CN107614663B - Ester for refrigerator oil and working fluid composition for refrigerator oil - Google Patents
Ester for refrigerator oil and working fluid composition for refrigerator oil Download PDFInfo
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- CN107614663B CN107614663B CN201680029198.3A CN201680029198A CN107614663B CN 107614663 B CN107614663 B CN 107614663B CN 201680029198 A CN201680029198 A CN 201680029198A CN 107614663 B CN107614663 B CN 107614663B
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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
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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
- 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
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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
- 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
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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
- C10N2030/08—Resistance to extreme temperature
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- 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 invention provides an ester lubricating oil for refrigerator oil, which has excellent lubricity and heat resistance. The ester for refrigerating machine oil is obtained from the following component (A), component (B), component (C) and component (D), and the proportion is that the component from the component (B) is 0.1-0.4 mol, the component from the component (C) is 0.8-2.8 mol and the component from the component (D) is 0.3-2.3 mol relative to 1.0 mol of the component from the component (A). The hydroxyl value of the ester is 5 to 40mgKOH/g, and satisfies the formulae (1) and (2). (A) Neopentyl glycol; (B) a linear diol having 2 to 6 carbon atoms and having hydroxyl groups at both ends; (C) a straight chain dicarboxylic acid having 4 to 10 carbon atoms and having carboxyl groups at both ends; (D) a C6-12 monohydric alcohol. B is more than or equal to 0.08OH/(AOH+BOH)≤0.15……(1)[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)AOHIs the number of moles of terminal hydroxyl groups from component (a) in the ester; b isOHIs the number of moles of terminal hydroxyl groups from component (B) in the ester; a. themolThe number of moles of the constituent component derived from the component (A) in the ester; b ismolThe number of moles of the constituent component derived from the component (B) in the ester.
Description
Technical Field
The present invention relates to an ester for a refrigerator oil having excellent lubricity and heat resistance. The present invention also relates to an ester for a refrigerator oil, which is used in a working fluid composition for a refrigerator oil containing a non-chlorine freon refrigerant or a natural refrigerant.
Background
In air conditioning equipment such as indoor air conditioners and combination air conditioners, low-temperature equipment such as domestic refrigerators and freezers, industrial refrigerators, and in-vehicle air conditioners for hybrid cars and electric cars, Hydrofluorocarbons (HFC) such as 1,1,1, 2-tetrafluoroethane (R-134a), pentafluoroethane (R-125), and R-410A which is a mixed refrigerant of difluoromethane (R-32) and R-125 are used as a refrigerant in place of a chlorine-containing Freon refrigerant causing ozone layer destruction or the like.
However, the above HFC refrigerant has a zero ozone depletion potential (GWP) of 1000 or more. Therefore, since the use of the refrigerant is controlled to be restricted for the purpose of reducing the greenhouse effect, it is considered to use a refrigerant having a low GWP. For example, a shift is being made to 2,3,3, 3-tetrafluoropropene (HFO-1234yf) having a GWP of 4, R-32 having a GWP of 675, and the like, which are used alone.
With the progress of the shift to HFC refrigerants having a low GWP, various esters for refrigerator oils have been proposed, which use, as base oils, polyol esters having high compatibility with these low GWP refrigerants. Among these alternative refrigerant substitutes, there has been proposed an ester for a refrigerating machine oil which is improved in lubricity and stability because the discharge temperature of the compressor is increased and the lubricating conditions in the compressor are severer when a refrigerant having a high pressure such as R-32 or a mixed refrigerant containing R-32 is used.
For example, patent document 1 discloses a lubricating oil for a refrigerating machine oil containing an ester of pentaerythritol, 2-ethylhexanoic acid and 3,5, 5-trimethylhexanoic acid as main components as an ester having high stability even in a compressor operated in a hot and severe environment, along with the use of a mixed refrigerant containing R-32.
In the case of Hydrocarbon (HC) refrigerants, since there is no fluorine in the HC molecules to improve lubricity, the lubricity improving effect of refrigerants such as HFC refrigerants cannot be expected, and since the solubility of HC refrigerants in refrigerating machine oil is high and the viscosity of oil is reduced, the lubricating conditions become severer. Patent document 2 proposes a complex ester having excellent lubricity and excellent heat resistance under such severe lubricating conditions, and discloses that lubricity is improved by using 1, 4-butanediol as a raw material, and heat resistance is improved by using a monohydric alcohol as a raw material.
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent publication Hei 10-8084
Patent document 2: WO2014/017596
Disclosure of Invention
Technical problem to be solved by the invention
However, the use conditions of the refrigerating machine oil become more severe due to the progress of downsizing of the equipment using the refrigerating machine oil (the amount of the refrigerating machine oil used per 1 unit is reduced) or energy saving (the operation time of the compressor is extended by inverter control). Therefore, the refrigerating machine oil exposed to a local high temperature condition is thermally decomposed by the frictional heat of the sliding portion of the compressor, and the generated decomposition product may corrode a metal member and adversely affect a resin material, and therefore, development of an ester for a refrigerating machine oil which can exhibit excellent lubricity and thermal stability even under severer conditions has been demanded.
The technical problem of the present invention is to provide an ester lubricating oil for refrigerating machine oil having excellent lubricity and heat resistance.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that an ester containing a specific diol, dicarboxylic acid, or monohydric alcohol as a constituent has excellent lubricity and heat resistance, thereby completing the present invention.
Namely, the present invention is as follows:
(1) an ester for a refrigerator oil, characterized in that:
the ester for refrigerating machine oil is obtained from the following component (A), component (B), component (C) and component (D),
in the ester, the amount of the component (A) is 0.1 to 0.4 mol, the amount of the component (B) is 0.8 to 2.8 mol, and the amount of the component (D) is 0.3 to 2.3 mol, based on 1.0 mol of the component (A),
the hydroxyl value of the ester is 5-40 mgKOH/g, which satisfies formula (1) and formula (2),
(A) the ratio of neopentyl glycol,
(B) a linear diol having 2 to 6 carbon atoms and having hydroxyl groups at both ends,
(C) a straight chain dicarboxylic acid having 4 to 10 carbon atoms and having carboxyl groups at both ends,
(D) a C6-12 monohydric alcohol,
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),
AOHis the number of moles of terminal hydroxyl groups from the component (a) in the ester;
BOHis the number of moles of terminal hydroxyl groups from the component (B) in the ester;
Amolis the number of moles of constituent components from the component (a) in the ester;
Bmolis the number of moles of the constituent component derived from the component (B) in the ester.
(2) A working fluid composition for a refrigerating machine oil, characterized by comprising a non-chlorine freon refrigerant or a natural refrigerant and the ester for a refrigerating machine oil according to (1).
In order to obtain the ester for refrigerator oil, it is preferable that the component (a), the component (B), the component (C), and the component (D) are subjected to a primary esterification reaction at a temperature of 100 to 150 ℃, and then subjected to a secondary esterification reaction at a temperature of 150 to 250 ℃.
Effects of the invention
The ester for refrigerating machine oil of the present invention has high heat resistance, and therefore, can be suitably used for a compressor of a refrigerating and air-conditioning apparatus which particularly requires thermal stability. Further, the ester for a refrigerator oil of the present invention has high compatibility with a non-chlorine freon refrigerant or a natural refrigerant, and is therefore suitable for a working fluid composition for a refrigerator containing these refrigerants.
Detailed Description
The ester for a refrigerator oil of the present invention will be described below.
In the present specification, the resin range defined by the symbols "to" includes the numerical values at both ends (upper limit and lower limit) of the symbols "to" respectively. For example, "2 to 5" means "2 or more and 5 or less".
The ester for refrigerator oil of the present invention is obtained by: neopentyl glycol (component (A)), a linear diol having hydroxyl groups on both carbon terminals of 2 to 6 carbon atoms (component (B)), a linear dicarboxylic acid having carboxyl groups on both carbon terminals of 4 to 10 carbon atoms (component (C)), and a monohydric alcohol having 6 to 12 carbon atoms (component (D)) are mixed and subjected to an esterification reaction.
The terms of the component (a), the component (B), the component (C) and the component (D) are used for convenience and the like, and one compound or two or more compounds may be contained in each component. In the case where two or more compounds are contained in each component, the amount of each component is the total amount of the two or more compounds belonging to the component.
As the neopentyl glycol as the component (a) used in the present invention, commercially available neopentyl glycol can be used, and as the form of the neopentyl glycol, solid neopentyl glycol or liquid neopentyl glycol diluted with water can be used.
The component (B) is a linear diol having hydroxyl groups on carbon atoms at both ends of 2 to 6 carbon atoms, and specific examples thereof include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol. Straight-chain dihydric saturated alcohols are preferred, and 1, 4-butanediol is particularly preferred. The component (B) can provide an ester having excellent viscosity index, low-temperature stability and lubricity.
The component (C) is a linear dicarboxylic acid having carboxyl groups on carbons at both ends of 4 to 10 carbon atoms, and specific examples thereof include succinic acid (carbon number 4), glutaric acid (carbon number 5), adipic acid (carbon number 6), pimelic acid (carbon number 7), suberic acid (carbon number 8), azelaic acid (carbon number 9), sebacic acid (carbon number 10), and the like. Preferably, a linear saturated dicarboxylic acid having 6 to 8 carbon atoms is used. The component (C) can provide an ester having excellent viscosity index and low-temperature stability.
The component (D) is a C6-12 monohydric alcohol, and may be either a straight-chain alcohol or a branched-chain alcohol. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 2-ethylhexanol, and 3,5, 5-trimethylhexanol. Preferably, the branched alcohol is a saturated branched alcohol having 6 to 10 carbon atoms, and an ester having excellent low-temperature stability can be obtained. Particular preference is given to using 2-ethylhexanol or 3,5, 5-trimethylhexanol.
The ester for a refrigerator oil of the present invention is an ester for a refrigerator oil, which is composed of: the amount of the component (B) is 0.1 to 0.4 mol, the amount of the component (C) is 0.8 to 2.8 mol, and the amount of the component (D) is 0.3 to 2.3 mol, based on 1.0 mol of the component (A).
If the amount of the component (B) is less than 0.1 mol based on 1.0 mol of the component (a), it is difficult to obtain a desired viscosity index and lubricity, and if it exceeds 0.4 mol, the low-temperature stability of the ester is deteriorated. The amount of the constituent component derived from the component (B) may preferably be 0.1 to 0.3 mol based on 1.0 mol of the constituent component derived from the component (a).
If the amount of the component derived from the component (C) is less than 0.8 mol based on 1.0 mol of the component derived from the component (a), it is difficult to obtain a high viscosity index, and if it exceeds 2.8, it is difficult to obtain lubricity. The amount of the component derived from the component (C) is preferably 0.9 mol or more and preferably 2.3 mol or less based on 1.0 mol of the component derived from the component (a).
When the amount of the component (D) is 0.3 to 2.3 moles based on 1.0 mole of the component (a), an ester having an appropriate viscosity for use as a refrigerator oil can be easily obtained. The amount of the constituent component derived from the component (D) is preferably 0.5 mol or more and preferably 2.1 mol or less with respect to 1.0 mol of the constituent component derived from the component (a).
The molar ratio of each of the above-mentioned components was analyzed and calculated by gas chromatography. After diluting 0.1g of the ester with a mixed solvent of 5g of toluene/methanol (80 wt%/20 wt%), 0.3g of 28% sodium methoxide methanol solution (Wako pure chemical industries, Ltd.) was added thereto, and the mixture was allowed to stand at 60 ℃ for 30 minutes to methanolyze the ester. The obtained ester decomposition solution was analyzed by gas chromatography, and the peak area ratios of the obtained component (a), component (B), component (C), and component (D) were calculated by converting them into molar ratios. Further, the components of the ester decomposition product can be identified by gas chromatography analysis of each component individually.
The ester of the present invention is an ester synthesized by blocking the carboxyl group of the component (C) by the components (a), (B) or (D) by adjusting the molar ratio of the constituent components derived from the components (a), (B), (C) and (D), and includes an ester having a terminal structure of an alkyl group derived from the component (D) as a subcomponent, and an ester having a terminal structure of a hydroxyl group derived from the component (a) or a hydroxyl group derived from the component (B).
Examples of specific terminal structures of the ester of the present invention will be described with reference to the formulae (3), (4) and (5). The formula (3) is a structure in which the ester has an alkyl group derived from the component (D) at the terminal, the formula (4) is a structure in which the ester has a hydroxyl group derived from the component (a) at the terminal, and the formula (5) is a structure in which the ester has a hydroxyl group derived from the component (B) at the terminal.
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
m is an integer of 1 to 5, R1Represents an alkyl group derived from the component (D).
By the above-described structural design, when used as a refrigerator oil, the ester is not easily hydrolyzed or thermally decomposed, and can be an ester having excellent stability.
The ester for a refrigerator oil of the present invention satisfies formula (1) and formula (2).
0.08≤BOH/(AOH+BOH)≤0.15···(1)
AOHIs the number of moles of terminal hydroxyl groups from component (a) in the ester;
BOHthe number of moles of the terminal hydroxyl group derived from the component (B) in the ester.
The formula (1) represents the molar ratio of the terminal hydroxyl group derived from the component (B) to the total amount of the terminal hydroxyl group derived from the component (a) and the terminal hydroxyl group derived from the component (B) in the ester.
[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)
AOHIs the number of moles of terminal hydroxyl groups from component (a) in the ester;
BOHis the number of moles of terminal hydroxyl groups from component (B) in the ester;
Amolthe number of moles of the constituent component derived from the component (A) in the ester;
Bmolthe number of moles of the constituent component derived from the component (B) in the ester.
The molecule of formula (2) is [ BOH/(AOH+BOH)]The molar ratio of the terminal hydroxyl group derived from the component (B) to the total amount of the terminal hydroxyl group derived from the component (A) and the terminal hydroxyl group derived from the component (B) in the ester is represented by formula (1).
On the other hand, the denominator of the formula (2) is [ B ]mol/(Amol+Bmol)]The molar ratio of the component derived from the component (B) to the total amount of the component derived from the component (a) and the component derived from the component (B) in the ester is expressed.
Therefore, the formula (2) indicates how small the molar ratio of the terminal hydroxyl group derived from the component (B) is relative to the molar ratio of the constituent component derived from the component (B) in the ester, in other words, how uneven the distribution of the component (B) in the terminal structure relative to the entire structure of the ester is.
The numerical values of the formulae (1) and (2) were measured as follows.
The numerical values of formula (1) and of the molecules of formula (2): b isOH/(AOH+BOH)。
Find out1The H-NMR spectrum was calculated by dividing the integrated value of the peak (3.2 to 3.4ppm) of α hydrogen relative to the hydroxyl group of the component (A) and the integrated value of the peak (3.6 to 3.8ppm) of α hydrogen relative to the hydroxyl group of the component (B) by the sum of the integrated values by the integrated value of α hydrogen relative to the hydroxyl group of the component (B).
Numerical value of denominator of formula (2): b ismol/(Amol+Bmol)
The number of moles of each constituent component derived from the component (a) and the component (B) was determined by the above-mentioned gas chromatography analysis, and the molar ratio was calculated.
The component (a) does not have hydrogen bonded to the β carbon (β hydrogen is not present), and therefore, the terminal hydroxyl group generated at the terminal of the ester structure is excellent in heat resistance as compared with the terminal structure derived from the component (B), that is, an ester derived from the component (a) having a large number of terminal ester structures is excellent in heat resistance as compared with an ester other than this, and as a result, an ester having more excellent heat resistance can be formed by the molar ratio of the hydroxyl group derived from the component (B) being 0.15 or less of the total number of hydroxyl groups, and an ester having excellent lubricity and heat resistance can be more easily obtained when the molar ratio of the terminal hydroxyl group derived from the component (B) to the total number of terminal hydroxyl groups derived from the component (a) and the component (B) is 0.08 to 0.15.
Further, an ester in which terminal hydroxyl groups derived from the component (B) are unevenly distributed so that the molar ratio becomes smaller than the molar ratio of the constituent component derived from the component (B) in the ester is more excellent in heat resistance. The degree of the maldistribution of the component (B) in the terminal structure can be represented by the molar ratio of the terminal hydroxyl groups derived from the component (B) relative to the molar ratio of the constituent components derived from the component (B) in the ester, and by setting this value to 0.9 or less, an ester having more excellent heat resistance can be obtained. This value is 0.9 or less, and more preferably 0.8 or less. The lower limit of this value is not particularly limited, but is preferably 0.2 or more, more preferably 0.3 or more, and still more preferably 0.5 or more.
The ester of the present invention is an ester in which the molar ratio of hydroxyl groups derived from the component (B) to all hydroxyl groups in the ester is decreased relative to the molar ratio of the component derived from the component (B) to the sum of the component derived from the component (a) and the component derived from the component (B), and for the above reasons, the ester satisfying the formulae (1) and (2) is an ester having further excellent heat resistance.
In the production of an ester, the component (a), the component (B), the component (C) and the component (D) are all put into a suitable reactor, and an esterification reaction is carried out under normal pressure and in a nitrogen atmosphere. In order to remove the water generated during the reaction more effectively, the esterification reaction may be carried out at 150 to 250 ℃. However, in order to obtain an ester having more excellent heat resistance, first, the esterification reaction is performed at 100 to 150 ℃. Then carrying out secondary esterification reaction at 150-250 ℃.
The primary esterification reaction is preferably carried out at 100 to 140 ℃, and more preferably at 100 to 130 ℃, whereby an ester having excellent heat resistance can be easily obtained. Further, the primary esterification reaction is preferably 1 to 10 hours, more preferably 2 to 8 hours, and thus an ester having excellent heat resistance can be easily obtained.
The secondary esterification reaction is preferably carried out at 160 to 260 ℃, and more preferably at 180 to 250 ℃. In this case, the secondary esterification reaction is carried out until the acid value is 10mgKOH/g or less, preferably 5mgKOH/g or less, and more preferably 2 mgKOH/g.
In addition, the esterification reaction may use a Bronsted acid (Bronsted acid) catalyst or a Lewis acid (Lewis acid) catalyst, but is preferably carried out without a catalyst.
After the esterification reaction, excess component (D) was distilled off under reduced pressure to obtain a crude ester. Further, the crude ester is subjected to a purification treatment with an adsorbent, whereby the target ester for refrigerator oil can be obtained.
The kinematic viscosity of the ester for refrigerator oil of the present invention at 40 ℃ is preferably 20 to 500mm2And s. More preferably 20 to 300mm2More preferably 20 to 250mm in terms of the total mass of the composition2(ii) s, most preferably 20 to 180mm2And s. The hydroxyl value is preferably 5 to 40mgKOH/g, more preferably 15 to 35 mgKOH/g.
The ester for refrigerating machine oil of the present invention can be used alone as a base oil, or can be used in combination with other base oils. Further, known additives, for example, a phenol-based antioxidant, a metal deactivator such as benzotriazole, thiadiazole or dithiocarbamate, an acid scavenger such as epoxy compound or carbodiimide, a phosphorus-based extreme pressure agent, and the like may be added as appropriate depending on the purpose.
The ester for a refrigerator oil of the present invention has high compatibility with a non-chlorine freon refrigerant or a natural refrigerant, and therefore can be suitably used for a working fluid composition for a refrigerator containing these refrigerants. As the non-chlorine type freon refrigerant, Hydrofluorocarbons (HFCs), Hydrofluoroolefins (HFOs), Hydrocarbons (HCs), or monomers of natural refrigerants, or mixtures thereof can be cited.
Specific examples of Hydrofluorocarbon (HFC) refrigerants are preferably 1,1,1, 2-tetrafluoroethane (R-134a), pentafluoroethane (R-125), difluoroethane (R-32), trifluoromethane (R-23), 1,1,2, 2-tetrafluoroethane (R-134), 1,1, 1-trifluoroethane (R-143a), 1, 1-difluoroethane (R-152a), and the like, and mixtures of any 1 or 2 or more. Examples of the mixed refrigerant include R-407C (R-134A/R-125/R-32 is 52/25/23 mass%), R-410R (R-125/R-32 is 50/50 mass%), R-404A (R-125/R-143/R-134A is 44/52/4 mass%), R-407E (R-134A/R-125/R-32 is 60/15/25 mass%), and R-410B (R-32/R-125 is 45/55 mass%). Among these, a refrigerant containing at least one of R-134a and R-32 is particularly preferable, and a single R-32 refrigerant can be more preferably exemplified.
Specific examples of the Hydrofluoroolefin (HFO) refrigerant include 1,2,3,3, 3-pentafluoropropene (HFO-1225ye), 1,3,3, 3-tetrafluoropropene (HFO-1234ze), 2,3,3, 3-tetrafluoropropene (HFO-1234yf), 1,2,3, 3-tetrafluoropropene (HFO-1234ye), and a mixture of 1,2,3, 3-trifluoropropene (HFO-1243 zf). From the viewpoint of the physical properties of the refrigerant, it is preferably 1 or 2 or more selected from the group consisting of HFO-1225ye, HFO-1234ze and HFO-1234 yf.
Further, as the Hydrocarbon (HC) refrigerant, propane (R290), isobutane (R600a), or the like, or a mixture thereof may be mentioned, and as the natural refrigerant, ammonia, carbon dioxide, or the like may be mentioned. Particularly preferred examples include R290, R600 and carbon dioxide.
In a working fluid composition for a refrigerator oil, the mass ratio of the ester for a refrigerator oil to a non-chlorine freon refrigerant or a natural refrigerant is 10:90 to 90:10 in a normal case. When the mass ratio of the refrigerant is within this range, the working fluid composition has appropriate viscosity, excellent lubricity, and high refrigeration efficiency, and therefore, this is preferable.
Examples
The present invention will be described in further detail with reference to examples below, but the present invention is not limited to the examples below.
Various analyses of the esters for refrigerator oils obtained in examples and comparative examples were carried out by the following methods.
Acid value: measured according to JIS K2501.
Hydroxyl value: measured according to JIS K0070.
Kinematic viscosity: measured according to JIS K2283.
Preparation of example 1
124g (1.19mol) of neopentyl glycol, 30g (0.34mol) of 1, 4-butanediol, 355g (2.43mol) of adipic acid, 339g (2.35mol) of 3,5, 5-trimethylhexanol were charged into a four-necked flask, and reacted at normal pressure for 3 hours while distilling off reaction water (reaction water) at 120 ℃ under a nitrogen atmosphere. Then, the reaction was continued at 200 ℃ for 7 hours until the acid value was 2 or less. Then, excess 3,5, 5-trimethylhexanol was removed by distillation at 200 ℃ under reduced pressure of 1 to 5kPa to obtain a crude ester. The crude ester was cooled, and an acidic white clay and a silica-alumina adsorbent were added thereto so as to be 1.0 mass% of the amount of the theoretically obtained ester, respectively, to carry out adsorption treatment. The adsorption treatment temperature, pressure and adsorption treatment time are set to 100 ℃, 1-5 kPa, 2 hours. Finally, filtration was performed using a 1 micron filter paper to obtain the target ester.
Preparation of example 2
Into a four-necked flask were charged 180g (1.73mol) of neopentyl glycol, 25g (0.28mol) of 1, 4-butanediol, 360g (2.47mol) of adipic acid, and 256g (1.78mol) of 3,5, 5-trimethylhexanol, and reacted at 115 ℃ for 4 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere. The subsequent steps were carried out in the same manner as in example 1 to obtain the target ester.
Preparation of example 3
Into a four-necked flask, 205g (1.97mol) of neopentyl glycol, 26g (0.28mol) of 1, 4-butanediol, 373g (2.55mol) of adipic acid, and 217g (1.50mol) of 3,5, 5-trimethylhexanol were charged, and reacted at 125 ℃ for 3 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere. The subsequent steps were carried out in the same manner as in example 1 to obtain the target ester.
Preparation of example 4
Into a four-necked flask were charged 174g (1.66mol) of neopentyl glycol, 46g (0.51mol) of 1, 4-butanediol, 373g (2.55mol) of adipic acid, and 238g (1.65mol) of 3,5, 5-trimethylhexanol, and reacted at 120 ℃ for 4 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere. The subsequent steps were carried out in the same manner as in example 1 to obtain the target ester.
Preparation of example 5
129g (1.23mol) of neopentyl glycol, 28g (0.26mol) of 1, 5-pentanediol, 393g (2.25mol) of suberic acid, and 300g (2.30mol) of n-octanol were charged into a four-necked flask, and reacted at 120 ℃ for 5 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere. The subsequent steps were carried out in the same manner as in example 1 to obtain the target ester.
Preparation of example 6
215g (2.07mol) of neopentyl glycol, 22g (0.29mol) of 1, 3-propanediol, 385g (2.64mol) of adipic acid, 214g (1.49mol) of 3,5, 5-trimethylhexanol were charged into a four-necked flask, and reacted at 120 ℃ for 4 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere. The subsequent steps were carried out in the same manner as in example 1 to obtain the target ester.
Preparation of example 7
Into a four-necked flask were charged 211g (2.03mol) of neopentyl glycol, 42g (0.36mol) of 1, 6-hexanediol, 385g (2.64mol) of adipic acid, and 206g (1.43mol) of 3,5, 5-trimethylhexanol, and reacted at 115 ℃ for 5 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere. The subsequent steps were carried out in the same manner as in example 1 to obtain the target ester.
Preparation of comparative example 1
Into a four-necked flask were charged 174g (1.66mol) of neopentyl glycol, 46g (0.51mol) of 1, 4-butanediol, 373g (2.55mol) of adipic acid, and 238g (1.65mol) of 3,5, 5-trimethylhexanol, and the reaction was continued at normal pressure for 7 hours until the acid value became 2 or less while distilling off the reaction water at 200 ℃ under a nitrogen atmosphere. Then, the excess 3,5, 5-trimethylhexanol was distilled off at 200 ℃ under reduced pressure of 1 to 5kPa to obtain a crude ester. The crude ester was cooled, and an acidic white clay and a silica-alumina adsorbent were added thereto so as to be 1.0 mass% of the amount of the theoretically obtained ester, respectively, to carry out adsorption treatment. The adsorption treatment temperature, pressure and adsorption treatment time are set to 100 ℃, 1-5 kPa, 2 hours. Finally, filtration was performed using a 1 micron filter paper to obtain the target ester.
Preparation of comparative example 2
104g (1.00mol) of neopentyl glycol, 27g (0.30mol) of 1, 4-butanediol, and 351g (2.40mol) of adipic acid were charged into a four-necked flask, and reacted at 200 ℃ for 3 hours under normal pressure while distilling off reaction water under a nitrogen atmosphere until the acid value became 270 or less, to obtain an ester intermediate. 361g (2.50mol) of 3,5, 5-trimethylhexanol was further added to the ester intermediate, and the reaction was continued for 7 hours until the acid value was 2 or less. Then, the excess 3,5, 5-trimethylhexanol was distilled off at 200 ℃ under reduced pressure of 1 to 5kPa to obtain a crude ester. The crude ester was cooled, and an acidic white clay and a silica-alumina adsorbent were added thereto so as to be 1.0 mass% of the amount of the theoretically obtained ester, respectively, to carry out adsorption treatment. The adsorption treatment temperature, pressure, and adsorption treatment time are set to 100 ℃,1 to 5kPa, and 2 hours. Finally, filtration was performed using a 1 micron filter paper to obtain the target ester.
Heat resistance (Heat test)
The ester for a refrigerator oil described above was evaluated for heat resistance by performing a heat test in which the ester for a refrigerator oil was heated in a thermostatic bath at 130 ℃ for 72 hours in an air atmosphere, and the acid value of the heated ester for a refrigerator oil was measured.
Lubricity (SRV test)
The above-mentioned ester for a refrigerator oil was evaluated for lubricity by an SRV tester. The SRV test was conducted using balls/disks, and SUJ-2 was used as each test piece. The test conditions were carried out at a test temperature of 60 ℃, a load of 100N, an amplitude of 1mm, and a vibration frequency of 50Hz, and the diameter of a wear scar after the lapse of 25 minutes from the test time was measured.
The preparation conditions of examples 1 to 7 and comparative examples 1 to 2 are summarized in tables 1 and 2, and the physical property values, heat resistance, and lubricity are summarized in tables 3 and 4. Table 1 and table 2 show the addition ratio of each component, and table 3 and table 4 show the measured values of the molar ratio of the constituent components derived from each component in the produced ester.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
As shown in tables 1 to 4, the esters of examples 1 to 7 are excellent in lubricity and also excellent in heat resistance, and therefore, are less likely to deteriorate even under severe lubricating conditions in a compressor, and can be used for a long period of time. Further, since the increase in the acid value in the heating test is suppressed, the generation of decomposition products which are a cause of corrosion of metals and the like in the compressor is also suppressed.
On the other hand, in comparative examples 1 to 2, since the increase in the acid value was large unlike the ester of the example, the progress of the decomposition of the ester by the heat test was confirmed as compared with the example.
Claims (2)
1. An ester for a refrigerator oil, characterized in that:
the ester for refrigerator oil is obtained from a component A, a component B, a component C and a component D in such proportions that the amount of a component derived from the component B is 0.1 to 0.4 mol, the amount of a component derived from the component C is 0.8 to 2.8 mol and the amount of a component derived from the component D is 0.3 to 2.3 mol based on 1.0 mol of the component derived from the component A,
the hydroxyl value of the ester is 5-40 mgKOH/g, which satisfies formula (1) and formula (2),
component A: the ratio of neopentyl glycol,
component B: a linear diol having 2 to 6 carbon atoms and having hydroxyl groups at both ends,
component C: a straight chain dicarboxylic acid having 4 to 10 carbon atoms and having carboxyl groups at both ends,
component D: a C6-12 monohydric alcohol,
0.08≤BOH/(AOH+BOH)≤0.15……(1)
[BOH/(AOH+BOH)]/[Bmol/(Amol+Bmol)]≤0.9……(2)
in the above formulas (1) and (2), AOHIs the number of moles of terminal hydroxyl groups from the component a in the ester; b isOHIs the number of moles of terminal hydroxyl groups from the component B in the ester; a. themolIs the number of moles of constituent components from the component a in the ester; b ismolThe number of moles of the constituent component derived from the component B in the ester.
2. A working fluid composition for a refrigerator oil, characterized by comprising a non-chlorine Freon refrigerant or a natural refrigerant and the ester for a refrigerator oil according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-115892 | 2015-06-08 | ||
| JP2015115892 | 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 |
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| Publication Number | Publication Date |
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| CN107614663A CN107614663A (en) | 2018-01-19 |
| CN107614663B true CN107614663B (en) | 2020-06-26 |
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| CN201680029198.3A Active CN107614663B (en) | 2015-06-08 | 2016-06-06 | Ester for refrigerator oil and working fluid composition for refrigerator oil |
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| 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) |
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| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH108084A (en) * | 1996-06-25 | 1998-01-13 | Kao Corp | Composition for refrigerator-working fluid |
| US6667285B1 (en) * | 1999-05-10 | 2003-12-23 | New Japan Chemical Co., Ltd. | Lubricating oil for refrigerator, hydraulic fluid composition for refrigerator and method for lubricating of refrigerator |
| CA2487587C (en) * | 2003-11-21 | 2012-04-24 | Nof Corporation | A polyol ester for use within a refrigeration lubricant composition compatible with chlorine-free hydrofluorocarbon refrigerants |
| 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 KR KR1020187000300A patent/KR102523681B1/en active IP Right Grant
- 2016-06-06 WO PCT/JP2016/066756 patent/WO2016199718A1/en active Application Filing
- 2016-06-06 CN CN201680029198.3A patent/CN107614663B/en active Active
- 2016-06-06 JP JP2017523626A patent/JP6614510B2/en active Active
- 2016-06-06 EP EP16807425.0A patent/EP3305878A4/en not_active Withdrawn
- 2016-06-08 TW TW105118146A patent/TWI689581B/en active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107614663A (en) | 2018-01-19 |
| JP6614510B2 (en) | 2019-12-04 |
| KR20180017079A (en) | 2018-02-20 |
| JPWO2016199718A1 (en) | 2018-03-22 |
| TWI689581B (en) | 2020-04-01 |
| KR102523681B1 (en) | 2023-04-19 |
| TW201700721A (en) | 2017-01-01 |
| EP3305878A1 (en) | 2018-04-11 |
| EP3305878A4 (en) | 2018-12-05 |
| WO2016199718A1 (en) | 2016-12-15 |
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