CN107614663A - Refrigerator oil is with ester and refrigerator oil working fluid composition - Google Patents
Refrigerator oil is with ester and refrigerator oil working fluid composition Download PDFInfo
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- CN107614663A CN107614663A CN201680029198.3A CN201680029198A CN107614663A CN 107614663 A CN107614663 A CN 107614663A CN 201680029198 A CN201680029198 A CN 201680029198A CN 107614663 A CN107614663 A CN 107614663A
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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
- 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
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
-
- 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
- C10N2020/101—Containing Hydrofluorocarbons
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- 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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The present invention provides a kind of refrigerator oil ester oil grease with excellent lubricity and heat resistance.Refrigerator oil ester is obtained by following compositions (A), composition (B), composition (C) and composition (D), its ratio is, relative to 1.0 moles of the constituent from composition (A), constituent from composition (B) is 0.1~0.4 mole, constituent from composition (C) is 0.8~2.8 mole, and the constituent from composition (D) is 0.3~2.3 mole.The hydroxyl value of ester is 5~40mgKOH/g, meets formula (1) and formula (2).(A) neopentyl glycol；(B) carbon number 2~6, two ends carbon on have hydroxyl straight-chain dihydric alcohol；(C) carbon number 4~10, two ends carbon on have carboxyl straight-chain dicarboxylic acids；(D) monohydric alcohol of carbon number 6~12.0.08≤BOH/(AOH+BOH)≤0.15……(1)[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)AOHTo come from the molal quantity of the terminal hydroxyl of composition (A) in ester；BOHTo come from the molal quantity of the terminal hydroxyl of composition (B) in ester；AmolTo come from the molal quantity of the constituent of composition (A) in ester；BmolTo come from the molal quantity of the constituent of composition (B) in ester.
Description
Technical field
The present invention relates to a kind of refrigerator oil ester with excellent lubricity and heat resistance.In addition, it is related to a kind of freezing
Machine oil ester, it is characterised in that refrigerator oil ester is used for cold containing non-chlorine class freon refrigerant or natural refrigerant
Freeze in machine oil working fluid composition.
Background technology
The cryogenic machines such as the air-conditioning such as room conditioning, assembled air-conditioner machine, home-use freezing freezer, industrial freezing
In the on-board air conditioner of machine and hybrid vehicle, electric automobile etc., in order to replace causing the chloride of the reasons such as depletion of the ozone layer
Freon refrigerant, using HFA 134a (R-134a), pentafluoroethane (R-125), as difluoromethane (R-32) with
The HFCs such as the R-410A of R-125 mix refrigerant (HFC) are used as refrigerant.
But although the depletion of the ozone layer coefficient of above-mentioned HFC refrigerant is zero, but global warming potential (GWP) is up to
More than 1000.Therefore, because for the purpose of reducing greenhouse effect and as the object of limitation, its use is controlled, so as to examine
Consider using refrigerant low GWP.For example, carrying out to 2,3,3, the 3- tetrafluoropropene (HFO- that GWP is used alone as 4
1234yf), GWP is 675 R-32 etc. conversion.
With the progress of the conversion of the HFC refrigerant to low GWP, proposition has the compatibility of GWP refrigerants low with these
Oily various refrigerator oil esters based on high polyol ester.In addition, in the refrigerant replacement of these candidates, make
During the refrigerant that the pressure such as the mix refrigerant with R-32 or containing R-32 increase, the discharge temperature of compressor increases, compressor
Interior lubricating condition becomes harsher, therefore proposes to be improved the refrigerator oil ester of lubricity and stability.
For example, in patent document 1, with the mix refrigerant containing R-32 is used, transported as in the harsh and unforgiving environments of heat
Still there is the ester of high stability in the compressor turned, disclose one kind with pentaerythrite and 2 ethyl hexanoic acid and 3,5,5- trimethyls
Refrigerator oil lubricating oil of the ester that caproic acid is formed as principal component.
In addition, in the case of hydro carbons (HC) refrigerant, because HC intramoleculars do not improve the fluorine of lubricity, therefore can not
Expect to bring lubricity to improve effect by refrigerant as HFC refrigerant etc., and because HC refrigerants are to refrigerator oil
Solubility is high, the viscosity of oil declines, therefore lubricating condition becomes harsher.In patent document 2, it is proposed that a kind of so tight
Still there is excellent lubricity and the complex ester of excellent heat resistance under cruel lubricating condition, disclose by the way that BDO is used for
Lubricity is improved in raw material, is used to monohydric alcohol improve heat resistance in raw material.
Prior art literature
Patent document
Patent document 1：Unexamined Patent 10-8084 publications
Patent document 2：WO2014/017596
The content of the invention
The technical problem to be solved in the present invention
But miniaturization (the refrigerator oil usage amount of every 1 is reduced) or energy-saving because of the machine using refrigerator oil
The progress of (inverter control causes the duration of runs of compressor to extend), the use condition of refrigerator oil become further harsh.
Therefore, because the frictional heat for the sliding part for passing through compressor, the refrigerator oil thermal decomposition under the conditions of localized hyperthermia, are present
The catabolite corroding metal parts of generation, the possibility for bringing adverse effect to resin material, so seek exploitation is a kind of to exist
Also the refrigerator oil ester of excellent lubricity and heat endurance can be shown under conditions of harsher.
The technical problem of the present invention is that provide a kind of refrigerator oil with excellent lubricity and heat resistance is lubricated with ester
Oil.
Solves the technological means of technical problem
In order to solve the above-mentioned technical problem, present inventor etc. has found after conscientiously studying, with specific dihydric alcohol, two
First carboxylic acid, monohydric alcohol have excellent lubricity and heat resistance as the ester of constituent, so as to complete the present invention.
That is, the present invention is as follows：
(1) a kind of refrigerator oil ester, it is characterised in that：
The refrigerator oil ester is obtained by following compositions (A), composition (B), composition (C) and composition (D),
Its ratio is, relative to 1.0 moles of the constituent from the composition (A) in the ester, from it is described into
The constituent for dividing (B) is 0.1~0.4 mole, and the constituent from the composition (C) is 0.8~2.8 mole, and is come
It is 0.3~2.3 mole from the constituent of the composition (D),
The hydroxyl value of the ester is 5~40mgKOH/g, meets formula (1) and formula (2),
(A) neopentyl glycol,
(B) carbon number 2~6, two ends carbon on have hydroxyl straight-chain dihydric alcohol,
(C) carbon number 4~10, two ends carbon on have carboxyl straight-chain dicarboxylic acids,
(D) monohydric alcohol of carbon number 6~12,
0.08≤BOH/(AOH+BOH)≤0.15……(1)
[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)
In the formula (1) and the formula (2),
AOHFor the molal quantity of the terminal hydroxyl from the composition (A) in the ester；
BOHFor the molal quantity of the terminal hydroxyl from the composition (B) in the ester；
AmolFor the molal quantity of the constituent from the composition (A) in the ester；
BmolFor the molal quantity of the constituent from the composition (B) in the ester.
(2) a kind of refrigerator oil working fluid composition, it is characterised in that the refrigerator oil working fluid composition
Refrigerator oil ester containing non-chlorine class freon refrigerant or natural refrigerant and according to (1).
In addition, in order to obtain the refrigerator oil ester, by composition (A), composition preferably at a temperature of 100~150 DEG C
(B), composition (C) and composition (D) are then anti-for secondary esterification at a temperature of 150 DEG C~250 DEG C for an esterification
Should.
Invention effect
The refrigerator oil ester of the present invention has high-fire resistance, therefore is applicable to especially need the freezing of heat endurance empty
In the compressor for adjusting machine.In addition, refrigerator oil ester and the non-chlorine class freon refrigerant or natural refrigerant of the present invention
Compatibility is high, therefore suitable for the working fluid composition for refrigerating machine containing these refrigerants.
Embodiment
Hereinafter, the refrigerator oil of the present invention is illustrated with ester.
In addition, included "~" both ends (upper limit and lower limit) using the range of resin of symbol "~" defined in this specification
Numerical value.Such as " 2~5 " represent " more than 2, less than 5 ".
The refrigerator oil of the present invention is obtained in the following manner with ester：By neopentyl glycol (composition (A)), carbon number 2~6
Two ends carbon on the straight-chain dihydric alcohol (composition (B)) with hydroxyl, carbon number 4~10 two ends carbon on
Monohydric alcohol (composition (the D)) mixing of the straight-chain dicarboxylic acids (composition (C)), carbon number 6~12 of carboxyl, and it is carried out ester
Change reaction.
In addition, the general name of the term of composition (A), composition (B), composition (C) and composition (D) for convenience, belongs to each composition
Compound can be one kind, or belong to each composition compound can also be more than two kinds.More than two kinds are included in each composition
In the case of compound, the amount of each composition is the total amount for more than two kinds compounds for belonging to the composition.
As the neopentyl glycol of the composition (A) used in the present invention, industrial obtainable neopentyl glycol can be used, as
The form of neopentyl glycol, solid-like neopentyl glycol can be used or through water-reducible liquid neopentyl glycol.
Composition (B), specifically, can to have the straight-chain dihydric alcohol of hydroxyl on the carbon of two ends of carbon number 2~6
Include ethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, 1,6-HD etc..The preferably binary of straight-chain
Saturated alcohols, particularly preferably using BDO.By composition (B), it is excellent that viscosity index (VI), low-temperature stability, lubricity can be obtained
Different ester.
Composition (C) to have the straight-chain dicarboxylic acids of carboxyl on the carbon of two ends of carbon number 4~10, it is specific and
Speech, can including butanedioic acid (carbon number 4), glutaric acid (carbon number 5), adipic acid (carbon number 6), pimelic acid, (carbon is former
Subnumber 7), suberic acid (carbon number 8), azelaic acid (carbon number 9), decanedioic acid (carbon number 10) etc..It is preferred that use straight chain
The binary saturated carboxylic acid of the carbon number 6~8 of shape.By composition (C), it is excellent with low-temperature stability that viscosity index (VI) can be obtained
Ester.
Composition (D) be carbon number 6~12 monohydric alcohol, they can be straight chain alcohol, branched-chain alcoho it is any.It is specific and
Speech, can include 1- hexanols, 1-heptanol, 1- octanols, 1 nonyl alcohol, 1- decyl alcohol, 1- tip-nips, DODECANOL, 1-, 2- ethyl hexyls
Alcohol, 3,5,5- trimethyl hexanols etc..The preferably saturation branched-chain alcoho of carbon number 6~10, it is excellent can to obtain low-temperature stability
Ester.Particularly preferably using 2-Ethylhexyl Alcohol, 3,5,5- trimethyl hexanols.
The refrigerator oil of the present invention is the refrigerator oil ester that is formed with following ratios with ester：Relative to from composition (A)
1.0 moles of constituent, the constituent from composition (B) is 0.1~0.4 mole, and the constituent from composition (C) is
0.8~2.8 mole, the constituent from composition (D) is 0.3~2.3 mole.
Relative to 1.0 moles of the constituent from composition (A), from composition (B) if the amount of constituent be less than 0.1
Mole, then it is difficult to obtain desired viscosity index (VI) and lubricity, if more than 0.4 mole, the low-temperature stability of ester is deteriorated.Phase
For 1.0 moles of the constituent from composition (A), the amount of the constituent from composition (B) is preferably rubbed for 0.1~0.3
You.
Relative to 1.0 moles of the constituent from composition (A), from composition (C) if the amount of constituent be less than 0.8
Mole, then it is difficult to obtain high viscosity index (VI), if more than 2.8, is difficult to obtain lubricity.Relative to the structure from composition (A)
Into 1.0 moles of composition, the amount of the constituent from composition (C) is preferably more than 0.9 mole, furthermore it is preferred that for 2.3 moles with
Under.
Relative to 1.0 moles of the constituent from composition (A), the amount of the constituent from composition (D) if 0.3~
2.3 moles, then it is readily available the ester of the suitable viscosity as refrigerator oil.Relative to the constituent 1.0 from composition (A)
Mole, the amount of the constituent from composition (D) is preferably more than 0.5 mole, and preferably less than 2.1 moles.
The molar ratio of above-mentioned each constituent is calculated by gas chromatography to analyze.With 5g toluene and methanols
(80wt%/20wt%) mixed solvent dilutes 0.1g esters, then adds 0.3g 28% methanol solution of sodium methylate (and the pure medicine work of light
Industry (strain)), 30 minutes are stood at 60 DEG C, Methanol Decomposition is carried out to ester.Ester decomposing solution by gas chromatography to acquisition
Analyzed, can be by the way that the peak area ratio of the composition (A) of acquisition, composition (B), composition (C), composition (D) be scaled into mol ratio
And calculated.In addition, the composition of ester catabolite can be differentiated by analyzing the single gas chromatography of each composition.
The present invention ester be, by adjust from each composition (A), (B), (C), (D) constituent molar ratio, lead to
The ester for crossing composition (A), (B) or (D) and blocking the carboxyl of composition (C) and synthesizing, except end structure is the alkane from composition (D)
Beyond the ester of base, in addition to as accessory ingredient ester end structure for the hydroxyl from composition (A), the hydroxyl from composition (B)
The ester of base.
As one of the specific end structure of the ester of the present invention, illustrated using formula (3), (4), (5).Formula (3) is
There is the structure of the alkyl from composition (D), formula (4) is to have the hydroxyl from composition (A) on the end of ester on the end of ester
Structure, formula (5) for ester end on have from composition (B) hydroxyl structure.
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
M be 1~5 integer, R1Represent the alkyl from composition (D).
By said structure design, when as refrigerator oil, it is not easy to cause hydrolysis or thermal decomposition, it is excellent stability can be turned into
Different ester.
The refrigerator oil ester of the present invention meets formula (1) and formula (2).
0.08≤BOH/(AOH+BOH)≤0.15···(1)
AOHFor the molal quantity of the terminal hydroxyl from composition (A) in ester；
BOHFor the molal quantity of the terminal hydroxyl from composition (B) in ester.
Formula (1) is represented relative to the total of terminal hydroxyl of the terminal hydroxyl from composition (A) with coming from composition (B) in ester
The molar ratio of terminal hydroxyl measure, from composition (B).
[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)
AOHTo come from the molal quantity of the terminal hydroxyl of composition (A) in ester；
BOHTo come from the molal quantity of the terminal hydroxyl of composition (B) in ester；
AmolTo come from the molal quantity of the constituent of composition (A) in ester；
BmolTo come from the molal quantity of the constituent of composition (B) in ester.
The molecule of formula (2) is [BOH/(AOH+BOH)], it is shown in formula (1), represents relative to coming from composition (A) in ester
The molar ratio of terminal hydroxyl and terminal hydroxyl total amount, from composition (B) of the terminal hydroxyl from composition (B).
On the other hand, the denominator of formula (2) is [Bmol/(Amol+Bmol)], its represent relative in ester from composition (A)
The molar ratio of constituent and constituent total amount, from composition (B) of the constituent from composition (B).
Therefore, formula (2) represents the molar ratio relative to the constituent from composition (B) in ester, from composition (B)
Terminal hydroxyl molar ratio it is small which kind of degree arrived, in other words, represent relative to (B) in the integrally-built end structure of ester
The skewness degree of composition.
In addition, each numerical value of formula (1) (2) determines in such a way.
The numerical value of the numerical value of formula (1) and the molecule of formula (2)：BOH/(AOH+BOH)。
Obtain1In H-NMR spectrum relative to the hydroxyl from composition (A) α hydrogen peak (3.2~3.4ppm) integration
Value, relative to the hydroxyl from composition (B) α hydrogen peak (3.6~3.8ppm) integrated value, by using relative to from composition
(B) integrated value of the α hydrogen of hydroxyl divided by each integrated value and and calculate.
The numerical value of the denominator of formula (2)：Bmol/(Amol+Bmol)
The molal quantity of each constituent from composition (A) and composition (B) is obtained by described gas chromatography analysis,
Calculate molar ratio.
Composition (A) is not associated with hydrogen (β hydrogen is not present) on β carbon, therefore in terminal hydroxyl caused by ester structure end,
Compared to the end structure from composition (B), the end structure excellent heat resistance from composition (A).That is, from composition (A)
The more existing ester in ester structure end is not with being excellent heat resistance compared with such ester.As a result, by from composition (B)
The molar ratio of hydroxyl account for less than the 0.15 of whole hydroxyls, the ester with more excellent heat resistance can be formed.Relative to from
The total amount of the terminal hydroxyl of composition (A) and the terminal hydroxyl from composition (B), the mol ratio of the terminal hydroxyl from composition (B)
When example is 0.08~0.15, it is easier to obtain the ester of lubricity and excellent heat resistance.Consider from the angle, the molar ratio enters
One step is preferably more than 0.09, in addition, more preferably less than 0.14.
Further, relative to the molar ratio of the constituent from composition (B) in ester, from composition (B) end
Terminal hydroxy group is in a manner of molar ratio diminishes and the heat resistance of the ester of skewness is more excellent.(B) composition in end structure
Skewness degree can be by relative to the molar ratio, from composition (B) of the constituent from composition (B) in ester
The molar ratio of terminal hydroxyl and represent, by the value be less than 0.9, the more excellent ester of heat resistance can be obtained.The value be 0.9 with
Under, more preferably less than 0.8.In addition, the lower limit of the value is not particularly limited, preferably more than 0.2, more preferably 0.3
More than, more preferably more than 0.5.
The ester of the present invention is, relative to the constituent from composition (B) in ester and the constituent from composition (A)
The mol ratio of whole hydroxyls is accounted for the hydroxyl that composition (B) is come from the mol ratio of constituent sum from composition (B), ester
The ester that rate reduces, by above-mentioned reason, meeting the ester of formula (1) and formula (2) turns into the further excellent ester of heat resistance.
When preparing ester, mentioned component (A), composition (B), composition (C) and composition (D) are all put into first suitable anti-
Answer in device, esterification is carried out under normal pressure, nitrogen atmosphere.In order to more effectively remove the water of dereaction generation, esterification is led to
It can often be carried out at 150~250 DEG C.But from the point of view of the ester with more excellent heat resistance is obtained, first 100~
An esterification is carried out at 150 DEG C.Then secondary esterification is carried out at 150 DEG C~250 DEG C.
Esterification is preferably carried out at 100~140 DEG C, is further preferably carried out at 100~130 DEG C, by
This, is readily available the ester of excellent heat resistance.In addition, an esterification is preferably 1~10 hour, more preferably 2~8 is small
When, thus, it is readily available the ester of excellent heat resistance.
Secondary esterification is preferably carried out at 160~260 DEG C, is further preferably carried out at 180~250 DEG C.Now,
Secondary esterification is carried out, until acid number is below 10mgKOH/g, preferably below 5mgKOH/g, further preferred 2mgKOH/g.
In addition, esterification can use bronsted sour (Bronsted acid) catalyst or lewis acid (Lewis
Acid) catalyst, but preferably carried out under without catalyst.
After esterification, distillation under reduced pressure removes excessive composition (D), obtains thick ester.Further, with adsorbent pair
Thick ester carries out purification processes, it can thus be concluded that to target refrigerator oil ester.
The refrigerator oil of the present invention is preferably 20~500mm in 40 DEG C of kinematic viscosity with ester2/s.More preferably 20~
300mm2/ s, more preferably 20~250mm2/ s, most preferably 20~180mm2/s.In addition, hydroxyl value be preferably 5~
40mgKOH/g, more preferably 15~35mgKOH/g.
The refrigerator oil ester of the present invention can use separately as base oil, can be also used in mixed way with other base oils.This
Outside, known additive, such as the antioxidant of phenols, BTA, thiadiazoles or two sulphur can be properly added according to purpose
For additives such as the sour agent for capturing such as the matal deactivators such as carbaminate, epoxide or carbodiimide, Phosphorus extreme pressure agents.
The refrigerator oil ester of the present invention is high with the compatibility of non-chlorine class freon refrigerant or natural refrigerant, therefore can
Suitable for the working fluid composition for refrigerating machine containing these refrigerants.As non-chlorine class freon refrigerant, can enumerate
Go out the monomer or their mixture of HFC (HFC), HF hydrocarbon (HFO), hydro carbons (HC) or natural refrigerant.
As the concrete example of HFC (HFC) refrigerant, preferably HFA 134a (R-134a), pentafluoroethane
(R-125), Difluoroethane (R-32), fluoroform (R-23), 1,1,2,2- HFC-134as (R-134), 1,1,1- HFC-143as
(R-143a), any one kind or two or more mixture such as 1,1- Difluoroethanes (R-152a).As above-mentioned mix refrigerant, example
R-407C (R-134a/R-125/R-32=52/25/23 mass %), R-410R (R-125/R-32=50/50 can such as be included
Quality %), R-404A (R-125/R-143/R-134a=44/52/4 mass %), R-407E (R-134a/R-125/R-32=
60/15/25 mass %), R-410B (R-32/R-125=45/55 mass %) etc..Among this, particularly preferably, contain R-
At least one of 134a and R-32 refrigerant, it can further preferably include single R-32 refrigerants.
As the concrete example of HF hydrocarbon (HFO) refrigerant, preferably 1,2,3,3,3- pentafluoropropenes (HFO-1225ye),
1,3,3,3- tetrafluoropropenes (HFO-1234ze), 2,3,3,3- tetrafluoropropenes (HFO-1234yf), 1,2,3,3- tetrafluoropropenes
And any one kind or two or more mixture in 3,3,3- trifluoro propenes (HFO-1243zf) etc. (HFO-1234ye).From refrigeration
From the point of view of agent physical property, the one kind or two or more of HFO-1225ye, HFO-1234ze and HFO-1234yf is preferably selected from.
In addition, as hydro carbons (HC) refrigerant, propane (R290) or iso-butane (R600a) etc. can be included or theirs is mixed
Compound, as natural refrigerant, ammonia or carbon dioxide etc. can be included.Especially preferably enumerate R290, R600 and carbon dioxide.
With working fluid composition under normal conditions, refrigerator oil ester of the invention is sharp with non-chlorine class fluorine for refrigerator oil
High refrigerant or the mass ratio of natural refrigerant are 10:90~90:10.The mass ratio of refrigerant is if the scope, then workflow
Body composition has appropriate viscosity, and lubricity is excellent and freezing efficiency is high, so it is preferred that.
Embodiment
Hereinafter, by embodiment, the present invention will be described in further detail, but the present invention is not by following embodiment institutes
Limit.
In addition, the refrigerator oil obtained in embodiment and comparative example is divided as follows with the various analyses of ester
Analysis.
Acid number：Determined according to JIS K2501.
Hydroxyl value：Determined according to JIS K0070.
Kinematic viscosity：Determined according to JIS K2283.
The preparation of embodiment 1
Neopentyl glycol 124g (1.19mol), 1,4- butanediols 30g (0.34mol), adipic acid are added into four-hole boiling flask
355g (2.43mol), 3,5,5- trimethyl hexanol 339g (2.35mol), remove reaction water in a nitrogen atmosphere with 120 DEG C of distillations
(reaction water), while react 3 hours at ambient pressure.Then, continue at 200 DEG C reaction 7 hours to acid number be 2 with
Under.Then by under 200 DEG C, 1~5kPa decompression distillation remove 3,5,5- excessive trimethyl hexanols, obtain thick ester.It is cold
Thick ester, the adsorbent of acidic white clay and silica-alumina class is added thereto namely to obtaining in theory
1.0 mass % of ester amount, carry out adsorption treatment.Adsorption treatment temperature, pressure and adsorption treatment time be set to 100 DEG C, 1~
5kPa, 2 hours.Finally filtered using 1 micron of filter paper, obtain target ester.
The preparation of embodiment 2
Neopentyl glycol 180g (1.73mol), 1,4- butanediols 25g (0.28mol), adipic acid are added into four-hole boiling flask
360g (2.47mol), 3,5,5- trimethyl hexanol 256g (1.78mol), distill to remove in a nitrogen atmosphere, at 115 DEG C and react
Water, while react 4 hours at ambient pressure.Process afterwards is carried out in the same manner as example 1, obtains target ester.
The preparation of embodiment 3
Neopentyl glycol 205g (1.97mol), 1,4- butanediols 26g (0.28mol), adipic acid are added into four-hole boiling flask
373g (2.55mol), 3,5,5- trimethyl hexanol 217g (1.50mol), distill to remove in a nitrogen atmosphere, at 125 DEG C and react
Water, while react 3 hours at ambient pressure.Process afterwards is carried out in the same manner as example 1, obtains target ester.
The preparation of embodiment 4
Neopentyl glycol 174g (1.66mol), 1,4- butanediols 46g (0.51mol), adipic acid are added into four-hole boiling flask
373g (2.55mol), 3,5,5- trimethyl hexanol 238g (1.65mol), distill to remove in a nitrogen atmosphere, at 120 DEG C and react
Water, while react 4 hours at ambient pressure.Process afterwards is carried out in the same manner as example 1, obtains target ester.
The preparation of embodiment 5
Neopentyl glycol 129g (1.23mol), 1,5- pentanediols 28g (0.26mol), suberic acid are added into four-hole boiling flask
393g (2.25mol), n-octyl alcohol 300g (2.30mol), removal reaction water is distilled in a nitrogen atmosphere, at 120 DEG C, while normal
Pressure reaction 5 hours.Process afterwards is carried out in the same manner as example 1, obtains target ester.
The preparation of embodiment 6
Neopentyl glycol 215g (2.07mol), 1,3- propane diols 22g (0.29mol), adipic acid are added into four-hole boiling flask
385g (2.64mol), 3,5,5- trimethyl hexanol 214g (1.49mol), distill to remove in a nitrogen atmosphere, at 120 DEG C and react
Water, while react 4 hours at ambient pressure.Process afterwards is carried out in the same manner as example 1, obtains target ester.
The preparation of embodiment 7
Neopentyl glycol 211g (2.03mol), 1,6-HD 42g (0.36mol), adipic acid are added into four-hole boiling flask
385g (2.64mol), 3,5,5- trimethyl hexanol 206g (1.43mol), distill to remove in a nitrogen atmosphere, at 115 DEG C and react
Water, while react 5 hours at ambient pressure.Process afterwards is carried out in the same manner as example 1, obtains target ester.
The preparation of comparative example 1
Neopentyl glycol 174g (1.66mol), 1,4- butanediols 46g (0.51mol), adipic acid are added into four-hole boiling flask
373g (2.55mol), 3,5,5- trimethyl hexanol 238g (1.65mol), remove reaction in a nitrogen atmosphere with 200 DEG C of distillations
Water, while continue reaction 7 hours at ambient pressure, it is less than 2 to acid number.Then, distill and go under 200 DEG C, 1~5kPa decompression
Except 3,5,5- trimethyl hexanols of excess, thick ester is obtained.Thick ester is cooled down, adds acidic white clay and silica-oxygen thereto
Change 1.0 mass %s of the adsorbent namely to the ester amount obtained in theory of aluminium class, carry out adsorption treatment.Adsorption treatment temperature
Degree, pressure and adsorption treatment time be set to 100 DEG C, 1~5kPa, 2 hours.Finally filtered, obtained using 1 micron of filter paper
Target ester.
The preparation of comparative example 2
Neopentyl glycol 104g (1.00mol), 1,4- butanediols 27g (0.30mol), adipic acid are added into four-hole boiling flask
351g (2.40mol), distill remove reaction water in a nitrogen atmosphere, at 200 DEG C, while react 3 hours at ambient pressure, to acid number
For less than 270, ester intermediate is obtained.3,5,5- trimethyl hexanol 361g (2.50mol) are further added into the ester intermediate,
Continue reaction 7 hours, until acid number is less than 2.Then, distillation removes excessive 3,5 under 200 DEG C, 1~5kPa decompression,
5- trimethyl hexanols, obtain thick ester.Thick ester is cooled down, adds the absorption of acidic white clay and silica-alumina class thereto
Agent carries out adsorption treatment namely to 1.0 mass % of the ester amount obtained in theory.Adsorption treatment temperature, pressure and absorption
Processing time be set to 100 DEG C, 1~5kPa, 2 hours.Finally filtered using 1 micron of filter paper, obtain target ester.
Heat resistance (heat run)
For above-mentioned refrigerator oil ester, the heat resistance of refrigerator oil ester is evaluated by implementing heat run, it is heat-resisting
Property experiment be in air atmosphere, heat 72 hours in 130 DEG C of thermostat, measure heat after refrigerator oil ester
Acid number.
Lubricity (SRV experiments)
For above-mentioned refrigerator oil ester, lubricity is evaluated by SRV testing machines.SRV experiments are carried out with ball/disk, examination
Test piece and use SUJ-2 systems respectively.Experimental condition is carried out with 60 DEG C of test temperature, load 100N, amplitude 1mm, vibration number 50Hz,
Grinding defect diameter of the determination test time after 25 minutes.
The preparation condition of embodiment 1~7 and comparative example 1~2 is summarized in table 1, table 2, and physics value, heat resistance, lubricity are total
Tie in table 3, table 4.In addition, table 1, table 2 describe the adding proportion of each composition, and table 3, table 4 describe to be come from generated ester
The measured value of the molar ratio of the constituent of each composition.
[table 1]
[table 2]
[table 3]
[table 4]
As shown in 1~table of table 4, the ester lubricity of embodiment 1~7 is excellent, and heat resistance is also excellent, therefore even in compression
Also it is difficult to deteriorate under harsh lubricating condition in machine, can be long-term use of.Further, since inhibit on the acid number in heat run
Rise, therefore further suppress the generation of the catabolite as corrosions such as the metals in compressor.
On the other hand, in comparative example 1~2, by the ascensional range of the acid number different from the ester of embodiment is big, therefore
Compared with embodiment, the progress of the decomposition of ester caused by heat run has been confirmed.
Claims (2)
- A kind of 1. refrigerator oil ester, it is characterised in that：The refrigerator oil ester is obtained by following compositions (A), composition (B), composition (C) and composition (D), and its ratio is, relatively 1.0 moles of the constituent from the composition (A) in the ester, the constituent from the composition (B) be 0.1~ 0.4 mole, the constituent from the composition (C) is 0.8~2.8 mole, and the constituent from the composition (D) For 0.3~2.3 mole,The hydroxyl value of the ester is 5~40mgKOH/g, meets formula (1) and formula (2),(A) neopentyl glycol,(B) carbon number 2~6, two ends carbon on have hydroxyl straight-chain dihydric alcohol,(C) carbon number 4~10, two ends carbon on have carboxyl straight-chain dicarboxylic acids,(D) monohydric alcohol of carbon number 6~12,0.08≤BOH/(AOH+BOH)≤0.15……(1)[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)In the formula (1) and the formula (2), AOHFor the molal quantity of the terminal hydroxyl from the composition (A) in the ester；BOH For the molal quantity of the terminal hydroxyl from the composition (B) in the ester；AmolTo come from the composition (A) in the ester Constituent molal quantity；BmolFor the molal quantity of the constituent from the composition (B) in the ester.
- 2. a kind of refrigerator oil working fluid composition, it is characterised in that the refrigerator oil working fluid composition contains Non- chlorine class freon refrigerant or natural refrigerant and refrigerator oil ester according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015115892 | 2015-06-08 | ||
| JP2015-115892 | 2015-06-08 | ||
| PCT/JP2016/066756 WO2016199718A1 (en) | 2015-06-08 | 2016-06-06 | Ester for refrigeration oil and working fluid composition for refrigeration oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107614663A true CN107614663A (en) | 2018-01-19 |
| CN107614663B CN107614663B (en) | 2020-06-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680029198.3A Active CN107614663B (en) | 2015-06-08 | 2016-06-06 | Ester for refrigerator oil and working fluid composition for refrigerator oil |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3305878A4 (en) |
| JP (1) | JP6614510B2 (en) |
| KR (1) | KR102523681B1 (en) |
| CN (1) | CN107614663B (en) |
| TW (1) | TWI689581B (en) |
| WO (1) | WO2016199718A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113728079A (en) * | 2019-04-25 | 2021-11-30 | 日油株式会社 | Ester for refrigerator oil and working fluid composition containing the same |
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| JPH01139694A (en) * | 1987-11-26 | 1989-06-01 | Nippon Steel Corp | Lubrication oil |
| EP0452816A2 (en) * | 1990-04-20 | 1991-10-23 | Nippon Oil Co. Ltd. | Use of synthetic lubricating oils in refrigerators |
| JP2001501991A (en) * | 1996-09-11 | 2001-02-13 | エクソン・ケミカル・パテンツ・インク | Polyol ester compositions having unconverted hydroxyl groups for use as lubricant-based raw materials |
| CN1364189A (en) * | 1999-07-05 | 2002-08-14 | 日石三菱株式会社 | Refrigerating oil composition |
| 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 |
| JP2013181133A (en) * | 2012-03-02 | 2013-09-12 | Jx Nippon Oil & Energy Corp | Refrigerator working fluid composition, refrigerant oil, and method for producing the same |
| WO2014017596A1 (en) * | 2012-07-26 | 2014-01-30 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricant base oil, refrigerator oil and working fluid composition for refrigerators |
| WO2014156738A1 (en) * | 2013-03-25 | 2014-10-02 | Ｊｘ日鉱日石エネルギー株式会社 | Working fluid composition for refrigerator |
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| JPH108084A (en) | 1996-06-25 | 1998-01-13 | Kao Corp | Composition for refrigerator-working fluid |
| CN1190477C (en) * | 1999-05-10 | 2005-02-23 | 新日本理化株式会社 | Lubrication oil for refrigerator, hydraulic fluid compoistion for refrigerator and method for lubrication of refrigerator |
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| JP4806967B2 (en) * | 2005-05-27 | 2011-11-02 | 日油株式会社 | Lubricating oil composition for refrigerator |
| JP5193485B2 (en) * | 2007-03-27 | 2013-05-08 | Ｊｘ日鉱日石エネルギー株式会社 | Refrigerator oil and working fluid composition for refrigerator |
-
2016
- 2016-06-06 JP JP2017523626A patent/JP6614510B2/en active Active
- 2016-06-06 CN CN201680029198.3A patent/CN107614663B/en active Active
- 2016-06-06 EP EP16807425.0A patent/EP3305878A4/en not_active Withdrawn
- 2016-06-06 WO PCT/JP2016/066756 patent/WO2016199718A1/en active Application Filing
- 2016-06-06 KR KR1020187000300A patent/KR102523681B1/en active IP Right Grant
- 2016-06-08 TW TW105118146A patent/TWI689581B/en active
Patent Citations (8)
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|---|---|---|---|---|
| JPH01139694A (en) * | 1987-11-26 | 1989-06-01 | Nippon Steel Corp | Lubrication oil |
| EP0452816A2 (en) * | 1990-04-20 | 1991-10-23 | Nippon Oil Co. Ltd. | Use of synthetic lubricating oils in refrigerators |
| JP2001501991A (en) * | 1996-09-11 | 2001-02-13 | エクソン・ケミカル・パテンツ・インク | Polyol ester compositions having unconverted hydroxyl groups for use as lubricant-based raw materials |
| CN1364189A (en) * | 1999-07-05 | 2002-08-14 | 日石三菱株式会社 | Refrigerating oil composition |
| 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 |
| JP2013181133A (en) * | 2012-03-02 | 2013-09-12 | Jx Nippon Oil & Energy Corp | Refrigerator working fluid composition, refrigerant oil, and method for producing the same |
| WO2014017596A1 (en) * | 2012-07-26 | 2014-01-30 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricant base oil, refrigerator oil and working fluid composition for refrigerators |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113728079A (en) * | 2019-04-25 | 2021-11-30 | 日油株式会社 | Ester for refrigerator oil and working fluid composition containing the same |
| CN113728079B (en) * | 2019-04-25 | 2022-08-05 | 日油株式会社 | Ester for refrigerator oil and working fluid composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI689581B (en) | 2020-04-01 |
| WO2016199718A1 (en) | 2016-12-15 |
| JPWO2016199718A1 (en) | 2018-03-22 |
| KR102523681B1 (en) | 2023-04-19 |
| EP3305878A4 (en) | 2018-12-05 |
| CN107614663B (en) | 2020-06-26 |
| TW201700721A (en) | 2017-01-01 |
| EP3305878A1 (en) | 2018-04-11 |
| JP6614510B2 (en) | 2019-12-04 |
| KR20180017079A (en) | 2018-02-20 |
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