CN1869177A - Refrigeration lubricant composition - Google Patents
Refrigeration lubricant composition Download PDFInfo
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- CN1869177A CN1869177A CNA2006100937128A CN200610093712A CN1869177A CN 1869177 A CN1869177 A CN 1869177A CN A2006100937128 A CNA2006100937128 A CN A2006100937128A CN 200610093712 A CN200610093712 A CN 200610093712A CN 1869177 A CN1869177 A CN 1869177A
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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
- 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
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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
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- 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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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Lubricants (AREA)
Abstract
This invention provides a lubricating oil compound used for refrigerator with low viscosity, upstanding lubricating property, and good long-term stability at low temperature, especially the lubricating oil compound used for refrigerator using non-chlorofluorocarbon cryogen. This lubricating oil compound comprises the ester made by reaction of mixed alcohol and mixed saturated straight chain carboxyl acid at specialized ratio, and the mobile viscosity of this compound at 40Deg C is 6-28mm<SUP>2</SUP>/s, the said mixed alcohol comprises 10-50mol% neopentyl glycol, 50-89mol% normosterol and 0.03-3mol% dipentaerythritol, the said mixed saturated straight chain carboxyl acid comprises 70-95mol% pentanoic acid and enanthic acid, and 5-30mol% octanoic acid.
Description
Technical field
The present invention relates to lubricating oil composition of freezer, relate to non-chlorine class fluon refrigeration agent with ice machine oil composition, the freezing plant that contains the hydraulic fluid for refrigerator of this lubricating oil composition and utilize this hydraulic fluid for refrigerator particularly.
Background technology
Chloride fluon refrigeration agent is used for refrigerator, air conditioning machinery etc. always.But, in recent years because the problems such as destruction of ozonosphere constantly convert chloride fluon refrigeration agent to 1,1,1,2-Tetrafluoroethane (R-134a), pentafluoride ethane (R-125), C2H4F2 C2H4F2 (R-32) and these non-chlorine class fluon refrigeration agents such as mixed solvent.Proposed thereupon various with the refrigerator oil (hereinafter referred to as refrigerator oil) of the high polyol ester of non-chlorine class fluon intermiscibility as base oil.
For refrigerator oil,, except requiring the intermiscibility with above-mentioned non-chlorine fluon refrigeration agent, also require various performances such as thermostability, hydrolytic resistance, low-temperature fluidity, electrical insulating property in order to ensure the stability of above-mentioned refrigerator, air conditioning machinery etc.Wherein, consider the actual hindered ester that uses the excellent heat resistance that forms by carboxylic acid with side chain and tetramethylolmethane from hydrolytic resistance and with the intermiscibility aspect of non-chlorine class fluon.For example, in patent documentation 1, disclose the ester that forms with mixed fatty acid refrigerator oil, and be documented in pyritous stability and improve as main component by tetramethylolmethane and 2 ethyl hexanoic acid and 3,5,5 Trimethylhexanoic acid.In addition, the intermiscibility of ester that record is formed by neopentyl glycol and branched carboxylic acids in patent documentation 2 and fluon, thermostability etc. are good.In addition, in patent documentation 3,, put down in writing the refrigerator oil that has added straight chain fatty acid as the refrigerator oil of oilness excellence.
On the other hand, because the raising of Environmental awareness in recent years for refrigerator or air conditioning machinery etc., also requires energy saving.In order to make refrigerator oil have energy saving, reduce viscosityization and be effective means, thereby be devoted to reduce the refrigerator oil viscosity.In order to reduce the refrigerator oil viscosity, it is effective using the ester that is formed by dibasic alcohol such as neopentyl glycol of excellences such as that viscosity is lower than pentaerythritol ester and hydrolytic resistance, thermostability, viscosity.But these esters viscosity sometimes are low, and oilness is not enough.
As the method that improves oilness, just like the method for above-mentioned patent documentation 3 described use straight-chain fatty acid esters.But the ester of well-known this uses straight chain fatty acid is owing to having crystallinity, thereby the reduction of low temperature permanent stability.
Therefore, expect a kind of low-temperature stability excellence and the refrigerator oil that viscosity is low, oilness is excellent.
[patent documentation 1] spy opens flat 10-8084 communique
[patent documentation 2] spy opens flat 5-209171 communique
[patent documentation 3] spy opens flat 11-228984 communique
Summary of the invention
The object of the invention is to provide low viscosity, oilness is good and the lubricating oil composition of freezer of the permanent stability excellence of low temperature range, particularly uses the lubricating oil composition of freezer of non-chlorine fluon refrigeration agent.The present invention also aims to provide hydraulic fluid for refrigerator that uses above-mentioned used for refrigerator lubricating composition and the refrigeration agent compression freezing plant that uses above-mentioned hydraulic fluid for refrigerator.
The inventor furthers investigate the oilness and the low-temperature stability of the low viscosity lubricating composition of the refrigerator that is used to utilize non-chlorine class fluon refrigeration agent, by making up the molecular designing that various polynary alcohol and carboxylic acids carry out ester.Found that: the saturated straight chain carboxylic acid that mixes by alcohol mixture that makes the neopentyl glycol, tetramethylolmethane and the Dipentaerythritol that contain specified amount and the valeric acid that contains specified amount (carbonatoms is 5 saturated straight chain carboxylic acid), enanthic acid (carbonatoms is 7 saturated straight chain carboxylic acid) and sad (carbonatoms is 8 saturated straight chain carboxylic acid) reacts the ester that makes and can address the above problem under the condition of the relation that satisfies certain amount, thereby has finished the present invention.
Used for refrigerator lubricating composition of the present invention contains by alcohol mixture and mixes the ester that the saturated straight chain carboxylic acid obtains, described alcohol mixture contains the tetramethylolmethane of the neopentyl glycol of 10～50 moles of %, 50～89 moles of % and the Dipentaerythritol of 0.03～3 mole of %, described mixing saturated straight chain carboxylic acid contains the sad of the valeric acid of 70～95 moles of % and enanthic acid and 5～30 moles of %, and this ester is that reaction makes under the condition of following relational expression satisfying:
And the kinematic viscosity of said composition under 40 ℃ is 6～28mm
2/ s.
The present invention also provides hydraulic fluid for refrigerator, and this hydraulic fluid for refrigerator contains above-mentioned lubricating oil composition of freezer and non-chlorine class fluon solvent.
The present invention also provides freezing plant, and this freezing plant is the refrigeration agent compression freezing plant that possesses compressor, condenser, expansion texture and vaporizer, and utilizes above-mentioned hydraulic fluid for refrigerator.
Lubricating oil composition of freezer viscosity of the present invention is low, oilness good and long-term low-temperature stability is good.Said composition is essential also excellent with intermiscibility, thermotolerance and electrical insulating property non-chlorine class fluon refrigeration agent as lubricating oil composition of freezer.Therefore, composition of the present invention is as utilizing non-chlorine class fluon refrigeration agent, particularly contain 1,1,1, the ice machine oil of at least a kind non-chlorine class fluon refrigeration agent of 2-Tetrafluoroethane and methylene fluoride or with hydraulic fluid for refrigerator that non-chlorine class fluon refrigerant mixed obtains be useful, the saving that also helps various freezing plant dyestuffs to consume.
Embodiment
Below to the contained ester of composition of the present invention, contain this ester lubricating oil composition of freezer, contain the hydraulic fluid for refrigerator of said composition and utilize the refrigeration agent compression freezing plant of this hydraulic fluid for refrigerator to describe.
(I) ester
It at the contained ester of lubricating oil composition of freezer of the present invention the mixture of the ester that makes by 3 kinds of alcohol (alcohol mixture) and 3 kinds of saturated straight chain carboxylic acids (mixing the saturated straight chain carboxylic acid).Particularly, this ester be make the tetramethylolmethane of the neopentyl glycol that contains 10～50 moles of %, 50～89 moles of % and 0.03～3 mole of % Dipentaerythritol alcohol mixture and contain the valeric acid of 70～95 moles of % and the sad mixing saturated straight chain carboxylic acid of enanthic acid and 5～30 moles of % reaction makes under the condition of following relational expression satisfying
The inventor finds: when making above-mentioned alcohol mixture and mixing the saturated straight chain carboxylic acid reaction, in these compositions, neopentyl glycol and mix valeric acid in the saturated straight chain carboxylic acid and the relation of sad amount can influence the long-term low-temperature stability and the oilness of gained low viscosity ester in the alcohol mixture.That is, find: make it satisfy the above-mentioned relation formula by the molecular designing of carrying out ester, can make the ester of low viscosity, the good and long-term low-temperature stability excellence of oilness.
As mentioned above, the alcohol mixture as the raw material of above-mentioned ester contains neopentyl glycol, tetramethylolmethane and Dipentaerythritol.In the present invention, use tetramethylolmethane, use neopentyl glycol in order to realize lowering viscousity, use Dipentaerythritol in order to make long-term low-temperature stability excellence in addition for the ester that makes the electrical insulating property excellence.
Content as neopentyl glycol in the alcohol mixture of the raw material of above-mentioned ester is 10～50 moles of %, is preferably 12～48 moles of %, more preferably 15～46 moles of %.When the content of neopentyl glycol was lower than 10 moles of %, the long-term low-temperature stability of gained ester was not enough, sometimes the viscosity that can not obtain to expect.When surpassing 50 moles of %, the oilness of gained ester is not enough, and electrical insulating property is also not enough.
Content as tetramethylolmethane in the alcohol mixture of the raw material of above-mentioned ester is 50～89 moles of %, is preferably 52～85 moles of %, more preferably 54～80 moles of %.When the content of this season penta tetrol was lower than 50 moles of %, the oilness of gained ester was not enough, and electrical insulating property is also not enough.If when surpassing 89 moles of %, the long-term low-temperature stability of gained ester is not enough.
Content as Dipentaerythritol in the alcohol mixture of the raw material of above-mentioned ester is 0.03～3 mole of %, is preferably 0.04～2.8 mole of %, more preferably 0.05～2.5 mole of %.When the content of Dipentaerythritol was lower than 0.03 mole of %, the low-temperature stability of gained ester was not enough.If surpass 3 moles of %, the fluon intermiscibility variation of gained ester, and the viscosity that can not obtain to expect sometimes.
As mentioned above, the mixing saturated straight chain carboxylic acid (mixing the saturated straight chain monocarboxylic acid) as the raw material of above-mentioned ester contains valeric acid, enanthic acid and sad.In the present invention, in order to obtain high lubricity, use straight chain fatty acid, particularly good sad (carbonatoms is 8 saturated straight chain carboxylic acid) of oilness is as essential composition, in addition, in order to improve the low-temperature stability that uses under the sad situation, be inferior to the straight-chain odd number acid that sad oilness is better, low-temperature stability is also excellent, i.e. valeric acid (carbonatoms is 5 saturated straight chain carboxylic acid) and enanthic acid (carbonatoms is 7 saturated straight chain carboxylic acid) though use.By using such mixing saturated straight chain carboxylic acid, can make the viscosity with expectation and the ester of oilness excellence.
Add up to 70～95 moles of % as the valeric acid in the mixing saturated straight chain carboxylic acid of the raw material of above-mentioned ester and the content of enanthic acid, be preferably 72～93 moles of %, more preferably 74～91 moles of %.When the total amount of valeric acid and enanthic acid was lower than 70 moles of %, the long-term low-temperature stability of gained ester was not enough, if when surpassing 95 moles of %, the oilness of gained ester is not enough.
In order to make the contained ester of composition of the present invention, make above-mentioned alcohol mixture and mix the saturated straight chain carboxylic acid and react satisfying under the condition of following relational expression:
If the value of above-mentioned relation formula in 5～25 scope, can make the ester of oilness and long-term low-temperature stability excellence.
Reaction when making above-mentioned ester is undertaken by the esterification or the transesterification reaction of routine.Preferred ratio of suitably regulating above-mentioned alcohol mixture and mixed fatty acid, the hydroxyl value that makes the gained mixed ester is 5.0mgKOH/g or following, and acid number is 0.05mgKOH/g or following.
The preparation method of the ester that uses for the present invention can prepare in the scope of not destroying above-mentioned performance by any method, is not particularly limited.Above-mentioned ester for example can followingly make.At first,, sneak into and mix the saturated straight chain carboxylic acid, make carboxyl reach 1.0～1.5 equivalents, perhaps consider, preferably reach 1.05～1.3 equivalents, and add catalyzer as required by the viewpoint of production efficiency and economy with respect to the hydroxyl of 1 equivalent alcohol mixture.In nitrogen gas stream, under 220～260 ℃, make this mixture reaction 3～15 hours, when hydroxyl value reaches moment below the 2.0mgKOH/g, under reduced pressure remove excess carboxylic acid.Afterwards, utilize alkali to carry out depickling after, utilize the operation such as adsorption treatment, steaming of atlapulgite, acidic white earth and synthetic adsorbent alone or in combination.
(II) ice machine oil composition
With the said composition total mass is benchmark, lubricating oil composition of freezer of the present invention preferably contains 80 quality % or above above-mentioned ester, further preferably contains 90 quality % or above above-mentioned ester, than outside, in the scope of not damaging performance of the present invention, can contain other esters, additive etc.
As above-mentioned other ester, can enumerate that for example to contain carbonatoms be that 5～10 neopentyl glycol and carbonatoms are 5～10 monocarboxylic ester.
As required, lubricating oil composition of freezer of the present invention can suitably contain known additive, for example phenol antioxidant; Metal agents such as benzotriazole, thiadiazoles, dithiocar-bamate; Sour trapping agent such as epoxy compounds or carbimide; Additives such as Phosphorus extreme pressure agent.Containing proportional is arbitrarily.
The kinematic viscosity of lubricating oil composition of freezer of the present invention under 40 ℃ is 6～28mm
2/ s.In addition, according to obtaining excellent oilness and considering, be preferably 7～20mm with the viewpoint of the intermiscibility of non-chlorine class fluon refrigeration agent and the good startability by using the refrigerator that this lubricating oil composition brings and the viewpoint of energy saving
2/ s, more preferably 8～18mm
2/ s.
Acid number to lubricating oil composition of freezer of the present invention is not particularly limited.Be preferably 0.05mgKOH/g or following, more preferably 0.03mgKOH/g or following, more preferably 0.01mgKOH/g or following.When acid number surpasses 0.05mgKOH/g, may corroding metal, and hydrolytic resistance is not enough sometimes.
Hydroxyl value to lubricating oil composition of freezer of the present invention is not particularly limited.Be preferably 5.0mgKOH/g or following, 3.0mgKOH/g or following more preferably, more preferably 2.0mgKOH/g or following most preferably is 1.0mgKOH/g or following.When hydroxyl value surpasses 5.0mgKOH/g, state in the use in the machine of composition, may give as the sealing agent of organic materials etc. and bring detrimentally affect.In addition, bring detrimentally affect may for contained additive.
(III) hydraulic fluid for refrigerator
Hydraulic fluid for refrigerator of the present invention contains above-mentioned lubricating oil composition of freezer and non-chlorine class fluon refrigeration agent.It to proportional being not particularly limited that contain of lubricating oil composition of freezer and non-chlorine class fluon refrigeration agent, preferably is lubricating oil composition of freezer by quality ratio: non-chlorine class fluon refrigeration agent=10: 90～90: 10.If the blend level of non-chlorine class fluon refrigeration agent is higher than above-mentioned scope, then the viscosity of gained hydraulic fluid for refrigerator reduces, and may cause insufficient lubrication.If be lower than above-mentioned scope, when the gained hydraulic fluid for refrigerator was used for machine, freezing efficiency may reduce.
As above-mentioned non-chlorine class fluon refrigeration agent, for example can enumerate 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 refrigeration agents can use separately, can also make 2 kinds or above mix refrigerant use.
Above-mentioned mix refrigerant has commercially available, can use for example 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 %), R-407E (R-134a/R-125/R-32=60/15/25 quality %), R-410B (R-32/R-125=45/55 quality %) etc.Especially preferably contain at least a kind mix refrigerant among R-134a and the R-32.
(IV) refrigeration agent compression freezing plant
Hydraulic fluid for refrigerator of the present invention with composition or the of the present invention freezing working fluid that contains said composition can be used for having at least compressor, condenser, expansion texture and vaporizer, also have a freezing plant of moisture eliminator as required.As such freezing plant, can enumerate air conditioner for automobile of air conditioning machinery, oily electric hybrid vehicle or used for electric vehicle such as low temperature machines such as refrigerator or industrial refrigerator, room air conditioner, cabinet air conditioner etc. particularly.
Embodiment
Describe the present invention in detail below by embodiment, still, the present invention is not subjected to the qualification of these embodiment.
Below, the test method of the ester that notebook embodiment and comparative example are prepared.
＜kinematic viscosity and viscosity index 〉: according to JIS K-2283, use the Cannon-Fenske kinematic viscosimeter, measures the kinematic viscosity of 40 ℃ and 100 ℃, the calculating viscosity index.
＜acid number 〉: measure according to JIS C-2101.
＜hydroxyl value 〉: measure according to JIS K-0070.
＜tone 〉: measure according to JOCS2.2.1.4-1996.
＜volume specific resistance 〉: according to JIS C-2101, measure 25 ℃ volume specific resistance (T Ω m).
＜pour point 〉: measure according to JIS K-2269.
＜long-term low temperature test 〉: the sample (ester) that the 400g amount of moisture is adjusted to below the 100ppm is put into stainless steel side jar, it was placed 1000 hours in-30 ℃ low temperature storehouse, confirm whether to separate out crystallization by naked eyes.
＜two phase separation temperatures 〉: 0.6g sample (ester) and 2.4g refrigeration agent R-134a or R-407C enclosed utilize ethanol bath refrigerative heavy wall パ イ レ ッ Network ス (registered trademark) pipe (the total length 300mm that is placed with dry ice, external diameter 10mm, internal diameter 6mm), heat up or cooling with 1 ℃/minute speed ,-30 ℃～+ 20 ℃ the cryogenic two separate temperature of the visual mensuration of scope.
＜sealed tube experiment 〉: in Glass tubing, enclose 10g and in advance moisture concentration is adjusted to each 1 of iron plate, copper sheet and the aluminium flake that sample (ester), 5g fluon R-410A and diameter below the 200ppm is 1.6mm, long 50mm, and seal.After 14 days, measure acid number that contains the fluon sample and the tone (APHA) of removing tinsel at 175 ℃ of following heating glass pipes.
＜Falex rub(bing)test 〉: according to ASTM D-2670, the speed of dividing with 150ml/ is blown into R-134a in sample, simultaneously the following Falex rub(bing)test of carrying out.At first, specimen temperature is set at 100 ℃, the heavy burden trial run that utilizes 150 pounds is after 1 minute, and operation is 1 hour under 300 pounds heavy burden, the abrasion loss of pin behind the mensuration end of run.
(embodiment 1.1: the preparation of ester)
In 1 liter of 4 mouthfuls of flask of thermometer, nitrogen ingress pipe, stirrer and prolong are housed, alcohol mixture shown in the table 1 and mixed carboxylic acid pack into, make that the hydroxyl of this alcohol mixture and mixed carboxylic acid's the equivalence ratio of carboxyl is 1: 1.1, under nitrogen gas stream, at 220 ℃, distill on one side down and remove reaction water, under normal pressure react on one side.In reaction, the monitoring hydroxyl value is in the moment that drops to 2.0mgKOH/g, termination reaction.Then, under the decompression of 1～5kPa, carry out stripping, with removing unreacted carboxylic acid in 1 hour.Add potassium hydroxide aqueous solution to the gained reaction mixture and wash, washing repeats 5 times, makes the pH of waste water reach neutral.Then, under 100 ℃, the condition of 1kPa, gained ester layer is carried out decompression dehydration, add acidic white earth respectively and silica-alumina class sorbent material carries out adsorption treatment, make that gained ester amount reaches 1.0 quality % in theory.Adsorption treatment temperature, pressure and adsorption treatment time are respectively 100 ℃, 1kPa and 3 hours.Use 1 micron strainer to filter at last, make ester (with it as ester A).The composition of gained ester A is as shown in table 1.
(embodiment 1.2～1.6)
Except using alcohol mixture shown in the table 1 and mixed carboxylic acid, operate similarly to Example 1, make ester (ester B～F).The composition of gained ester B～E is as shown in table 1.
(comparative example 1.1～1.8)
Except using alcohol mixture shown in the table 1 and mixed carboxylic acid, operate similarly to Example 1, make ester (ester G～N).The composition of gained ester G～N is as shown in table 1.
[table 1]
| Ester | |||||||||||
| Alcohol mixture (mole %) | Mixed carboxylic acid (mole %) | Relational expression *2Value | Ester | ||||||||
| NPG | PE | diPE | Valeric acid (C5) | Enanthic acid (C7) | Sad (C8) | 2 ethyl hexanoic acid | Different n-nonanoic acid | ||||
| Embodiment | 1.1 | 34.5 | 65.0 | 0.50 | 45.0 | 40.0 | 15.0 | - | - | 11.5 | A |
| 1.2 | 42.5 | 57.4 | 0.08 | 50.0 | 24.0 | 26.0 | - | - | 22.1 | B | |
| 1.3 | 38.0 | 80.0 | 2.00 | 60.0 | 30.0 | 10.0 | - | - | 6.3 | C | |
| 1.4 | 40.0 | 59.7 | 0.30 | 50.0 | 30.0 | 20.0 | - | - | 16.0 | D | |
| 1.5 | 20.0 | 76.0 | 2.00 | 20.0 | 55.0 | 25.0 | - | - | 25.0 | E | |
| 1.6 | 20.0 | 78.9 | 1.10 | 65.0 | 18.0 | 17.0 | - | - | 5.2 | F | |
| Comparative example | 1.1 | 26.5 | 70.0 | 1.50 | 15.0 | 70.0 | 15.0 | - | - | 28.5 | G |
| 1.2 | 19.7 | 80.0 | 0.30 | 55.0 | 35.0 | 10.0 | - | - | 3.6 | H | |
| 1.3 | 33.5 | 66.0 | 0.50 | - | - | 15.0 | 80.0 | 5.0 | - | I | |
| 1.4 | 20.0 | 80.0 | 0 | 20.0 | 55.0 | 25.0 | - | - | 25.0 | J | |
| 1.5 | 4.7 | 94.8 | 0.40 | 4.5 | 85.0 | 10.5 | - | - | 11.0 | K | |
| 1.6 | 31.5 | 66.0 | 2.50 | 37.0 | 23.0 | 40.0 | - | - | 34.1 | L | |
| 1.7 | 10.0 | 90.0 | 10.0 | 20.0 | 55.0 | 25.0 | - | - | 12.5 | M | |
| 1.8 | 43.7 | 55.0 | 1.30 | 60.0 | 37.0 | 3.0 | - | - | 2.2 | N | |
* 1 ... NPG: neopentyl glycol, PE: tetramethylolmethane, diPE: Dipentaerythritol
* 2 ... the mole % of (the mole % of sad mole %/valeric acid) * NPG
Make the ester A～N shown in the table 1.Wherein, the condition of the ester of the discontented unabridged version invention of the ester G～N of comparative example 1.1～1.8 use.That is, the relation (value of relational expression) of the amount of valeric acid, enanthic acid and the neopentyl glycol of comparative example 1.1 and 1.2 ester G and H is improper.The ester I of comparative example 1.3 does not contain valeric acid and enanthic acid.The ester J of comparative example 1.4 does not contain Dipentaerythritol.The content of the neopentyl glycol of the ester K of comparative example 1.5 is low, the content height of tetramethylolmethane.For the ester L and the N of comparative example 1.6 and 1.8, the total amount of valeric acid and enanthic acid and sad content are outside scope, and the value of relational expression is also improper.The content height of the Dipentaerythritol of the ester M of comparative example 1.7.
(embodiment 2.1)
The ester A that the foregoing description 1.1 is made makes lubricating oil (lubricating oil 1).By aforesaid method, measure kinematic viscosity, viscosity index, tone, acid number, hydroxyl value, volume specific resistance mensuration, pour point and the two-phase separation temperature (low temperature) of 140 ℃ of lubricating oil and 100 ℃.In addition, carry out long-term low-temperature test, shield test reactor and Falex rub(bing)test.The result is as shown in table 2.
(embodiment 2.2～2.6)
Ester B～F that the foregoing description 1.2～1.6 is made makes lubricating oil (lubricating oil 2～6).Each lubricating oil is carried out the test identical with embodiment 2.1.The result is shown in table 2 in the lump.
(comparative example 2.1～2.8)
Ester G～N that the foregoing description 1.1～1.8 is made makes lubricating oil (lubricating oil 7～14).Each lubricating oil is carried out the test identical with embodiment 2.1.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 | Tone (APHA) | Acid number (mgKOH/g) | Hydroxyl value (mgKOH/g) | Volume specific resistance (T Ω m) | Pour point (℃) | Long-term low-temperature test *1 | Two phase separation temperatures | Sealed tube test | The Falex rub(bing)test | |||||||
| 40℃ | 100℃ | R-407C (low temperature) | R-134a (low temperature) | Tone (APHA) | Acid number (mgKOH/g) | Pin abrasion loss (mg) | |||||||||||
| Embodiment | 2.1 | A(100) | 1 | 13.0 | 3.30 | 126 | 43 | 0.01 | 0.2 | 2.5 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 64 | 0.25 | 6 |
| 2.2 | B(100) | 2 | 12.8 | 3.24 | 122 | 46 | 0.01 | 0.3 | 2.8 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 61 | 0.24 | 5 | |
| 2.3 | C(100) | 3 | 12.0 | 3.05 | 112 | 51 | 0.01 | 0.2 | 2.4 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 70 | 0.27 | 8 | |
| 2.4 | D(100) | 4 | 8.1 | 2.31 | 95 | 39 | 0.01 | 0.1 | 1.6 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 58 | 0.20 | 6 | |
| 2.5 | E(100) | 5 | 17.6 | 3.85 | 111 | 42 | 0.01 | 0.1 | 2.2 | -35 | ○ | -6℃ | -14℃ | 61 | 0.24 | 5 | |
| 2.6 | F(100) | 6 | 15.4 | 3.40 | 92 | 50 | 0.01 | 0.4 | 1.9 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 72 | 0.22 | 6 | |
| Comparative example | 2.1 | G(100) | 7 | 15.9 | 3.70 | 121 | 75 | 0.01 | 0.4 | 1.9 | ＜-50 | × | -15℃ | -24℃ | 93 | 0.26 | 6 |
| 2.2 | H(100) | 8 | 14.0 | 3.40 | 118 | 39 | 0.01 | 0.1 | 1.6 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 80 | 0.23 | 12 | |
| 2.3 | I(100) | 9 | 27.0 | 4.62 | 84 | 50 | 0.01 | 0.4 | 1.9 | -20 | ○ | Below-30 ℃ | Below-30 ℃ | 56 | 0.03 | 16 | |
| 2.4 | J(100) | 10 | 17.3 | 3.81 | 100 | 47 | 0.01 | 0.4 | 1.8 | -35 | × | -7℃ | -15℃ | 61 | 0.29 | 5 | |
| 2.5 | K(100) | 11 | 28.9 | 4.21 | 116 | 48 | 0.01 | 0.9 | 0.1 | -30 | × | Below 20 ℃ | 17℃ | 67 | 0.28 | 6 | |
| 2.6 | L(100) | 12 | 15.8 | 3.82 | 113 | 65 | 0.01 | 0.3 | 3.5 | -35 | × | 8℃ | 0℃ | 89 | 0.29 | 4 | |
| 2.7 | M(100) | 13 | 22.1 | 4.82 | 127 | 51 | 0.01 | 0.4 | 1.9 | -25 | ○ | 17℃ | 9℃ | 72 | 0.28 | 5 | |
| 2.8 | N(100) | 14 | 11.0 | 2.90 | 107 | 49 | 0.01 | 0.9 | 0.1 | ＜-50 | ○ | Below-30 ℃ | Below-30 ℃ | 73 | 0.26 | 21 | |
* 1 ... kept 100 hours down at-30 ℃.There is not the situation of precipitate to be designated as zero, have the situation of precipitate to be designated as *.
As shown in Table 2, the lubricating oil of embodiment (lubricating oil 1～6) is 6～28mm 40 ℃ kinematic viscosity
2/ s has desired viscosity, has excellent lubrication as can be known according to above-mentioned kinematic viscosity and Falex rub(bing)test, and, even also have the excellent stability that in long-term low-temperature test, does not also produce precipitate.In addition, the pour point of these lubricating oil 1～6 is low, good with the intermiscibility of fluon refrigeration agent as can be known from two phase separation temperatures, and, few by sealed tube test thermooxidizing deterioration as can be known, satisfying other the desired properties as refrigerator oil, thereby be good refrigerator oil, is non-chlorine class fluon refrigeration agent refrigerator oil especially.
The discontented unabridged version scope of invention of ester relative therewith, that the lubricating oil of comparative example (lubricating oil 7～14) is contained, therefore, oilness and long-term low-temperature stability are all not enough.That is, comparative example 2.1 and 2.4～2.6 lubricating oil (lubricating oil 7 and 10～12) are in long-term low-temperature stability test, and stability is not enough owing to produce precipitate.Comparative example 2.2,2.3 and 2.8 lubricating oil (lubricating oil 8,9 and 14) in the Falex rub(bing)test, the pin serious wear, oilness is not enough.And though the long-term low-temperature stability of the lubricating oil 13 of comparative example 2.7 and oilness excellence, two separate temperature height is with the non-constant of the intermiscibility of fluon refrigeration agent.
Industrial applicability
Lubricating oil composition of freezer viscosity of the present invention is low, and lubricity is good, and long-term low-temperature stability is good. In addition, intermiscibility, heat resistance and the electrical insulating property of said composition necessary and non-chlorine class fluon cold-producing medium as lubricating oil composition of freezer are also excellent. Therefore, composition of the present invention is as utilizing non-chlorine class fluon cold-producing medium, particularly contain 1,1,1, the ice machine oil of at least a kind non-chlorine class fluon cold-producing medium of 2-HFC-134a and difluoromethane or with hydraulic fluid for refrigerator that non-chlorine class fluon refrigerant mixed obtains be useful, the saving that also helps various refrigerating plant dyestuffs to consume. Lubricating oil composition of freezer of the present invention and contain this lubricating oil and the hydraulic fluid for refrigerator of non-chlorine class fluon cold-producing medium can be used for the air conditioner for automobile etc. of the air conditioners such as low temperature machine, industrial refrigerator, room air conditioner, cabinet air conditioner, oily electric hybrid vehicle or the used for electric vehicle such as refrigerator particularly.
Claims (3)
1, a kind of composition, it is the lubricating oil composition of freezer that contains the ester that is obtained by alcohol mixture and mixing saturated straight chain carboxylic acid, described alcohol mixture contains the tetramethylolmethane of the neopentyl glycol of 10～50 moles of %, 50～89 moles of % and the Dipentaerythritol of 0.03～3 mole of %, described mixing saturated fatty acid contains the sad of the valeric acid of 70～95 moles of % and enanthic acid and 5～30 moles of %
This ester is to make satisfying under the condition of following relational expression reaction:
And the kinematic viscosity of said composition under 40 ℃ is 6～28mm
2/ s.
2, a kind of hydraulic fluid for refrigerator, it contains described lubricating oil composition of freezer of claim 1 and non-chlorine class fluon solvent.
3, a kind of freezing plant, it is the refrigeration agent compression freezing plant that possesses compressor, condenser, expansion texture and vaporizer, and uses the described hydraulic fluid for refrigerator of claim 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005156071A JP4806967B2 (en) | 2005-05-27 | 2005-05-27 | Lubricating oil composition for refrigerator |
| JP2005156071 | 2005-05-27 | ||
| JP2005-156071 | 2005-05-27 |
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| Publication Number | Publication Date |
|---|---|
| CN1869177A true CN1869177A (en) | 2006-11-29 |
| CN1869177B CN1869177B (en) | 2012-01-04 |
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| CN2006100937128A Active CN1869177B (en) | 2005-05-27 | 2006-05-26 | Refrigeration lubricant composition |
Country Status (4)
| Country | Link |
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| JP (1) | JP4806967B2 (en) |
| KR (1) | KR101237765B1 (en) |
| CN (1) | CN1869177B (en) |
| MY (1) | MY144475A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812349A (en) * | 2010-05-11 | 2010-08-25 | 上海海都化学科技有限公司 | Lubricating oil and grease base oil, and preparation method and applications thereof |
| CN104271547A (en) * | 2012-04-26 | 2015-01-07 | 日油株式会社 | Ester for refrigerator oils and method for producing same |
| CN106281575A (en) * | 2007-04-18 | 2017-01-04 | 出光兴产株式会社 | Lubricating oil composition for refrigerator and compressor using the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093822B (en) * | 2013-02-05 | 2016-11-16 | 科聚亚公司 | Refrigeration oil containing hydrocarbon coolant and compositions |
| EP3305878A4 (en) * | 2015-06-08 | 2018-12-05 | NOF Corporation | Ester for refrigeration oil and working fluid composition for refrigeration oil |
| CN105132088A (en) * | 2015-07-08 | 2015-12-09 | 新疆福克油品股份有限公司 | Synthetic ester refrigerator oil composition |
| WO2018105575A1 (en) * | 2016-12-05 | 2018-06-14 | 日油株式会社 | Refrigerating machine oil composition, and working fluid composition for refrigerating machines containing same |
| EP3617504A4 (en) | 2017-04-28 | 2020-04-22 | Panasonic Appliances Refrigeration Devices Singapore | Hermetically sealed refrigerant compressor and refrigeration device using same |
| EP3617503A1 (en) | 2017-04-28 | 2020-03-04 | Panasonic Appliances Refrigeration Devices Singapore | Hermetically sealed refrigerant compressor and refrigeration device using same |
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|---|---|---|---|---|
| JPH07506869A (en) * | 1992-06-03 | 1995-07-27 | ヘンケル・コーポレイション | Polyol ester lubricant for hermetic refrigeration compressor |
| FI111711B (en) | 1997-04-11 | 2003-09-15 | Fortum Oil & Gas Oy | Especially polyol and complex esters for use with fluorinated coolants |
| US20010019120A1 (en) * | 1999-06-09 | 2001-09-06 | Nicolas E. Schnur | Method of improving performance of refrigerant systems |
| JP3622896B2 (en) * | 1999-10-08 | 2005-02-23 | 花王株式会社 | Refrigerator oil base oil |
| CN1101459C (en) * | 2000-03-31 | 2003-02-12 | 北京燕山石油化工公司研究院 | Lubricating oil for refrigerating machine |
| US20020055442A1 (en) * | 2000-04-26 | 2002-05-09 | Schnur Nicholas E. | Method of reducing wear of metal surfaces and maintaining a hydrolytically stable environment in refrigeration equipment during the operation of such equipment |
| JP5016158B2 (en) | 2000-07-26 | 2012-09-05 | 出光興産株式会社 | Lubricating oil composition for refrigerator and working fluid composition for refrigerator using the same |
| JP2002107067A (en) | 2000-09-29 | 2002-04-10 | Nippon Kentetsu Co Ltd | Sealing seat |
| JP4929555B2 (en) * | 2000-10-16 | 2012-05-09 | 日油株式会社 | Method for producing ester |
| US6617289B2 (en) * | 2000-10-16 | 2003-09-09 | Nof Corporation | Method for producing ester |
| JP3909744B2 (en) * | 2001-07-31 | 2007-04-25 | 株式会社ジャパンエナジー | Refrigerating machine oil for hydrocarbon refrigerant |
| JP2003073681A (en) * | 2001-09-03 | 2003-03-12 | Hitachi Ltd | Working medium composition for refrigerator and refrigerator using the composition |
| JP4961666B2 (en) * | 2004-12-02 | 2012-06-27 | 日油株式会社 | Lubricating oil composition for refrigerator |
-
2005
- 2005-05-27 JP JP2005156071A patent/JP4806967B2/en active Active
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- 2006-05-25 MY MYPI20062404A patent/MY144475A/en unknown
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281575A (en) * | 2007-04-18 | 2017-01-04 | 出光兴产株式会社 | Lubricating oil composition for refrigerator and compressor using the same |
| CN101812349A (en) * | 2010-05-11 | 2010-08-25 | 上海海都化学科技有限公司 | Lubricating oil and grease base oil, and preparation method and applications thereof |
| CN101812349B (en) * | 2010-05-11 | 2013-05-01 | 上海海都化学科技有限公司 | Lubricating oil and grease base oil, and preparation method and applications thereof |
| CN104271547A (en) * | 2012-04-26 | 2015-01-07 | 日油株式会社 | Ester for refrigerator oils and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060122770A (en) | 2006-11-30 |
| JP4806967B2 (en) | 2011-11-02 |
| KR101237765B1 (en) | 2013-02-28 |
| JP2006328275A (en) | 2006-12-07 |
| CN1869177B (en) | 2012-01-04 |
| MY144475A (en) | 2011-09-30 |
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