CN1782042A - Lubricating oil composition of freezer - Google Patents

Lubricating oil composition of freezer Download PDF

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Publication number
CN1782042A
CN1782042A CNA2005101289448A CN200510128944A CN1782042A CN 1782042 A CN1782042 A CN 1782042A CN A2005101289448 A CNA2005101289448 A CN A2005101289448A CN 200510128944 A CN200510128944 A CN 200510128944A CN 1782042 A CN1782042 A CN 1782042A
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Prior art keywords
lubricating oil
ester
acid
oil composition
freezer
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Chinese (zh)
Inventor
山田宗宏
静延彦
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JAPAN OIL AND GREASE Ltd
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JAPAN OIL AND GREASE Ltd
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Priority to CN201210480112.2A priority Critical patent/CN103013619B/en
Publication of CN1782042A publication Critical patent/CN1782042A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C10M105/44—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a lubricating oil composition for refrigerator which is low viscous, has high specific volume resistance and exhibits excellent low-temperature stability. The lubricating oil composition for refrigerator is mainly composed of a mixed ester obtained from a mixed alcohol and a 5-10C saturated monocarboxylic acid, the mixed alcohol comprising 1-90 mol% of neopentyl glycol, 10-80 mol% of pentaerythritol and 0.01-20 mol% of dipentaerythritol and satisfying the above relational equation, and has a kinematic viscosity at 40 DEG C of 6-28 mm<2>/s.

Description

Lubricating oil composition of freezer
Technical field
The present invention relates to lubricating oil composition of freezer, specifically be the lubricating oil composition of freezer that no chlorofluoromethane refrigeration agent is used, contain the hydraulic fluid for refrigerator of this lubricating oil composition, and the freezing plant that has used this hydraulic fluid for refrigerator.
Background technology
Chloride fluothane refrigeration agent is used in refrigerator, air conditioning machinery etc.But, in recent years because problem such as infringement ozonosphere etc., with 1,1,1,2-Tetrafluoroethane (R-134a), pentafluoride ethane (R-125), C2H4F2 C2H4F2 (R-32) and with the chloride fluothane refrigeration agent of these the no chlorofluoromethane refrigeration agent replacement of mixed solvent etc. with one-tenth trend.Meanwhile, with the good polyol ester of no chlorofluoromethane intermiscibility be that the lubricating oil composition of freezer (below, be sometimes referred to as refrigerator oil) of base oil is also attempted.
Refrigerator oil is in order to ensure above-mentioned refrigerator, the stability of air conditioning machinery etc., except need with the intermiscibility of above-mentioned no chlorofluoromethane refrigeration agent, also be required to have oilness, thermostability, hydrolytic resistance, low-temperature fluidity, various characteristicses such as electrical insulating property.In these characteristics, consider hydrolytic resistance and with the intermiscibility of no chlorofluoromethane, the ester class of being obstructed that be made of carboxylic acid with side chain and tetramethylolmethane, excellent heat resistance (hindered ester) is actually used.Such as disclosing the ester that forms with the mixed fatty acid by tetramethylolmethane and 2 ethyl hexanoic acid and 3,5,5 Trimethylhexanoic acid in the patent documentation 1 is the refrigerator oil of main component, makes moderate progress on high-temperature stability.Straight or branched lipid acid and 3 by tetramethylolmethane and carbon number to be 6～8 is disclosed in the patent documentation 2,5, the ester that the mixed fatty acid of 5-tri-methyl hexanoic acid forms is the refrigerator oil of main component, has put down in writing the intermiscibility and the electrical insulating property that can improve thus with refrigeration agent.
On the other hand, because the raising of Environmental awareness in recent years, refrigerator and air conditioning machinery etc. also is required energy saving.As refrigerator oil, in order to give the energy saving of refrigerator etc., lowering viscousity is the most effective means, and everybody is making great efforts to reduce the refrigerator oil viscosity.
In order to reach the target of refrigerator oil lowering viscousity, use by also lower, and the ester that the good dibasic alcohol such as neopentyl glycol in aspect such as hydrolytic resistance, thermostability, viscosity form is more effective than pentaerythritol ester viscosity.But, the problem of electrical insulation capability difference is arranged because the volume intrinsic resistance of these esters is low.Like this, just produced so-called if for energy-conservation reduction viscosity, then electrical isolation reduce, with original purpose reverse effect, obtain refrigerator oil all excellent on lowering viscousity and electrical insulating property and be unusual difficulty.
And, be on the device of purpose because refrigerator oil is used in the refrigeration, therefore the stability under low-temperature condition is very important, particularly requires to place for a long time under low-temperature condition also can not separate out the crystalline performance.But what above-mentioned patent documentation 1 and 2 was put down in writing makes up resulting mixed ester by polyvalent alcohol and specific carboxylic acid, all the long-standing low-temperature stability of keeping is not carried out research fully.
Therefore, the refrigerator oil of the good and low viscosity of low-temperature stability, electrical insulating property height (volume intrinsic resistance height) is that everybody expects, but as mentioned above, its manufacturing is difficult.
(patent documentation 1) spy opens flat 10-8084 communique
(patent documentation 2) spy opens flat 6-330061 communique
Summary of the invention
The object of the present invention is to provide low viscosity, volume intrinsic resistance height and under low-temperature region the lubricating oil composition of freezer of permanent stability excellence, particularly use the lubricating oil composition of freezer of no chlorofluoromethane refrigeration agent.The present invention also aims to provide hydraulic fluid for refrigerator that uses above-mentioned lubricating oil composition of freezer and the refrigeration agent compression freezing plant that uses above-mentioned hydraulic fluid for refrigerator.
Present inventors, the volume solid resistance and the low-temperature stability of the low-viscosity lubricating oil composition that uses in the refrigerator for the no chlorofluoromethane refrigeration agent of use have carried out deep research, and make up various alcohol and carboxylic acids and carried out molecular designing.Found that, to constitute by neopentyl glycol, tetramethylolmethane, Dipentaerythritol, and satisfy the alcohol mixture of relation of certain amount and carbon number and be after 5～10 the saturated monocarboxylic acid combination, can obtain volume intrinsic resistance height and long-term good, the low viscous ester of low-temperature stability, and then finish the present invention.
The invention provides a kind of lubricating oil composition of freezer, it is being that the ester that 5～10 saturated monocarboxylic acid obtains is a main component by alcohol mixture and carbon number, this alcohol mixture is made of the tetramethylolmethane of the neopentyl glycol of 1～90 mole of %, 10～80 moles of % and the Dipentaerythritol of 0.01～20 mole of %, and satisfies following relational expression:
Formula 1
Figure A20051012894400051
And the kinematic viscosity of said composition in the time of 40 ℃ is 6～28mm 2/ s.
Preferred embodiment, 85 moles of saturated monocarboxylic acid that constitute above-mentioned mixed ester are the saturated monocarboxylic acid with α-side chain more than the %.
Preferred embodiment, molecular weight is that the amount of 370～1000 ester is 10～65 moles of % in the above-mentioned mixed ester.
In addition, the invention provides the hydraulic fluid for refrigerator that constitutes by above-mentioned lubricating oil composition of freezer and no chlorofluoromethane refrigeration agent.
And, the invention provides a kind of freezing plant, it is the refrigeration agent compression freezing plant that possesses compressor, condenser, decompressor and vaporizer, uses above-mentioned freezing working fluid.
Lubricating oil composition of freezer viscosity of the present invention is low, volume intrinsic resistance height and long-term low-temperature stability are good.And necessary intermiscibility, thermotolerance, oilness with no chlorofluoromethane refrigeration agent as lubricating oil composition of freezer might as well.So, composition of the present invention contains 1 as no chlorofluoromethane refrigeration agent, particularly use, 1,1, in 2-Tetrafluoroethane and the methylene fluoride ice machine oil of the no chlorofluoromethane refrigeration agent of at least one or as with the hydraulic fluid for refrigerator of no chlorofluoromethane refrigerant mixed be useful, the energy saving of various freezing plants is also had effect.
Embodiment
Below to mixed ester that composition of the present invention contained, contain this mixed ester lubricating oil composition of freezer, contain the hydraulic fluid for refrigerator of said composition and use the refrigeration agent compression freezing plant of this hydraulic fluid for refrigerator to describe.
Mixed ester
The mixed ester that lubricating oil composition of freezer of the present invention contained is to be that 5～10 saturated monocarboxylic acid gets by alcohol mixture and carbon number, this alcohol mixture is combined by the tetramethylolmethane of the neopentyl glycol of 1～90 mole of %, 10～80 moles of % and the Dipentaerythritol of 0.01～20 mole of %, and satisfies the following relationship formula:
Formula 2
Figure A20051012894400061
Present inventors are at degradation problem under the volume intrinsic resistance of the ester that is made of dibasic alcohol such as neopentyl glycol, carried out ester molecular designing, make it satisfy the above-mentioned relation formula, can provide that a kind of volume intrinsic resistance does not descend, long-time low-temperature stability excellence, low viscous ester.Just neopentyl glycol, tetramethylolmethane and Dipentaerythritol, mix by satisfying the above-mentioned relation formula, and be this alcohol mixture and carbon number 5～10 saturated monocarboxylic acid combination, discovery can access volume intrinsic resistance height (can not descend), good, the low viscous mixed ester of low-temperature stability for a long time.
The mixed ester that is contained in the lubricating oil composition of freezer of the present invention is considered from aspects such as stability to hydrolysiies, and the 85 moles of % of saturated monocarboxylic acid that preferably constitute this mixed ester are above for having the saturated monocarboxylic acid of α-side chain.
The mixed ester that is contained in the lubricating oil composition of freezer of the present invention considers that from aspects such as long low-temperature stability, volume intrinsic resistance and thermotolerances the molecular weight that preferably contains 10～65 quality % is 370～1000 ester.
Below, describe for the manufacture method of above-mentioned mixed ester.
As mentioned above, form by the tetramethylolmethane of the neopentyl glycol of 1～90 mole of %, 10～80 moles of % and the Dipentaerythritol of 0.01～20 mole of % as the alcohol mixture of above-mentioned mixed ester raw material.When using the alcohol mixture of above-mentioned 3 kinds to make ester, synthetic mixed ester beyond above-mentioned compositing range, in energy saving, any point defectiveness all on oilness and the thermotolerance can't be met the mixed ester of volume intrinsic resistance and long-term low-temperature stability.
As the carbon number of above-mentioned alcohol mixture raw material is 5～10 saturated monocarboxylic acid, and not without special restriction.Can be straight chain saturated monocarboxylic acid and saturated monocarboxylic acid with side chain any.And just long-term low-temperature stability, with the intermiscibility of no chlorofluoromethane refrigeration agent, and aspect such as erosion resistance consider that preferably carbon number is that 5～7 straight chain saturated monocarboxylic acid or carbon number are 7～10 side chain saturated monocarboxylic acid.The carbon number of saturated monocarboxylic acid can obtain the good ester of oilness 5 when above.Carbon number 10 can obtain when following low-temperature stability good and with the good mixed ester of no chlorofluoromethane refrigeration agent intermiscibility.
Above-mentioned carbon number be 5～10 saturated monocarboxylic acid such as having: valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 3 methylvaleric acid, the 4-methylvaleric acid, 2 Ethylbutanoic acid, the 3-ethyl butyric acid, enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 5-methylhexanoic acid, 2,2-dimethyl valeric acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 2 ethyl hexanoic acid, the 2-methyl enanthic acid, the 3-methyl enanthic acid, the 4-methyl enanthic acid, the 5-methyl enanthic acid, the 6-methyl enanthic acid, 2,2-dimethyl caproic acid, 3,5-dimethyl caproic acid, n-nonanoic acid, different n-nonanoic acid, capric acid, neodecanoic acid etc.From the oilness of the mixed ester that obtains with stability to hydrolysis is all good and the corrosion of metal aspect is considered, preferably use α-side chain saturated monocarboxylic acid, more preferably use 2 ethyl hexanoic acid.Above-mentioned carbon number is that 5～10 saturated monocarboxylic acid can use separately, from hydrolytic resistance, oilness, with aspects such as intermiscibility, thermotolerance, low-temperature stability and the viscosity consideration of no chlorofluoromethane, also can be used in combination more than 2 kinds.
By with above-mentioned alcohol mixture and carbon number being 5～10 saturated monocarboxylic acid combination, even use neopentyl glycol, also can obtain the volume intrinsic resistance and not reduce, can keep high-resistance, for a long time the mixed ester of low-temperature stability excellence.Such as, viscosity as required, in the scope that satisfies above-mentioned formula (1), neopentyl glycol, tetramethylolmethane, Dipentaerythritol combination are obtained alcohol mixture, with this alcohol mixture and carbon number is that 5～10 saturated monocarboxylic acid reacts, this saturated monocarboxylic acid preferably contains the saturated monocarboxylic acid that has α-side chain saturated monocarboxylic acid more than the 85 quality %, or the molecular weight that contains 10～65 quality % in the mixed ester that obtains is at the saturated monocarboxylic acid of 370～1000 ester.
Reaction can be undertaken by common esterification or transesterification reaction.Above-mentioned alcohol mixture and above-mentioned carbon number are that the ratio of 5～10 saturated monocarboxylic acid is suitably adjusted according to following: the hydroxyl value of the mixed ester that obtains is below 5.0mg KOH/g, and acid number is below 0.05mgKOH/g.
The manufacture method of the mixed ester that the present invention is used can obtain in order to following method specifically.At first, for hydroxyl 1 equivalent of alcohol mixture, be 1.0～1.5 equivalents, see that from production efficiency and economical point being preferably 1.05～1.3 equivalents mixes, and adds catalyzer as required according to mixed carboxylic acid's carboxyl.Make this mixture under nitrogen gas stream, 220 ℃～260 ℃ reactions 3～15 hours are under reduced pressure removed unnecessary carboxylic acid when following when hydroxyl value becomes 2.0mg KOH/g.Afterwards, with after the alkali depickling, with atlapulgite, acidic white earth and synthetic be that sorbent material absorbs processing, carry out operations such as decatize, can implement or make up these operations of execution separately.
The ice machine oil composition
Lubricating oil composition of freezer of the present invention, principal constituent are above-mentioned mixed esters, can add mixed ester other ester in addition as required, can contain additive etc." concrete content, be benchmark with whole lubricating oil composition of freezer, be more than the 50 quality %, more than the preferred 70 quality %, more preferably more than the 90 quality %.Also can be 100 quality %.
As the ester beyond the above-mentioned mixed ester that contains in the lubricating oil composition of freezer of the present invention, can list the ester of following pure and mild monocarboxylic acid or polycarboxylic acid formation etc., for example, alcohol moiety is 5～15 amyl-based polyol (2 for except neopentyl glycol, tetramethylolmethane, Dipentaerythritol 2 yuan～8 yuan and carbon number, 2-diethyl-1, ammediol, 2-normal-butyl-2-ethyl-1,3 propylene glycol, trimethylolethane, trihydroxyethyl ethane, TriMethylolPropane(TMP), tripentaerythritol, dipentaerythritol etc.).Above-mentioned ester can suitably contain in the scope of the characteristic that does not influence ice machine oil composition of the present invention.
As the additive that can contain in the lubricating oil composition of freezer of the present invention, antioxidant such as phenol system is arranged, metal inerting agents such as benzotriazole, thiadiazoles, dithiocarbamate, the oxygen trapping agent of epoxy compounds, carbodiimide etc., the high pressure agent of phosphorus system etc.Contain proportional for any.
Lubricating oil composition of freezer of the present invention, the kinematic viscosity in the time of 40 ℃ is 6～28mm 2/ s.From obtain excellent oilness and with the aspect of the intermiscibility of no chlorofluoromethane refrigeration agent, and use the good startability of refrigerator of this lubricating oil composition and the aspect consideration of energy saving, preferred 6.5～27.5mm 2/ s, more preferably 7～27mm 2/ s.
The acid number of lubricating oil composition of freezer of the present invention is not particularly limited.Below the preferred 0.05mg KOH/g, more preferably below the 0.03mg KOH/g, further preferred 0.01mgKOH/g.Acid number seldom can corroding metal when 0.05mg KOH/g is following, and hydrolytic resistance is good.
The hydroxyl value of lubricating oil composition of freezer of the present invention is not particularly limited.Below the preferred 5.0mg KOH/g, more preferably below the 3.0mg KOH/g, further preferred 2.0mgKOH/g is most preferably below the 1.0mg KOH/g.Hydroxyl value is not easy to reduce the volume intrinsic resistance of above-mentioned composition when 5.0mg KOH/g is following, can guarantee sufficient electrical insulation capability.So, state in the use on the machine of composition, can be to not producing detrimentally affect as the employed sealing agent of organic materials.Nor can produce detrimentally affect to the additive that contains.
Hydraulic fluid for refrigerator
Hydraulic fluid for refrigerator of the present invention is made of above-mentioned lubricating oil composition of freezer and no chlorofluoromethane refrigeration agent.The proportion compatibility of lubricating oil composition of freezer and no chlorofluoromethane refrigeration agent does not have particular restriction, and preferred mass ratio is a lubricating oil composition of freezer: no chlorofluoromethane refrigeration agent is 10: 90～90: 10.The compatibility of no chlorofluoromethane refrigeration agent than above-mentioned scope height, will cause the viscosity degradation of gained hydraulic fluid for refrigerator such as fruit, causes insufficient lubrication easily.If lower, when the freezing working fluid with gained is used for machine, may cause freezing efficiency to descend than above-mentioned scope.
As no chlorofluoromethane refrigeration agent, specifically have 1,1,1,2-Tetrafluoroethane (R-134a), pentafluoride ethane (R-125), C2H4F2 C2H4F2 (R-32), Halothane (R-23), 1,1,2,2-Tetrafluoroethane (R-134), 1,1,1-Halothane (R-143a), 1,1-C2H4F2 C2H4F2 (R-152a) etc.These can use separately, and the mix refrigerant that also can be used as more than 2 kinds uses.
Above-mentioned mix refrigerant can bought on the market, such as using R-407C (R-134a/R-125/R-32=52/25/23 quality %), R-410A (R-125/R-32=50/50 quality %), R-404A (R-125/R-143a/R-134a=44/52/4 quality %), R407E (R-134a/R-125/R-32=60/15/25 quality %), R410B (R-32/R-125=45/55 quality %), wherein, especially preferably contain mix refrigerant at least a among R-134a and the R-32.
Refrigeration agent compression freezing plant
Refrigeration agent compression freezing plant of the present invention has compressor, condensed device, and decompressor, and vaporizer are as the above-mentioned hydraulic fluid for refrigerator of refrigeration agent in the freezing plant, at these device internal recycle.This freezing plant can also have moisture eliminator.Such freezing plant has, air-conditionings such as domestic air conditioning, combined air conditioner; Cryogenic unit such as refrigerator, freezer; The industry refrigerator; And the car air-conditioner of hybrid vehicle, electromobile etc. etc.
Embodiment
Below specify the present invention with embodiment.
Below be described in the test method of the ester that makes in present embodiment and the comparative example:
＜kinematic viscosity and viscosity index〉be benchmark with JIS K-2283, use the Cannon-Fenske viscometer, the kinematic viscosity when being determined at 40 ℃ and 100 ℃ calculates viscosity index.
＜acid number〉be that benchmark is measured with JIS C-2101.
＜hydroxyl value〉be that benchmark is measured with JIS K-0070.
＜color and luster〉be that benchmark is measured with JOCS 2.2.1.4-1996.
＜volume specific resistance〉be benchmark with JIS C-2101, the volume specific resistance when being determined at 25 ℃ (T Ω m).
＜yield point〉be that benchmark is measured with JIS K-2269.
＜long-term low-temperature test〉whether sample 400g that amount of moisture is adjusted to below the 100ppm encloses in the stainless steel square jar, places 1000 hours in-28 ℃ low temperature storehouse, have crystallization to analyse life with visual method observation.
＜two phase separation temperatures〉sample (ester) of 0.6g and the refrigeration agent R-134a of 2.4g be added with heavy wall PYREX (login trade mark) pipe (total length 300mm, external diameter 10mm, internal diameter 6mm) with the ethanol bath cooling of dry ice, ratio with 1 ℃ of/minute kind heats up or cooling, in-70 ℃～+ 80 ℃ scope, two phase separation temperatures when being determined at high temperature and low temperature by range estimation.
＜sealed tube test〉the fluothane R-410A that amount of moisture is adjusted to sample 10g, 5g below the 200ppm, and the iron of long 10mm, copper, and each inclosure Glass tubing of tinsel of aluminium in, seal.After 175 ℃ of heating 14 days, measure acid number that contains the fluothane sample and the color and luster (APHA) of removing tinsel.
＜Falex rub(bing)test〉be benchmark with ASTM D-2670, the ratio of dividing with 150ml/ on one side in sample is blown into R134a, Yi Bian carry out the Falex rub(bing)test.The temperature of sample is set to 100 ℃, with after 150 pounds the loads trial run 1 minute, operation 2 hours under 250 pounds load again after operation is over, is measured the abrasion loss of pin.
Synthesis example 1: the modulation of ester
Pack in the 1 liter of 4 mouthfuls of flask that installs thermometer, nitrogen ingress pipe, stirrer and cooling tube alcohol mixture shown in the table 1 and saturated monocarboxylic acid, the equivalence ratio of the hydroxyl of alcohol mixture and the carboxyl of saturated monocarboxylic acid is 1: 1.1, under nitrogen gas stream, remove reaction water and under normal pressure, react while distill down at 220 ℃.Monitor hydroxyl value in the reaction, stopped reaction when it is lower than 2.0mg KOH/g., under the decompression of 1～5kPa carry out stripping, unreacted carboxylic acid was removed with 1 hour thereafter.Adding potassium hydroxide aqueous solution in the reaction mixture that obtains washes.Water washing process has repeated 5 times, makes the pH of draining become neutrality.Then,, add acidic white earth and sial soil series sorbent material, carry out adsorption treatment, so that their amount is the amount of the ester that obtains in theory, i.e. 1.0 quality % the ester layer that obtains decompression dehydration under 100 ℃, the condition of 1kPa.The time of the temperature of adsorption treatment, pressure and adsorption treatment, be respectively 100 ℃, 1kPa, and 3 hours.Thereafter, the strainer filtration with 1 μ m obtains ester (ester A).Ester A for obtaining uses aforesaid method, the kinematic viscosity when being determined at 40 ℃ and 100 ℃.The results are shown in table 1.
Synthesis example 2～7
Except using alcohol mixture shown in the table 1 and saturated monocarboxylic acid, obtain ester (ester B～G) with embodiment 1 same way.To each ester, the kinematic viscosity when being determined at 40 ℃ and 100 ℃ with above-mentioned way.The result is shown in table 1 in the lump.
Compare synthesis example 1～5
Except using alcohol mixture shown in the table 1 and saturated monocarboxylic acid, obtained ester (ester H～L) with embodiment 1 same way.To each ester, the kinematic viscosity when being determined at 40 ℃ and 100 ℃ with above-mentioned way.The result is shown in table 1 in the lump.
Table 1
Ester Measurement result
Alcohol mixture Saturated monocarboxylic acid (mole %) Ester The amount of the ester of molecular weight 370～10000 (mole %) Kinematic viscosity (mm 2/s)
Form *1(mole %) The value of relational expression *2 40℃ 100℃
NPG PE diPE
Synthesis example 1 87.0 12.9 0.1 1.48 2 ethyl hexanoic acid (95) 3,5,5 Trimethylhexanoic acid (5) A 12.9 10.62 2.571
2 68.0 30.5 1.5 0.30 2 ethyl hexanoic acid (97) caproic acid (3) B 30.8 15.23 3.235
3 50.0 48.0 2.0 0.48 2 ethyl hexanoic acid (100) C 48.0 22.01 4.055
4 47.0 50.0 3.0 0.35 2 ethyl hexanoic acid (100) D 50.0 23.14 4.187
5 89.85 10.1 0.05 2.25 2 ethyl hexanoic acid (88) 3,5,5 Trimethylhexanoic acid (12) E 10.1 10.68 2.593
6 70.0 29.1 0.9 0.48 2 ethyl hexanoic acid (90) 2 methyl caproic acid (7) valeric acid (3) F 29.5 14.22 3.111
7 80.0 19.0 1.0 0.24 2 ethyl hexanoic acid (93) 3,5,5-tri-methyl hexanoic acid (5) 2,5,5-tri-methyl hexanoic acid (1) 6,6-acid dimethyl (1) G 19.0 12.86 2.921
Compare synthesis example 1 100 - - - 2 ethyl hexanoic acid (100) H 0.0 7.473 2.043
2 47.0 53.0 - - 2 ethyl hexanoic acid (100) I 53.0 24.85 4.349
3 92.0 - 8.0 0 2 ethyl hexanoic acid (90) valeric acid (10) J 3.7 10.21 2.544
4 49.2 50.7 0.1 10.30 2 ethyl hexanoic acid (100) K 50.7 21.50 4.019
5 32.0 65.1 2.9 0.70 2 ethyl hexanoic acid (100) L 65.1 30.20 4.903
*1...NPG: neopentyl glycol, PE: tetramethylolmethane, diPE: Dipentaerythritol
*2...PE the mole %/(NPG the mole % * diPE the mole %)
As shown in Table 1, the ester of synthesis example 1～7 (ester A～G) satisfies the condition of the ester that the present invention uses, and the ester of synthesis example 1～5 (ester H～L) do not satisfy relatively.That is to say, compare the ester H～J of synthesis example 1～3, do not use the alcohol of 3 kinds.Relatively the relational expression value of the ester K of synthesis example 4 is 10.30, does not satisfy 0.2～7.0 scope.Relatively the viscosity of ester L in the time of 40 ℃ of synthesis example 5 is 30.20mm 2/ s, than higher, therefore the words of using separately can not satisfy the range of viscosities (6～28mm of lubricating oil composition of the present invention 2/ s).
Example 1: the performance evaluation of lubricating oil
1 resulting ester A has modulated lubricating oil (being called lubricating oil 1) with synthesis example.For lubricating oil 1, use above-mentioned way, carry out following test: the mensuration of the kinematic viscosity when 40 ℃ and 100 ℃, viscosity index, color and luster, acid number, hydroxyl value, volume specific resistance, yield point, two phase separation temperatures, long-term stable experiment, sealed tube test, and Falex test.The results are shown in table 2.
Example 2～7: the performance evaluation of lubricating oil
(ester B～G) has modulated lubricating oil (being called lubricating oil 2～7) with synthesis example 2～7 resulting esters.Carry out following test for various lubricating oil with above-mentioned way: the mensuration of the kinematic viscosity when 40 ℃ and 100 ℃, viscosity index, color and luster, acid number, hydroxyl value, volume specific resistance, yield point, two phase separation temperatures, long-term stable experiment, sealed tube test, and Falex test.The result is shown in table 2 in the lump.
Comparative example 1～5
(ester H～L) has modulated lubricating oil (being called lubricating oil 8～12) with synthesis example 1～5 resulting ester relatively.Carry out following test for various lubricating oil with above-mentioned way: the mensuration of the kinematic viscosity when 40 ℃ and 100 ℃, viscosity index, color and luster, acid number, hydroxyl value, volume specific resistance, yield point, two phase separation temperatures, long-term stable experiment, sealed tube test, and Falex test.The result is shown in table 2 in the lump.
Table 2
Ester content (quality %) Lubricating oil Measurement result
Kinematic viscosity (mm 2/s) Viscosity index Color and luster (APHA) Acid number (mgKOH/g) Hydroxyl value (mgKOH/g) Volume specific resistance (TQm) Yield point (℃) Long-term low-temperature test *1 Two phase separation temperatures Sealed tube test The Falex test
40℃ 100℃ Low temperature (℃) High temperature (℃) Color and luster (APHA) Acid number (mgKOH/g) Pin abrasion loss (mg)
Embodiment 1 A(100) 1 10.62 2.571 54 43 0.01 0.2 1.9 ＜-50 ○ ＜-50 80＜ 64 0.11 18
2 B(100) 2 15.23 3.235 61 63 0.01 0.5 3.4 ＜-50 ○ -38 80＜ 75 0.13 17
3 C(100) 3 22.01 4.055 66 40 0.01 0.8 4.9 ＜-50 ○ -28 80＜ 68 0.12 16
4 D(100) 4 23.14 4.187 69 39 0.01 0.7 5.3 ＜-50 ○ -27 80＜ 63 0.13 15
5 E(100) 5 10.68 2.593 58 42 0.01 0.1 1.4 ＜-50 ○ ＜-50 80＜ 68 0.12 19
6 F(100) 6 14.22 3.111 63 54 0.01 0.4 2.7 ＜-50 ○ -48 80＜ 76 0.09 17
7 G(100) 7 12.86 2.921 62 49 0.01 0.2 2.5 ＜-50 ○ ＜-50 80＜ 75 0.08 18
Comparative example 1 H(100) 8 7.473 2.043 48 49 0.01 0.6 0.3 ＜-50 ○ ＜-50 80＜ 79 0.15 20
2 I(100) 9 24.85 4.349 67 46 0.01 0.5 4.2 -47.5 × -29 80＜ 70 0.14 15
3 J(100) 10 10.21 2.544 64 68 0.01 0.4 0.4 ＜-50 ○ ＜-50 80＜ 90 0.17 19
4 K(100) 11 21.50 4.019 69 40 0.01 0.8 5.4 ＜-50 × -29 80＜ 69 0.13 17
5 L(100) 12 30.20 4.903 76 40 0.01 0.9 6.3 -40 △ -23 80＜ 65 0.11 14
* 1... kept 1000 hours down at-28 ℃.Be designated as zero when will not have precipitate, be designated as △ when precipitate is arranged, gelation or be designated as when solidifying *.
As shown in Table 2, the lubricating oil that satisfies condition of the present invention of example 1～7 (lubricating oil 1～7), the excellent stability that viscosity is low, volume resistance is high, tool does not produce precipitate yet in long-term low-temperature test.These lubricating oil 1～7, yield point is low, and it is good to see with the intermiscibility of fluothane refrigeration agent from two phase separation temperatures, and it is also few to test the oxidative degradation that sees hot from the seal of tube, can satisfy the performance requriements of other refrigerator oils, is the lubricating oil of excellent property.In contrast to this, by (lubricating oil 8～10 of ester H～L) constitute, volume specific resistance is low or produced precipitate when long-term low-temperature test with any synthetic ester in the alcohol that does not contain 3 kinds that the present invention uses.By the alcohol mixture that has used above-mentioned 3 kinds but do not satisfy the lubricating oil 11 that the ester K of relational expression constitutes, when long-term low-temperature test, produced precipitate.Lubricating oil 12 usefulness above-mentioned 3 kinds alcohol mixture and also satisfy the above-mentioned relation formula, but the kinematic viscosity height in the time of 40 ℃, low-temperature stability is also poor.
Industrial applicability
Lubricating oil composition of freezer of the present invention has low viscosity, the high and good advantage of low-temperature stability of volume intrinsic resistance. And because and fluothane, the particularly intermiscibility without chlorofluoromethane good, therefore be suitable as to have used without the ice machine oil of chlorofluoromethane solvent or be mixed with said composition and use with hydraulic fluid for refrigerator without the chlorofluoromethane cold-producing medium. Lubricating oil composition of freezer of the present invention and contain this lubricant oil composite and without the hydraulic fluid for refrigerator of chlorofluoromethane cold-producing medium, specifically be used in the air conditioner of domestic air conditioning, combined air conditioner etc.; The Cryo Equipment of refrigerator, freezer etc.; The industry refrigerator; And the compressor of the used for automobile air conditioning of hybrid vehicle, Electric power car etc. etc.

Claims (5)

1. lubricating oil composition of freezer, it is being that the mixed ester that 5～10 saturated monocarboxylic acid makes is a main component by alcohol mixture and carbon number; This alcohol mixture is made of the tetramethylolmethane of the neopentyl glycol of 1～90 mole of %, 10～80 moles of % and the Dipentaerythritol of 0.01～20 mole of %, and satisfies following relational expression:
Formula 1
Figure A2005101289440002C1
And the kinematic viscosity of said composition in the time of 40 ℃ is 6～28mm 2/ s.
2. lubricating oil composition of freezer as claimed in claim 1,85 moles of saturated monocarboxylic acid that constitute above-mentioned mixed ester are the saturated monocarboxylic acid with α-side chain more than the %.
3. lubricating oil composition of freezer as claimed in claim 1 or 2, molecular weight is that the amount of 370～1000 ester is 10～65 moles of % in the above-mentioned mixed ester.
4. hydraulic fluid for refrigerator is by as each described lubricating oil composition of freezer of claim 1～3 with do not have the chlorofluoromethane refrigeration agent and constitute.
5. freezing plant, it is the refrigeration agent compression freezing plant with compressor, condenser, decompressor and vaporizer, uses hydraulic fluid for refrigerator as claimed in claim 4.
CNA2005101289448A 2004-12-02 2005-12-02 Lubricating oil composition of freezer Pending CN1782042A (en)

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