CN112410094A - Base oil for refrigerator oil, and working fluid composition for refrigerator - Google Patents

Base oil for refrigerator oil, and working fluid composition for refrigerator Download PDF

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Publication number
CN112410094A
CN112410094A CN202011294406.7A CN202011294406A CN112410094A CN 112410094 A CN112410094 A CN 112410094A CN 202011294406 A CN202011294406 A CN 202011294406A CN 112410094 A CN112410094 A CN 112410094A
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China
Prior art keywords
acid
fatty acid
oil
refrigerator
refrigerator oil
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CN202011294406.7A
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CN112410094B (en
Inventor
胡余生
郭小青
徐嘉
史正良
林新俊
黄毓华
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Gree Green Refrigeration Technology Center Co Ltd of Zhuhai
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Gree Green Refrigeration Technology Center Co Ltd of Zhuhai
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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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates

Abstract

This applicationRelates to the technical field of refrigerator oil products, in particular to refrigerator oil base oil, and also relates to refrigerator oil containing the refrigerator oil base oil and a working fluid composition for a refrigerator. The refrigerator oil base oil is an ester synthesized by pentaerythritol and a plurality of fatty acids, wherein the fatty acids comprise a first fatty acid, and the first fatty acid is C5The fatty acid further comprises at least one of a second fatty acid and a third fatty acid, the second fatty acid being C8‑C9The third fatty acid is C5‑C8The dibasic fatty acid of (1). The invention provides a refrigerating machine oil and a working fluid composition for a refrigerating machine, which can simultaneously achieve the compatibility, lubricity, thermal stability and/or chemical stability of a refrigerant when the R32 refrigerant is used.

Description

Base oil for refrigerator oil, and working fluid composition for refrigerator
Technical Field
The application relates to the technical field of refrigerator oil products, in particular to refrigerator oil base oil, and also relates to refrigerator oil and a working fluid composition for a refrigerator, which contain the refrigerator oil base oil.
Background
With the increasing depletion of the ozone layer, CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons) which have been used as refrigerants for refrigerators have been the subject of limitation, and HFC (hydrofluorocarbon) refrigerants have been used instead of them. Among HFC refrigerants, HFC-134a, R407C, and R410A have high Global Warming Potential (GWP) and are subject to restriction even though the Ozone Depletion Potential (ODP) is 0. R32 (difluoromethane) refrigerant has attracted attention as one of chlorine-free HFCs and candidate refrigerants with low GWP because of its characteristics such as environmental friendliness, high energy efficiency, and easy handling. However, the refrigerating machine oil widely used in the HFC refrigerant at present is difficult to be compatible with the R32 refrigerant. When the refrigerating machine oil is not compatible with the refrigerant, the oil and the refrigerant are easily layered on an evaporator in a refrigerating system, and the refrigerating machine oil is difficult to return to a compressor of the refrigerating system, so that moving parts of the compressor lack oil, poor lubrication causes abrasion, and further reliability of the compressor is affected. Meanwhile, the oil retained in the evaporator affects the heat exchange efficiency of the evaporator, which causes the efficiency of the refrigeration system to be reduced; the refrigerating machine oil with good compatibility with R32 is mixed with the R32 refrigerant working fluid composition under the working condition of high temperature and high pressure of the refrigerating machine, the viscosity is too small, the lubrication is poor, and the abrasion of the moving parts of the compressor is increased.
According to the descriptions of patent publications such as CN103097501B, CN103865607B, CN103865608B, CN104093694B, CN102725259B, CN103732572B, CN102958902B and CN102958901B in the prior art, in order to solve the above problems, the refrigerating machine oil containing R32 refrigerant has been used mostly as base oil of fatty acid synthetic polyol ester composed of polyol and isobutyric acid (2-methylpropionic acid) containing 4 carbon atoms, but in actual use, it is found that synthetic polyol ester containing 4 carbon atoms isobutyric acid is easy to cause reduction of thermal/chemical stability, and is easy to decompose and deteriorate particularly under high temperature, oxygen and moisture environments, resulting in failure of oil product, although it has good compatibility with R32.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: at present, the refrigerating machine oil widely used for the HFC refrigerant is difficult to dissolve with the R32 refrigerant, so that the oil return property of the refrigerating machine oil in a refrigerating system is poor, and the oil quantity of the refrigerating machine in a compressor is reduced to cause poor lubrication; the refrigerating machine oil with good compatibility with the R32 refrigerant has too low viscosity when mixed with the R32 refrigerant working fluid composition under the working condition of high temperature and high pressure of the refrigerating machine, so that poor lubrication is caused, and the abrasion of the moving parts of the compressor is increased. In order to solve the technical problems, the application provides a refrigerating machine oil base oil, a refrigerating machine oil and a working fluid composition for a refrigerating machine.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a refrigerator oil base.
The refrigerator oil base oil according to the embodiment of the application is an ester synthesized by pentaerythritol and a plurality of fatty acids, wherein the fatty acids comprise a first fatty acid, and the first fatty acid is C5The fatty acid further comprises at least one of a second fatty acid and a third fatty acid, the second fatty acid being C8-C9The third ester of (a)The fatty acid is C5-C8The dibasic fatty acid of (1).
Further, in the refrigerator oil base oil, the molar ratio of the first fatty acid in the fatty acid is 20-50%.
Further, in the refrigerator oil base, the first fatty acid is at least one of n-pentanoic acid and 3-methylbutyric acid.
Further, in the refrigerator oil base oil, the second fatty acid is at least one of 2-ethylhexanoic acid and 3,5,5, -trimethylhexanoic acid.
Further, in the refrigerator oil base, the third fatty acid is adipic acid.
In order to achieve the above object, according to a second aspect of the present invention, there is also provided a refrigerator oil.
The refrigerator oil according to the embodiment of the application comprises the refrigerator oil base oil provided by the first aspect of the application.
Further, the refrigerator oil also comprises an additive, wherein the additive comprises at least one of an extreme pressure antiwear agent, an antioxidant, an antifoaming agent, an acid trapping agent and a metal deactivator.
In order to achieve the above object, according to a third aspect of the present invention, there is also provided a working fluid composition for a refrigerator.
The working fluid composition for the refrigerator according to the embodiment of the application comprises the refrigerator oil provided by the second aspect of the application and R32 refrigerant.
Further, in the working fluid composition for the refrigerator, the kinematic viscosity of the refrigerator oil at 40 ℃ is 60-120 mm2The pour point is below-35 ℃, the low-temperature two-phase separation temperature of the refrigerator oil and the R32 refrigerant is lower than 10 ℃, and the dissolution viscosity of the working fluid composition for the refrigerator is 2.0mm under the conditions that the actual operation working condition of a compressor is 110 ℃ and 4.2MPa2More than s.
The refrigerating machine oil and the working fluid composition for the refrigerating machine provided by the invention can simultaneously achieve the compatibility, the lubricity and the thermal/chemical stability of the refrigerant when the R32 refrigerant is used.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail.
The applicant has found that polyol esters of pentaerythritol and linear or branched monobasic fatty acids having 5 carbon atoms have good compatibility with R32 refrigerant, but have the disadvantages of low solubility viscosity and insufficient lubricating performance. The polyol ester formed by pentaerythritol and branched fatty acid with 8-9 carbon atoms and dibasic fatty acid with 5-8 carbon atoms has good low-temperature fluidity and stability with R32 refrigerant, but has poor compatibility with R32 refrigerant, is easy to stay in a system, causes oil shortage of a compressor, causes poor lubrication of a friction pair of the compressor, and reduces the energy efficiency of the system. The applicant has further studied and found that a pentaerythritol mixed acid ester obtained by mixing pentaerythritol with a fatty acid of the above specific type and ratio range can balance the compatibility with the R32 refrigerant, low-temperature fluidity, stability and lubricity, and is a refrigerator oil base having excellent overall performance.
Specifically, the refrigerator oil base oil provided by the embodiment of the invention is an ester synthesized from pentaerythritol and a plurality of fatty acids, wherein the fatty acids comprise a first fatty acid, and the first fatty acid is C5The fatty acid further comprises at least one of a second fatty acid and a third fatty acid, the second fatty acid being C8-C9The third fatty acid is C5-C8The dibasic fatty acid of (1).
The refrigerating machine oil base oil is formed into the refrigerating machine oil by selectively adding additives, and the refrigerating machine oil is mixed with the R32 refrigerant to obtain the working fluid composition for the refrigerating machine. Compared with the prior refrigerating machine oil, the refrigerating machine oil has good low-temperature fluidity and good compatibility with R32 refrigerant, the refrigerating machine oil is ensured to return to the pump body of the compressor in time in the compression-condensation-evaporation cycle of the refrigerating system, the abrasion of the friction pair of the compressor caused by oil shortage is avoided, meanwhile, the dissolving viscosity is high, so that a sufficiently thick oil film can be ensured between the friction pairs of the pump body parts of the compressor, thereby improving the wear resistance of the working fluid composition, improving the running reliability of the compressor, having good thermal/chemical stability, avoiding the increase of the acid value of the oil product caused by the deterioration of the refrigerating oil, thereby causing corrosion of parts or copper plating and affecting the efficiency and reliability of the refrigeration system, so that the refrigerator oil has good low-temperature fluidity, stability, lubricity and compatibility with R32 refrigerant.
In the refrigerator oil base oil, the first fatty acid may specifically be n-valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, or 2, 2-dimethylpropionic acid, wherein n-valeric acid is preferred as the linear monobasic fatty acid, 3-methylbutyric acid is preferred as the branched monobasic fatty acid, and the molar ratio of the first fatty acid in the fatty acids is 20 to 50%, more preferably 30 to 40%.
In the refrigerator oil base, specific examples of the second fatty acid include 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 4-ethylhexanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 2-ethylheptanoic acid, 3-ethylheptanoic acid, 4-ethylheptanoic acid, 3,5, 5-trimethylhexanoic acid, and the like, and 2-ethylhexanoic acid and 3,5,5, -trimethylhexanoic acid having high stability are preferable.
In the refrigerator oil base, specific examples of the third fatty acid include glutaric acid, adipic acid, pimelic acid, suberic acid, and preferably adipic acid.
It is to be noted that the pentaerythritol ester in the present invention may be a full ester in which all the hydroxyl groups of pentaerythritol are esterified, may be a partial ester in which a part of the hydroxyl groups of pentaerythritol are not esterified but remain, and may be a mixture of a full ester and a partial ester, and is preferably a full ester.
In order to further improve the performance of the refrigerator oil, various known additives for refrigerator oils may be further contained as necessary. Examples of the additives include an extreme pressure anti-wear agent, an antioxidant, an anti-foaming agent, an acid scavenger, and a metal deactivator, and these additives may be used alone or in combination of two or more, and the content of the additives is usually not more than 5% by mass based on the total amount of the refrigerator oil.
The extreme pressure antiwear agent in the additive is used for further improving the wear resistance and extreme pressure performance of the refrigerating machine oil and working fluid composition for the refrigerating machine, and the extreme pressure antiwear agent can be one or two of compounds such as phosphate ester, sulfur phosphate ester and the like. Wherein the phosphate ester includes, but is not limited to, dibutyl phosphate, tributyl phosphate, diphenyl phosphate, triphenyl phosphate, or naphthyl phosphate; phosphothioesters include, but are not limited to, dibutyl thiophosphate, tributyl thiophosphate, diphenyl thiophosphate, triphenyl thiophosphate, or dithiophosphate.
The antioxidant in the additive is used for further improving the thermal oxidation stability of the refrigerating machine oil and the working fluid composition for the refrigerating machine, and the antioxidant can be a composition formed by mixing at least one or more of compounds such as phenols, amines, metal organic matters, boron compounds, copper compounds and the like. Preferably, the antioxidant in the embodiment of the present invention is a composition formed by mixing one or more of phenols and amines, wherein the phenol antioxidant includes, but is not limited to, 2, 4-di-tert-ethylphenol, 2, 4-di-tert-propylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-ethylphenol, 2, 6-di-tert-propylphenol, 2, 6-di-tert-butylphenol; amine antioxidants include, but are not limited to, naphthylamine, phenylnaphthylamine, N-naphthyl-alpha-naphthylamine.
The acid scavenger in the additive is used for further improving the thermo-chemical stability of the refrigerating machine oil and the working fluid composition for a refrigerating machine, and may be at least one of alkyl glycidyl ester and ether, specifically, 2-dimethyl octyl glycidyl ester, tert-butyl phenyl glycidyl ester, glycidyl benzoate, octyl glycidyl ether, decyl glycidyl ether, pentaerythritol glycidyl ether, and the like. The acid catcher in the embodiment of the invention is mainly used for neutralizing acid generated in the polyol ester deterioration process and slowing down the corrosion effect on metal.
As the antifoaming agent in the additive, silicon type and non-silicon type can be exemplified. Examples of the silicon type antifoaming agent include dimethylsilicone oil. Examples of the non-silicon type antifoaming agent include homopolymers or copolymers of acrylic acid esters or methacrylic acid esters. A composite antifoaming agent consisting of two or more antifoaming agents may also be used.
Examples of the metal deactivator in the additive include benzotriazole derivatives and the like.
The refrigerating machine oil according to the embodiment of the present invention is generally present in the form of a working fluid composition for a refrigerator, which is mixed with a refrigerant in a compressor of the refrigerator. The refrigerant can be R32 (difluoromethane) refrigerant. The content of the refrigerating machine oil in the working fluid composition is not particularly limited, and 1 to 500 parts by mass of the refrigerating machine oil is preferably used, and more preferably 2 to 400 parts by mass of the refrigerating machine oil is used, based on 100 parts by mass of the refrigerant.
The refrigerating machine oil and working fluid composition according to the embodiment of the present invention can be preferably used for an air conditioner having a reciprocating or rotary hermetic compressor, a refrigerator, an open or hermetic vehicle air conditioner, a dehumidifier, a refrigerator, a freezer, a refrigerator-freezer, a vending machine, a cooling device for showcases and the like, a refrigerator having a centrifugal compressor, and the like.
In order to make the technical solutions in the embodiments of the present application better understood, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Examples
The present invention will be described more specifically below based on examples and comparative examples, but the present invention is not limited to the following examples. The base oils, additives and index test methods used in the respective examples and comparative examples are listed below. In examples 1 to 25 and comparative examples 1 to 16, base oils 1 to 35 and additives 1 to 6 shown below, respectively, were compounded to prepare sample oils so as to form the composition ratios shown in tables 1 to 5, and properties of the sample oils obtained in examples 1 to 25 and comparative examples 1 to 16 and indices measured by the following respective index test methods were recorded in tables 1 to 5, wherein the compounding ratios of the components in tables 1 to 5 were in mass%.
(base oil)
Base oil 1: pentaerythritol and a carboxyl group in a molar ratio of 20: 10: 70, 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid to obtain mixed acid, and esterifying to obtain pentaerythritol ester.
Base oil 2: pentaerythritol and a carboxyl group molar ratio of 30: 15: 55, 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid to obtain mixed acid, and esterifying to obtain pentaerythritol ester.
Base oil 3: pentaerythritol and a carboxyl group molar ratio of 35: 15: 50 of 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid to obtain pentaerythritol ester.
Base oil 4: pentaerythritol and a carboxyl group molar ratio of 40: 10: 50 of 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid to obtain pentaerythritol ester.
Base oil 5: pentaerythritol and a carboxyl group molar ratio of 50: 10: 40, 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid, and carrying out esterification reaction to obtain pentaerythritol ester.
Base oil 6: pentaerythritol and a carboxyl group in a molar ratio of 20: 20: 60 of n-pentanoic acid, 2-ethylhexanoic acid and 3,5, 5-trimethylhexanoic acid to obtain pentaerythritol ester.
Base oil 7: pentaerythritol and a carboxyl group molar ratio of 35: 15: 50 of n-pentanoic acid, 2-ethylhexanoic acid and 3,5, 5-trimethylhexanoic acid to obtain pentaerythritol ester.
Base oil 8: pentaerythritol and a carboxyl group molar ratio of 50: 5: 45 of n-pentanoic acid, 2-ethylhexanoic acid and 3,5, 5-trimethylhexanoic acid, and carrying out esterification reaction.
Base oil 9: pentaerythritol and a carboxyl group in a molar ratio of 20: 65: 15, 3-methyl butyric acid, 2-ethyl caproic acid and adipic acid to obtain mixed acid, and carrying out esterification reaction to obtain pentaerythritol ester.
10 of base oil: pentaerythritol and a carboxyl group molar ratio of 50: 35: 15, 3-methyl butyric acid, 2-ethyl caproic acid and adipic acid to obtain mixed acid, and carrying out esterification reaction to obtain pentaerythritol ester.
Base oil 11: pentaerythritol and a carboxyl group molar ratio of 40: 55: 5, 3-methyl butyric acid, 3,5, 5-trimethyl hexanoic acid and adipic acid to obtain mixed acid, and performing esterification reaction to obtain pentaerythritol ester.
Base oil 12: pentaerythritol and a carboxyl group in a molar ratio of 20: 70: 10, n-pentanoic acid, 3,5, 5-trimethylhexanoic acid and adipic acid to obtain pentaerythritol ester.
Base oil 13: pentaerythritol and a carboxyl group molar ratio of 50: 40: 10, n-pentanoic acid, 3,5, 5-trimethylhexanoic acid and adipic acid to obtain pentaerythritol ester.
Base oil 14: pentaerythritol and a carboxyl group molar ratio of 30: 15: 45: 10, n-pentanoic acid, 3-methylbutyric acid, 3,5, 5-trimethylhexanoic acid and adipic acid.
15 parts of base oil: pentaerythritol and a carboxyl group molar ratio of 50: 20: 15: 15, n-pentanoic acid, 2-ethylhexanoic acid, 3,5, 5-trimethylhexanoic acid and adipic acid.
Base oil 16: pentaerythritol and a carboxyl group in a molar ratio of 20: 80 and 3,5, 5-trimethylhexanoic acid to obtain mixed acid, and carrying out esterification reaction to obtain the pentaerythritol ester.
Base oil 17: pentaerythritol and a carboxyl group molar ratio of 35: and (3) carrying out esterification reaction on mixed acid formed by 3-methylbutyric acid and 3,5, 5-trimethylhexanoic acid to obtain pentaerythritol ester.
Base oil 18: pentaerythritol and a carboxyl group molar ratio of 50: 50 of 3-methyl butyric acid and 3,5, 5-trimethyl hexanoic acid to form mixed acid, and carrying out esterification reaction to obtain pentaerythritol ester.
Base oil 19: pentaerythritol and at a carboxyl group molar ratio of 45: 55, and 3,5, 5-trimethylhexanoic acid, and carrying out esterification reaction on the mixed acid to obtain the pentaerythritol ester.
20, base oil: esters of pentaerythritol with n-butyric acid.
Base oil 21: esters of pentaerythritol with 2-methylpropionic acid.
Base oil 22: esters of pentaerythritol with n-pentanoic acid.
Base oil 23: esters of pentaerythritol with 3-methylbutyric acid.
Base oil 24: esters of pentaerythritol with 2-ethylhexanoic acid.
Base oil 25: esters of pentaerythritol with 3,5, 5-trimethylhexanoic acid.
Base oil 26: pentaerythritol and a molar ratio of carboxyl groups of 15: 85 of 3-methyl butyric acid and 3,5, 5-trimethyl hexanoic acid to form mixed acid, and carrying out esterification reaction to obtain pentaerythritol ester.
Base oil 27: pentaerythritol and a carboxyl group molar ratio of 60: 40 and 3,5, 5-trimethylhexanoic acid, and carrying out esterification reaction on the mixed acid to obtain the pentaerythritol ester.
Base oil 28: pentaerythritol and a molar ratio of carboxyl groups of 15: 15: 70, 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid to obtain mixed acid, and esterifying to obtain pentaerythritol ester.
Base oil 29: pentaerythritol and a carboxyl group molar ratio of 60: 10: 30, 3-methyl butyric acid, 2-ethyl caproic acid and 3,5, 5-trimethyl caproic acid to obtain mixed acid, and esterifying to obtain pentaerythritol ester.
30 parts of base oil: pentaerythritol and a carboxyl group molar ratio of 55: 15: 20: 10, n-pentanoic acid, 2-ethylhexanoic acid, 3,5, 5-trimethylhexanoic acid and adipic acid to obtain pentaerythritol ester.
Base oil 31: pentaerythritol and a carboxyl group molar ratio of 55: 15: 20: 10, 2-methyl propionic acid, 2-ethyl hexanoic acid, 3,5, 5-trimethyl hexanoic acid and adipic acid to obtain mixed acid, and carrying out esterification reaction to obtain pentaerythritol ester.
Base oil 32: pentaerythritol and a carboxyl group molar ratio of 25: 75 n-butyric acid, 3,5, 5-trimethylhexanoic acid.
Base oil 33: pentaerythritol and a carboxyl group molar ratio of 30: 70 of 2-methylpropanoic acid, 3,5, 5-trimethylhexanoic acid.
Base oil 34: pentaerythritol and a carboxyl group molar ratio of 35: 65 2-methylpropanoic acid, 2-ethylhexanoic acid.
Base oil 35: pentaerythritol and a carboxyl group molar ratio of 50: 42: 8, 2-methyl propionic acid, 3,5, 5-trimethyl hexanoic acid and adipic acid to obtain mixed acid, and performing esterification reaction to obtain pentaerythritol ester.
(additives)
Additive 1: 2, 6-di-tert-butyl-p-cresol
Additive 2: phosphoric acid triphenyl ester
Additive 3: tricresyl phosphate
Additive 4: tertiary carboxylic acid glycidyl ester
Additive 5: octyl glycidyl ether
Additive 6: benzotriazole derivatives
(test for compatibility with refrigerant)
Referring to SH/T0699-2000' testing method for the compatibility of refrigerating machine oil and refrigerant, a mixture of refrigerating machine oil and refrigerant with oil content of 5% -50% is tested and slowly cooled from 25 ℃ to-30 ℃, the temperature of phase separation or white turbidity generated by the mixture is taken as the two-phase separation temperature under the oil content determination, two-phase separation curves are drawn according to the two-phase separation temperatures corresponding to different oil contents, the highest determination temperature on the curves is the two-phase separation temperature of the tested oil product and the refrigerant, and the lower the two-phase separation temperature is, the better the compatibility of the refrigerating machine oil and the refrigerant is.
In addition, "< -30" indicates that no two-phase separation or turbidity was observed in the measurement temperature region of the present test, and "separation" indicates that two-phase separation or turbidity had occurred at 25 ℃ at room temperature in the refrigerator oil.
(high temperature dissolution viscosity test with refrigerant composition)
80g of refrigerating machine oil is added into a 200ml pressure-resistant container provided with an online viscometer and a densimeter, the container is degassed in vacuum, an appropriate amount of R32 refrigerant is added, the temperature is raised to 110 ℃, the dynamic viscosity and the density of the composition are measured after the pressure is stabilized at 4.2MPa, and the kinematic viscosity of the composition is calculated.
(Heat stability test)
The thermal stability test was evaluated by the thermal decomposition temperature under the following conditions: placing a proper amount of refrigerator oil in a thermogravimetric analyzer (TGA), taking nitrogen as protective gas, wherein the flow rate is 50mL/min, the temperature rise interval is 40-600 ℃, the temperature rise rate is 10 ℃/min, the temperature at which a sample starts to decompose is taken as the thermal decomposition temperature, and the higher the thermal decomposition temperature is, the better the thermal stability of the refrigerator oil is.
(chemical stability test)
30g of refrigerator oil with the water content of 1000ppm and a catalyst iron rod, a copper rod and an aluminum rod are added into a 200mL autoclave, vacuum degassing is carried out by a vacuum pump, then a proper amount of R32 refrigerant is filled, the pressure is maintained at 4.5-5 Mpa when the temperature is raised to 150 ℃, the acid value of the refrigerator oil is measured after heating for 168 hours at 150 ℃, and the smaller the acid value is, the better the stability of the refrigerator oil is.
(lubricity test)
Lubricity test the lubricity was evaluated by the Falex ring block test of a refrigerant oil and refrigerant composition, and by the size of the wear scar width on the block specimen, the smaller the wear scar width, the better the lubricity.
Test materials: block sample (SKH51), loop sample (FC 300);
test start temperature: 60 ℃;
test time: 1 hour;
rotating speed: 800 rpm;
loading: 150 lbf;
refrigerant pressure: 0.5 MPa.
TABLE 1 sample oils of examples 1-10, compositions and indices of properties thereof
Figure BDA0002784924620000121
TABLE 2 sample oils of examples 11 to 20 having compositions and property indexes
Figure BDA0002784924620000131
TABLE 3 sample oils of examples 21 to 25 having compositions and property indexes
Figure BDA0002784924620000141
TABLE 4 sample oils of comparative examples 1 to 10, compositions and indexes of properties thereof
Figure BDA0002784924620000142
TABLE 5 sample oils of comparative examples 11 to 16 in composition and indexes of properties thereof
Figure BDA0002784924620000151
The refrigerator oil obtained by the embodiments of the invention has a pour point below-35 ℃ and good low-temperature fluidity; the refrigerating machine oil and the R32 refrigerant have good intermiscibility, the low-temperature two-phase separation temperature is lower than 10 ℃, so that the refrigerating machine oil is ensured to return to a compressor pump body in time in the compression-condensation-evaporation cycle of a refrigerating system, the abrasion of a friction pair of the compressor caused by oil shortage is avoided, and the dissolution viscosity is 2.0mm under the conditions that the actual operation working condition of the compressor is 110 ℃ and the actual operation working condition is 4.2MPa2And the refrigerating machine oil has good thermal/chemical stability, and avoids the phenomenon that the acid value of the oil product is increased due to the degradation of the refrigerating machine oil, so that the part corrosion or copper plating phenomenon is caused, and the efficiency and the reliability of a refrigerating system are influenced, so that the refrigerating machine oil has low-temperature fluidity, stability, lubricity and good compatibility with an R32 refrigerant.
Some embodiments in this specification are described in a progressive or parallel manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The refrigerator oil base oil is characterized by being an ester synthesized from pentaerythritol and a plurality of fatty acids, wherein the fatty acids comprise a first fatty acid, and the first fatty acid is C5The fatty acid further comprises at least one of a second fatty acid and a third fatty acid, the second fatty acid being C8-C9The third fatty acid is C5-C8The dibasic fatty acid of (1).
2. The refrigerator oil base according to claim 1, wherein the first fatty acid is present in a molar ratio of 20 to 50% in the fatty acid.
3. The refrigerator oil base according to claim 1, wherein the first fatty acid is present in an amount of 30 to 40 mol% based on the fatty acid.
4. The refrigerator oil base of claim 1, wherein the first fatty acid is at least one of n-pentanoic acid and 3-methylbutyric acid.
5. The refrigerator oil base of claim 1, wherein the second fatty acid is at least one of 2-ethylhexanoic acid and 3,5,5, -trimethylhexanoic acid.
6. The refrigerator oil base of claim 1 wherein the third fatty acid is adipic acid.
7. A refrigerator oil comprising the refrigerator oil base oil according to any one of claims 1 to 6.
8. The refrigerator oil of claim 7 further comprising an additive comprising at least one of an extreme pressure antiwear agent, an antioxidant, an anti-foaming agent, an acid scavenger, and a metal deactivator.
9. A working fluid composition for refrigerators comprising the refrigerator oil according to claim 7 or 8 and R32 refrigerant.
10. The working fluid composition according to claim 9, wherein the kinematic viscosity of the refrigerator oil at 40 ℃ is 60 to 120mm2The pour point is below-35 ℃, the low-temperature two-phase separation temperature of the refrigerator oil and the R32 refrigerant is lower than 10 ℃, and the dissolution viscosity of the working fluid composition for the refrigerator is 2.0mm under the conditions that the actual operation working condition of a compressor is 110 ℃ and 4.2MPa2More than s.
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Publication number Priority date Publication date Assignee Title
CN113956908A (en) * 2021-10-14 2022-01-21 珠海格力节能环保制冷技术研究中心有限公司 Refrigerator oil composition and use thereof
CN115074166A (en) * 2022-06-29 2022-09-20 江西师范大学 Preparation method of high-temperature-resistant synthetic ester

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CN104837966A (en) * 2012-12-05 2015-08-12 吉坤日矿日石能源株式会社 Cooling-equipment working-fluid composition
CN111484890A (en) * 2019-01-28 2020-08-04 瑞孚化工（上海）有限公司 Refrigerating machine oil composition and application thereof

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CN104039939A (en) * 2011-12-27 2014-09-10 日本太阳石油株式会社 Refrigerator oil composition
CN104837966A (en) * 2012-12-05 2015-08-12 吉坤日矿日石能源株式会社 Cooling-equipment working-fluid composition
CN111484890A (en) * 2019-01-28 2020-08-04 瑞孚化工（上海）有限公司 Refrigerating machine oil composition and application thereof

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CN113956908A (en) * 2021-10-14 2022-01-21 珠海格力节能环保制冷技术研究中心有限公司 Refrigerator oil composition and use thereof
CN113956908B (en) * 2021-10-14 2024-02-09 珠海格力节能环保制冷技术研究中心有限公司 Refrigerator oil composition and use thereof
CN115074166A (en) * 2022-06-29 2022-09-20 江西师范大学 Preparation method of high-temperature-resistant synthetic ester

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