeration lubrication oil ratio example within the compressor higher, and work viscosity is lower.
Summary of the invention
The present invention for solve problem
Generally speaking, refrigeration lubrication oil viscosity is higher, and the mutual solubility of itself and refrigerant is poorer.In the present invention; by adjustment molecular structure to change polarity; make reaction and the polyol ester class product that obtains and the refrigeration lubrication oil constituent containing that have two kinds of characteristics below simultaneously: excellent refrigerant mutual solubility; with there is higher work viscosity when running operation; enough lubrication protections and sufficient sealing function is provided by this to mechanical part; and simultaneously because fully dissolving each other with refrigerant, avoid in vaporizer, cause the problem that it cannot get back in compressor (hereinafter referred to as oil return) and heat biography reduces because being separated.
Originally neoteric polyol ester class product (POE) and the refrigeration lubrication oil constituent containing described product need possess high viscosity index (VI); enough viscosity protections are had under being provided in high-temperature operation condition; and under cold operation condition; the unlikely rising of viscosity too much causes running resistance excessive, causes COP to reduce.
Polyol ester class product (POE) of the present invention and containing that refrigeration lubrication oil constituent except above-mentioned, " work viscosity ", except " refrigerant mutual solubility " and " viscosity index ", also other strict requirement for refrigeration lubrication oil must be met, such as, tube sealing thermal oxidation stability test, hydrolysis stability, acid value, hydroxyl valency, pour point, flash-point, moisture and dielectric strength etc.
Embodiment
In refrigeration lubrication oil constituent of the present invention, the content of polyol ester class product, between 50 % by weight to 100 % by weight, is preferably more than 70 % by weight, is more preferably more than 95 % by weight.
In polyol ester class product mixtures in refrigeration lubrication oil constituent of the present invention, the saturated or unsaturated C of tripentaerythritol (TriPE) and one or more straight or branched
4-20fatty acid response and the polyol ester class product that obtains can be 0-100 weight ratio, the saturated or unsaturated C of Dipentaerythritol (DiPE) and one or more straight or branched
4-20fatty acid response and the polyol ester class product that obtains can be 0-100 weight ratio, the saturated or unsaturated C of tetramethylolmethane (PE) and one or more straight or branched
4-20fatty acid response and the polyol ester class product obtained can be 0-99 weight ratio.
In refrigeration lubrication oil constituent of the present invention, can be added one or more in addition and be selected from by the additive in following formed group: sour trapping agent, extreme-pressure additive (extremepressureadditive), antioxidant or metal passivator.
Refrigeration lubrication oil constituent of the present invention can be as used in combination in alkyl glycol compound (PAG), polyvinyl ether compounds (PVE) with the synthesis refrigeration lubrication oil of other kind.The amount ratio of the refrigeration lubrication oil of refrigeration lubrication oil constituent of the present invention and other kind between 100:0 and 20:80, can be preferably 100:0 and 50:50.
Refrigeration lubrication oil constituent of the present invention is applicable to following type refrigerant: hydrofluorocarbons (HFC) refrigerant (such as R134a, R410A, R404A, R407C), HF hydrocarbon (HFO) refrigerant (such as R1234ze, R1234yf), be particularly useful for R134a or R410A.
Refrigeration lubrication of the present invention oil constituent and the amount ratio of refrigerant can be 99/1-1/99, are more preferably the scope of 95/5-10/90.Be less than the occasion of above-mentioned scope in the amount of refrigeration agent, find that refrigerating capacity reduces, and in the occasion higher than above-mentioned scope, lubricity reduce.Refrigeration lubrication oil constituent of the present invention can be used for various refrigerant condenser.
Synthetic method
Polyol ester class product (POE) of the present invention is by the saturated or unsaturated C of tripentaerythritol (TriPE), Dipentaerythritol (DiPE), tetramethylolmethane (PE) or its mixture and straight or branched
4-20fatty acid response and obtaining, this polyol ester class product (POE) has following character: with the temperature of dissolving each other of hydrofluorocarbons (HFC) refrigerant, HF hydrocarbon (HFO) refrigerant lower than-25 DEG C (polyol ester class products of 20%), and at the kinematic viscosity of 40 DEG C between 46 ~ 460cSt.
The C comprised in refrigeration lubrication oil constituent of the present invention
4-20lipid acid, is preferably C
5-10lipid acid, such as positive valeric acid, n-caproic acid, positive enanthic acid, n-caprylic acid, pelargonic acid, n-capric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2 methyl caproic acid, 2-ethylpentanoic, 2 ethyl hexanoic acid, 3,5,5 Trimethylhexanoic acid or neodecanoic acid etc.
The completely not esterified and part ester obtained of all hydroxyls of polyvalent alcohol is comprised at polyol ester class product of the present invention, or can be all esterified and complete ester obtained of all hydroxyls, or can be the mixture of part ester and complete ester, but preferably is the product of complete esterification.
The synthetic method of polyol ester class product (POE) of the present invention comprises esterif iotacation step and purification step.
Esterif iotacation step: by the saturated of one or more appropriate straight or branched or unsaturated C
4-20lipid acid is selected from the polyol reaction of tripentaerythritol, Dipentaerythritol or tetramethylolmethane with one, two or three when catalyst exists (or without catalyst).Temperature of reaction looks initiator and catalyst is different, between 150 to 250 DEG C, better for 180 to 240 DEG C, is more preferably under 200 to 230 DEG C, reacts to hydroxyl valency lower than below 10mgKOH/g, better below 5mgKOH/g, better below 3mgKOH/g.
Conventional catalyst comprises stannous oxalate, tin protoxide, butyl titanate, metatitanic acid tripropyl ester or methylsulphonic acid etc.
Purification step:
Remove moisture: by dry under system height vacuum, remove moisture to below 50ppm.
Remove residual acid: by adding alkali (sodium hydroxide) neutralization and distillation, the acid value of polyol ester class product is down to below 0.05mgKOH/g.
Remove catalyst and impurity: by adding activated carbon and filtration adjuvant (perlite), really remove catalyst and impurity with filter type.
For preventing because of heat, invading extraneous gas in freeze cycle or moisture or residue in the impact of the residue things such as rust-preventive agent in freeze cycle and cause oil ageing, deterioration or resolve into acidic component and then etching system inside, sour trapping agent can be added in refrigeration oil.The sour trapping agent be applicable to is glycidyl ester, glycidyl ether and α-epoxy alkane etc.As glycidyl ester, carbon number of can illustrating is generally 3-30, is preferably 4-24, is more preferred from the straight-chain of 6-16, branched, the saturated or unsaturated aliphatic of ring-type or the glycidyl ester of aromatic carboxylic acid.Can enumerate as 2 ethyl hexanoic acid glycidyl ester, 3,5,5 Trimethylhexanoic acid glycidyl ester, capric acid glycidyl ester, lauric acid glycidyl ester, tertiary carboxylic acid glycidyl ester, tetradecanoic acid glycidyl ester etc.As glycidyl ether, carbon number of can illustrating is generally 3-30, is preferably 4-24, is more preferred from the straight-chain of 6-16, branched, the saturated or unsaturated aliphatic of ring-type or aromatic glycidyl ether.Can enumerate as 2 ethyl hexanoic acid glycidyl ether, different nonyl glycidyl ether, decyl glycidyl ether, lauric acid glycidyl ether, tetradecanoic acid glycidyl ether etc.As α-epoxy alkane, carbon number of can illustrating is generally 4-50, is preferably 4-24, is more preferred from the α-epoxy alkane of 6-16.The consumption of acid trapping agent is generally 0-2 % by weight, is preferably 0-1 % by weight.
For preventing the abrasion of the metal covering of compressor slipper, improving oilness and reduce heat of friction, extreme-pressure additive can be added as abrasion activator in refrigeration oil.The additive be applicable to can be phosphorus system extreme-pressure additive and sulphur system extreme-pressure additive.As phosphorus system extreme-pressure additive, phosphotriester and tris phosphite can be used.As phosphotriester, tritolyl phosphate, triphenylphosphate, tricresyl phosphate (tributyl phenyl) ester, mono phosphoric acid ester phenyl two (tributyl phenyl) ester, diphenyl phosphate (tributyl phenyl) ester etc. can be enumerated.As tris phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (ethylhexyl) ester, tridecyl phosphite, trilauryl phosphite etc. can be enumerated.As sulphur system extreme-pressure additive, sulfuration grease, sulfide aliphatic acid, sulfuration ester, olefine sulfide, thiocarbamates, sulphur terpenes, dialkyl dipropionate class etc. can be enumerated.The consumption of extreme-pressure additive is generally 0-4 % by weight, is preferably 0.2-2 % by weight.
Enter in refrigerating circulation system for preventing extraneous gas and cause oil ageing or deterioration, preferably antioxidant is added, such as 2,6-bis--tributyl-4-methylphenol, 2,6-bis--tributyl-4-ethylphenol, 2, the phenol system antioxidants such as 2 '-methylene-bis (4-methyl-6-tributyl phenol), or the amine system antioxidant such as phenyl-a-naphthylamine, N-N '-diphenyl-p-phenylenediamine.The consumption of antioxidant is generally 0-1 % by weight, is preferably 0-0.5 % by weight.
For inertia protective membrane can be formed in metallic surface or generate inner complex with metal ion thus suppress the oxygenizement of metal or the freezing oil product of its ionic catalysis, metal passivator can be added in refrigeration oil.The metal passivator be applicable to is Methylbenzotriazole derivative (Tolutriazole), benzotriazole derivatives (Benzotriazole), thiadiazoles derivative (thiadiazde) etc.The consumption of metal passivator is generally 0-0.5 % by weight, is preferably 0-0.2 % by weight.
Except polyol ester class product (POE), poly-stretch alkyl diol (polyalkyleneglycol (PAG), polyalkylene glycol) and polyvinyl ether (Polyvinylether (PVE)) is also often used as refrigeration lubrication oil.PAG is propylene oxide (propyleneoxide, and/or oxyethane (ethyleneoxide PO), EO) polymkeric substance, controls viscosity by polymerizable molecular amount, and controls its mutual solubility in refrigerant by molecular chain end-blocking (single end-blocking or two end-blocking).PAG and HFC has good mutual solubility, has excellent compatibility with rubber-plastic material, and it has high viscosity index and superior low temperature characteristic.PVE is the polymkeric substance with side chain ether.By adjustment polymerization chain length and polymer side chain carbon chain lengths, PVE and HFC has good mutual solubility, and possesses the additive intermiscibility of excellent hydrolysis resistance and excellence simultaneously,
Analysis test method:
The stability of tube sealing thermooxidizing:
According to ANSI/ASHRAE standard 97-2007, by refrigeration lubrication oil and refrigerant with the weight ratio of 1:1, to insert in withstand voltage Glass tubing, and place that standard metal sheet (copper, aluminium, stainless steel) seals afterwards.Again withstand voltage Glass tubing is placed in 175 DEG C of baking ovens and reaches 14 days, by observation tinsel, refrigeration lubrication oil and refrigerant changing conditions before and after heating, the stability of com-parison and analysis refrigeration lubrication oil under tube sealing thermooxidizing.
Hydrolysis stability:
According to ASTMD-2619, be placed in test container by 75g refrigeration lubrication oil, and put into testing standard copper sheet with 25g water, in 93 DEG C of heating 48 hours, the changing conditions of the copper sheet before and after observation test and refrigeration lubrication oil, to assess refrigeration lubrication oil hydrolysis stability.
Kinematic viscosity and viscosity index: according to ASTM-D445, measure the kinematic viscosity 40 DEG C and 100 DEG C, and two kinds of kinematic viscosities calculate viscosity index according to this.
Density: according to ASTM-D7042, measures the density of refrigeration lubrication oil 15 DEG C, 40 DEG C and 100 DEG C.
Flash-point: according to ASTM-D92, measures refrigeration lubrication oil open type flash-point numerical value.
Pour point: according to ASTM-D97, measures the characteristic of refrigeration lubrication oil low temperature pour point.
The solubleness of refrigerant in refrigeration oil and mixture movement viscosity: by the refrigeration lubrication of predetermined amount oil and refrigerant under low temperature and high vacuum, insert in a pressurized vessel, mixture is first heated to 100 DEG C, progressively be cooled to 0 DEG C again, in the whole process of cooling, the monitoring temperature of mixture, pressure and kinematic viscosity, and refrigerant in sampling analysis mixture and the actual composition of refrigeration lubrication oil.
By the solubility curve of monitoring data through calculating and plotting resulting mixture and the kinematic viscosity curve of mixture.Utilize solubility curve and kinematic viscosity curve, can calculate under specific compressor operation condition, the actual motion viscosity of mixture and the refrigerant solubleness in refrigeration oil.
Two-phase laminated flow temperature: according to ANSI/ASHRAE standard 86-1994, encloses the refrigeration lubrication of specified quantitative oil and refrigerant in withstand voltage Glass tubing, and Glass tubing is placed in low-temperature bake oven, progressively lowers the temperature and observes refrigerant and refrigeration lubrication oil troubled water.When appearance vaporific in vain, finally to two-phase laminated flow time, its temperature is two-phase laminated flow temperature.
Dielectric strength: according to ASTMD-877, determines any insoluble degradation production in refrigeration lubrication oil, within the required timed interval repeatedly between puncture test, measures dielectric strength.
Moisture measures: ASTME-1064 measures with KarlFischer moisture meter.
Acid value: according to ASTMD-974 with the titration of 0.05NKOH standard solution.
Embodiment 1.TriPE+ (iC9, MBA, nC5)
Raw material: tripentaerythritol (TriPE), and lipid acid: isoC9 (3,5,5 Trimethylhexanoic acid)+MBA (2-Methyl Butyric Acid)+nC5 (positive valeric acid) (% by weight=25%:60%:15%)
Additive: tritolyl phosphate 1%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 2. mixed ester 1
Synthetic ester 1:TriPE+neo10 (neodecanoic acid)+MBA, wherein neo10:MBA=80:20 (% by weight)
Synthetic ester 2: Dipentaerythritol (DiPE)+MBA
Mixed ester 1=synthetic ester 1 (% by weight=45%)+synthetic ester 2 (% by weight=55%)
Additive: tritolyl phosphate 1%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 3. mixed ester 2
Synthetic ester 3:TriPE+iC9+MBA, wherein iC9:MBA=25:75 (% by weight)
Synthetic ester 4:DiPE+MBA
Mixed ester 2=synthetic ester 3 (% by weight=50%)+synthetic ester 4 (% by weight=50%)
Additive: tritolyl phosphate 1%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 4.DiPE+ (nC5+iC9)
Raw material: Dipentaerythritol (DiPE), and lipid acid: nC5 (positive valeric acid)+isoC9 (3,5,5 Trimethylhexanoic acid) (% by weight=25%:75%)
Additive: tritolyl phosphate 1%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 5. (TriPE+DiPE)+MBA
Raw material: tripentaerythritol (TriPE)+Dipentaerythritol (DiPE) (% by weight=57%:43%) and lipid acid MBA (2-Methyl Butyric Acid)
Additive: tritolyl phosphate 1%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 6. mixed ester 3
Synthetic ester 3:TriPE+iC9+MBA, wherein iC9:MBA=25:75 (% by weight)
Synthetic ester 5:(PE+DPE)+(nC5+iC9), wherein
PE:DPE=92:8 (% by weight)
NC5:iC9=35:65 (% by weight)
Mixed ester 3=synthetic ester 3 (% by weight=70%)+synthetic ester 5 (% by weight=30%)
Additive: tritolyl phosphate 1%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 7.DiPE+ (nC5+iC9)
Raw material: Dipentaerythritol (DiPE), and lipid acid: nC5 (positive valeric acid)+isoC9 (3,5,5 Trimethylhexanoic acid) (% by weight=55%:45%)
Additive: tritolyl phosphate 1.5%, tertiary carbonic acid glycidyl ester 0.5%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 8.DiPE+ (nC5+iC9)
Raw material: Dipentaerythritol (DiPE), and lipid acid: nC5 (valeric acid)+isoC9 (3,5,5 Trimethylhexanoic acid) (% by weight=75%:25%)
Additive: tritolyl phosphate 1.5%, tertiary carbonic acid glycidyl ester 0.5%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Embodiment 9.DiPE+nC5
Raw material: Dipentaerythritol (DiPE), and lipid acid: nC5 (valeric acid)
Additive: tritolyl phosphate 1.5%, tertiary carbonic acid glycidyl ester 0.5%, 2,6-bis--tributyl-4-methylphenol 200ppm, Methylbenzotriazole derivative 200ppm
Basic physical properties:
Comparative example 1.Lubrizol (CPI): Solest220
Basic physical properties:
Comparative example 2.Lubrizol (CPI): Solest120
Basic physical properties:
Comparative example 3.JXNipponOil:Ze-GlesRB68EP
Basic physical properties:
The essential property of refrigeration lubrication oil of the present invention:
Moisture is refrigeration lubrication the most basic oily requirement.For POE class lubricating oil, the existence of high-moisture easily causes the reversed reaction that esterification occurs in refrigeration systems to occur, and causes ester class to be cracked into acids, and then reduces the stability of refrigeration lubrication oil.And when cold operation, too much moisture easily freezes, easily cause system damage and reduce heat passing area.The embodiment of the present invention 1 ~ 9, all with nitrogen treatment, guarantees that moisture meets the specification of general POE refrigeration lubrication oil.
Acid value on the topmost impact of refrigeration system mainly from two aspects: too high acid value easily accelerates scission reaction, and easily causes the corrosion of the metal material of internal system.The all purified process of the embodiment of the present invention 1 ~ 9, guarantees that acid value meets the specification of general POE refrigeration lubrication oil.
Easy with the refrigeration system of electric material contacts, dielectric strength is the basic important parameter of assessment refrigeration lubrication oil.Too low dielectric strength easily causes operation process to be short-circuited, and causes motor burnout.Affect the principal element of dielectric strength except refrigeration lubrication oil structure self character, particularly important with the removal (comprising the raw material of remained unreacted, catalyst etc.) of reacting rear impurity.The all purified process of the embodiment of the present invention 1 ~ 9, guarantees that dielectric strength meets the specification of general POE refrigeration lubrication oil.
Table 1: the high viscosity refrigeration lubrication oil of embodiment 1 ~ 6 and comparative example 1 ~ 2 compares (40 DEG C of Yun move Nian Du≤120cSt) with the mutual solubility of R134a refrigerant
Generally speaking, viscosity is higher, poorer with the mutual solubility of refrigerant.But can find from upper table, in the present invention, the kinematic viscosity of the POE of embodiment 1 ~ 6, from 220cSt ~ 400cSt, is high compared with the kinematic viscosity 120 ~ 220cSt of comparative example 1 ~ 2, but has the two-phase laminated flow temperature lower compared with comparative example 1 ~ 2.
The POE of the embodiment of the present invention 1 ~ 6 and the mutual solubility of refrigerant more can meet vaporizer oil return and the hot requirement passed compared with the commercial goods of comparative example 1 ~ 2; and because viscosity is higher; the stopping property protection that compressor more can be provided better; reduce the possibility of coolant leakage, make compressor operation efficiency higher (especially for screw-type compressor).
Table 2: the middle low-viscosity refrigeration lubrication oil of embodiment 7 ~ 8 and comparative example 3 compares (40 DEG C of kinematic viscosity <120cst) with the mutual solubility of R134a refrigerant
The POE of the embodiment of the present invention 7 ~ 8 is compared to the commercial goods of comparative example 3; there is identical or more high viscosity; and it is more excellent significantly with the mutual solubility of R134a refrigerant; except guaranteeing that vaporizer oil return is without except anxiety, the seal protection of compressor more can be provided, prevent coolant leakage and improve operation efficiency.
Table 3: the middle low-viscosity refrigeration lubrication of embodiment 7 ~ 8 and comparative example 3 is oily and R410A refrigerant
The comparison (40 DEG C of kinematic viscosity <120cst) of mutual solubility
The conventional R410A refrigerant of the rotary compressor (Rotarycompressor) that domestic air conditioning is conventional.Generally speaking, because polarity difference is comparatively large, the mutual solubility of identical polyol ester class refrigeration lubrication oil and R410A refrigerant often comparatively R134a for poor.But show from the mutual solubility analytical results of upper table, even if embodiment 7 kinematic viscosity is up to 90cst (providing better sealing property), still comparatively commercially available prod is excellent for the mutual solubility of itself and R410A, and embodiment 8 is same with the mutual solubility of R410A excellent, but viscosity comparatively embodiment 7 is low, the starting point is to reduce running resistance (Dragforce)
Table 4: comprise the work ratio of viscosities of the refrigeration lubrication oil of high viscosity ISO220 grade and the mixture of R134a refrigerant comparatively
In screw-type compressor, the refrigeration lubrication oil with ISO220 viscosity grade is common matched combined with R134a refrigerant.In the operational condition 1 ~ 2 time of table 4, relatively the POE of the embodiment of the present invention 4 can find with the commercial goods of comparative example 1: although the oily original motion viscosity of refrigeration lubrication same be 220cSt, but the POE of the embodiment of the present invention 4 except two-phase laminated flow temperature preferably except, no matter be the operational condition 1 time at high loading (highload), or in the operational condition 2 times of underload (Lowload), the mixture movement viscosity of embodiment 4 is all higher, guarantee that oil-bound film is thicker, the better and good seal of oilness.
Table 5: comprise the work ratio of viscosities of the refrigeration lubrication oil of middle low-viscosity ISO68 ~ 90 grade and the mixture of R134a refrigerant comparatively
The POE of the embodiment of the present invention 7 ~ 8 is except two-phase laminated flow temperature is better, no matter be the operational condition 1 time at high loading (highload), or in the operational condition 2 times of underload (Lowload), the mixture movement viscosity of embodiment 7 ~ 8 is all high compared with the commercial goods of comparative example 3, guarantee that oil-bound film is thicker, the better and good seal of oilness.
Table 6: comprise the work ratio of viscosities of the refrigeration lubrication oil of middle low-viscosity ISO68 ~ 90 grade and the mixture of R410A refrigerant comparatively
The rotary compressor that domestic air conditioning is commonly used commonly uses the refrigeration lubrication oil of R410A refrigerant collocation ISO68 viscosity grade.The POE of the embodiment of the present invention 7 ~ 8 is except two-phase laminated flow temperature is better, no matter be the operational condition 3 times at high loading, or in the operational condition 4 of middle-low load and operational condition 5 times, the mixture movement viscosity of embodiment 7 ~ 8 is all high compared with the commercial goods of comparative example 3, guarantee that oil-bound film is thicker, the better and good seal of oilness.
Table 7: tube sealing heat-resistant quality is compared (R134a)
* the unchanged zero Little color changes delta of judgement criteria: ◎ significantly colour-change
Testing method: ANSI/ASHRAE standard 97-2007
Tube sealing heat-resistant quality is compared (R410A)
* the unchanged zero Little color changes delta of judgement criteria: ◎ significantly colour-change
Testing method: ANSI/ASHRAE standard 97-2007
In refrigeration systems, assessment refrigeration lubrication oil stability, the most frequently used is tube sealing thermal oxidation stability method of testing.This method from generally assess the maximum different of lubricating oil stability method, be that its test operates under being in High Temperature High Pressure refrigerant environment, can accelerate differentiate refrigeration lubrication oil stability difference.Thermal oxidation stability is poorer, easily causes system congestion, corrosion and increases abrasion.
No matter the POE of the embodiment of the present invention is under R134a or R410A environment, all possess excellent heat oxidation stability.
Hydrolysis stability compares (ASTMD-2619)
Although generally speaking, in refrigeration system, the chance of contact wetting is very little, for large-scale refrigerating system, still likely causes a little moisture to enter refrigeration system because of negligence of operation.Therefore, hydrolysis refrigeration lubrication oil is provided just to become important property assessment instrument.
As above show, according to hydrolysis test result, POE of the present invention has good hydrolysis stability.
Claims (13)
1. a refrigeration lubrication oil constituent, it comprises the saturated or unsaturated C by tripentaerythritol (TriPE), Dipentaerythritol (DiPE), tetramethylolmethane (PE) or its mixture and one or more straight or branched
4-20fatty acid response and the polyol ester class product obtained.
2. a refrigeration lubrication oil constituent, it comprises by the saturated or unsaturated C of tripentaerythritol (TriPE) with one or more straight or branched
4-20fatty acid response and obtain polyol ester class product, by the saturated or unsaturated C of Dipentaerythritol (DiPE) with one or more straight or branched
4-20fatty acid response and the polyol ester class product that obtains or by the saturated or unsaturated C of tetramethylolmethane (PE) with one or more straight or branched
4-20fatty acid response and the mixture of the polyol ester class product obtained.
3. refrigeration lubrication oil constituent as claimed in claim 1 or 2, wherein this polyol ester class product has following character: with the temperature of dissolving each other of hydrofluorocarbons (HFC) refrigerant, HF hydrocarbon (HFO) refrigerant lower than-25 DEG C (the polyol ester class product of 20% is in refrigerants), and at the kinematic viscosity (kinematicviscosity) of 40 DEG C between 46 ~ 460cSt.
4. refrigeration lubrication oil constituent as claimed in claim 1 or 2, wherein this lipid acid can be C
5-10lipid acid.
5. refrigeration lubrication oil constituent as claimed in claim 4, wherein this lipid acid comprises positive valeric acid, n-caproic acid, positive enanthic acid, C
8-10mixing acid, 2-Methyl Butyric Acid, 2 ethyl hexanoic acid, 3,5,5 Trimethylhexanoic acid or neodecanoic acid.
6. refrigeration lubrication oil constituent as claimed in claim 1 or 2, it comprises extreme-pressure additive, metal passivator, sour trapping agent, antioxidant or other synthesis refrigeration lubrication oil in addition.
7. refrigeration lubrication oil constituent as claimed in claim 6, wherein these other synthesis refrigeration lubrication oil stretches alkyl diol (PAG) or polyvinyl ether (PVE) for poly-.
8. refrigeration lubrication oil constituent as claimed in claim 3, wherein this refrigerant comprises hydrofluorocarbons (HFC) refrigerant or HF hydrocarbon (HFO) refrigerant.
9. refrigeration lubrication oil constituent as claimed in claim 8, wherein this hydrofluorocarbons (HFC) refrigerant can be R134a, R410A, R404A or R407C, and this HF hydrocarbon (HFO) refrigerant can be R1234ze or R1234yf.
10. refrigeration lubrication oil constituent as claimed in claim 8, wherein this refrigerant is R134a or R410A.
11. refrigeration lubrication oil constituents as claimed in claim 6, wherein the amount ratio of this refrigeration lubrication oil constituent and refrigerant can be 99/1 ~ 1/99.
12. refrigeration lubrication oil constituents as claimed in claim 6, wherein this extreme-pressure additive addition is 0-4 % by weight, this metal passivator 0-0.5 % by weight, this sour trapping agent 0-2 % by weight, and this antioxidant 0-1 % by weight.
13. refrigeration lubrication oil constituents as claimed in claim 6, wherein this polyol ester class product is 20 ~ 100% to the ratio of this PAG or PVE.
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| CN201410390065.1A CN105331422A (en) | 2014-08-08 | 2014-08-08 | High-performance refrigeration lubricating oil composition |
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| CN106762663A (en) * | 2016-11-23 | 2017-05-31 | 广东美芝精密制造有限公司 | Rotary compressor and the refrigeration plant with the rotary compressor |
| CN107287008A (en) * | 2017-06-15 | 2017-10-24 | 珠海格力节能环保制冷技术研究中心有限公司 | A kind of refrigerator oil and preparation method thereof and working fluid composition for refrigerating machine |
| CN107828460A (en) * | 2017-10-20 | 2018-03-23 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigeration oil, its application and compressor |
| CN109804037A (en) * | 2016-10-10 | 2019-05-24 | 阿科玛法国公司 | The purposes of composition based on tetrafluoropropene |
| CN111218322A (en) * | 2018-11-27 | 2020-06-02 | 北京蓝星清洗有限公司 | Pentaerythritol ester lubricating oil base oil and preparation method thereof |
| CN112143547A (en) * | 2020-09-22 | 2020-12-29 | 上海桉欣新能源科技有限公司 | Lubricating oil for refrigeration compressor and preparation method thereof |
| US11306232B2 (en) | 2016-10-10 | 2022-04-19 | Arkema France | Tetrafluoropropene-based azeotropic compositions |
| CN115491241A (en) * | 2022-10-20 | 2022-12-20 | 中国石油化工股份有限公司 | Pentaerythritol ester base oil and preparation method thereof |
| CZ309434B6 (en) * | 2016-02-24 | 2023-01-11 | Mitsubishi Electric Corporation | Refrigerant for refrigeration equipment |
| WO2024009684A1 (en) * | 2022-07-08 | 2024-01-11 | Ｅｎｅｏｓ株式会社 | Refrigerator oil and working fluid composition |
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| CZ309434B6 (en) * | 2016-02-24 | 2023-01-11 | Mitsubishi Electric Corporation | Refrigerant for refrigeration equipment |
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| JP2019534936A (en) * | 2016-10-10 | 2019-12-05 | アルケマ フランス | Use of compositions based on tetrafluoropropene |
| US10954467B2 (en) | 2016-10-10 | 2021-03-23 | Arkema France | Use of tetrafluoropropene based compositions |
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| CN106762663A (en) * | 2016-11-23 | 2017-05-31 | 广东美芝精密制造有限公司 | Rotary compressor and the refrigeration plant with the rotary compressor |
| CN107287008A (en) * | 2017-06-15 | 2017-10-24 | 珠海格力节能环保制冷技术研究中心有限公司 | A kind of refrigerator oil and preparation method thereof and working fluid composition for refrigerating machine |
| CN107828460A (en) * | 2017-10-20 | 2018-03-23 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigeration oil, its application and compressor |
| CN111218322A (en) * | 2018-11-27 | 2020-06-02 | 北京蓝星清洗有限公司 | Pentaerythritol ester lubricating oil base oil and preparation method thereof |
| CN112143547A (en) * | 2020-09-22 | 2020-12-29 | 上海桉欣新能源科技有限公司 | Lubricating oil for refrigeration compressor and preparation method thereof |
| CN112143547B (en) * | 2020-09-22 | 2022-07-15 | 上海桉欣新能源科技有限公司 | Lubricating oil for refrigeration compressor and preparation method thereof |
| WO2024009684A1 (en) * | 2022-07-08 | 2024-01-11 | Ｅｎｅｏｓ株式会社 | Refrigerator oil and working fluid composition |
| CN115491241A (en) * | 2022-10-20 | 2022-12-20 | 中国石油化工股份有限公司 | Pentaerythritol ester base oil and preparation method thereof |
| CN115491241B (en) * | 2022-10-20 | 2023-12-15 | 中国石油化工股份有限公司 | Pentaerythritol ester base oil and preparation method thereof |
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