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CN112266809A - 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
CN112266809A
CN112266809A CN202011311000.5A CN202011311000A CN112266809A CN 112266809 A CN112266809 A CN 112266809A CN 202011311000 A CN202011311000 A CN 202011311000A CN 112266809 A CN112266809 A CN 112266809A
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CN
China
Prior art keywords
acid
refrigerator
oil
refrigerator oil
polyol ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011311000.5A
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Chinese (zh)
Inventor
胡余生
林新俊
廖维晓
郭小青
史正良
徐嘉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gree Green Refrigeration Technology Center Co Ltd of Zhuhai
Zhuhai Gree Energy Saving Environmental Protection Refrigeration Technology Research Center Co Ltd
Original Assignee
Gree Green Refrigeration Technology Center Co Ltd of Zhuhai
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gree Green Refrigeration Technology Center Co Ltd of Zhuhai filed Critical Gree Green Refrigeration Technology Center Co Ltd of Zhuhai
Priority to CN202011311000.5A priority Critical patent/CN112266809A/en
Publication of CN112266809A publication Critical patent/CN112266809A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic

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

Abstract

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. The refrigerator oil base oil comprises a first polyol ester and a second polyol ester, wherein the first polyol ester is composed of pentaerythritol and C4～C10A monobasic fatty acid of (1), C4～C10At least one of the polybasic fatty acidsTwo fatty acids are synthesized by esterification; the second polyol ester is prepared from dipentaerythritol and C4～C12At least one fatty acid of the monobasic fatty acid (c) is esterified and synthesized. 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.

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; in the case of a refrigerating machine oil having good compatibility with R32, the working fluid composition containing R32 refrigerant exhibits too low a viscosity when mixed under high-temperature and high-pressure conditions in a refrigerator, resulting in poor lubrication, and increases wear of moving parts of the compressor.
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; in the case of a refrigerating machine oil having good compatibility with R32, the working fluid composition containing R32 refrigerant exhibits too low a viscosity when mixed under high-temperature and high-pressure conditions in a refrigerator, resulting in poor lubrication, and increases wear of moving parts of the compressor. 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 according to the embodiment of the application comprises a first polyol ester and a second polyol ester, wherein the first polyol ester is composed of pentaerythritol and C4～C10A monobasic fatty acid of (1), C4～C10At least two fatty acids of the polybasic fatty acid are synthesized by esterification; the second polyol ester is prepared from dipentaerythritol and C4～C12At least one fatty acid of the monobasic fatty acid (c) is esterified and synthesized.
Further, in the refrigerator oil base oil, the C4～C10The polybasic fatty acid (b) is 0.2 to 0.5 mole per 1 mole of pentaerythritol.
Further, in the refrigerator oil base oil, the mass ratio of the first polyol ester to the second polyol ester is (50:50) to (95: 5).
Further, in the refrigerator oil base oil, the C4～C10The monobasic fatty acid of (a) is at least one of n-butyric acid and 3,5, 5-trimethylhexanoic acid.
Further, in the refrigerator oil base oil, the C4～C10The polybasic fatty acid of (a) is adipic acid.
Further, in the refrigerator oil base oil, the C4～C12The monobasic fatty acid of (a) is at least one of n-pentanoic acid, isopentanoic acid, 3,5, 5-trimethylhexanoic acid and isooctanoic 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 anti-wear agent, an antioxidant, an anti-foaming agent and an acid trapping agent.
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 50-150 mm2The pour point is below-35 ℃, the low-temperature two-phase separation temperature of the refrigerator oil and the R32 refrigerant is lower than 5 ℃, 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 the 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 refrigerator oil base oil provided by the embodiment of the invention is formed by mixing a first polyol ester and a second polyol ester, wherein the first polyol ester is formed by pentaerythritol and C4～C10A monobasic fatty acid of (1), C4～C10At least two fatty acids of the polybasic fatty acid are synthesized by esterification; the second polyol ester is prepared from dipentaerythritol and C4～C12At least one fatty acid of the monobasic fatty acid (c) is esterified and synthesized.
The kinematic viscosity of the refrigerating machine oil obtained by the embodiment of the invention at 40 ℃ is 50 ℃150mm2The pour point is below-35 ℃, the two-layer separation temperature of the refrigerant and R32 is lower than 5 ℃, and the dissolution viscosity of the working fluid composition for the refrigerator is 2.0mm under the conditions that the actual operation condition of the compressor is 110 ℃ and the 4.2MPa2More than s. Compared with the prior refrigerating machine oil, the refrigerating machine oil has the following characteristics: the refrigerator oil has a pour point below-35 ℃ and good low-temperature fluidity; the refrigerating machine oil and the R32 refrigerant have good compatibility, the two-layer separation temperature is lower than 5 ℃, 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/s or more, a sufficiently thick oil film is ensured between the friction pairs of the parts of the pump body of the compressor, so that the abrasion resistance of the working fluid composition is improved, and the operation reliability of the compressor is improved, therefore, the refrigerating machine oil has low-temperature fluidity, lubricating property and good compatibility with R32 refrigerant.
In order to better realize the characteristics of the refrigerator oil, base oil with excellent combination property can be obtained by adjusting the molar ratio of the mixed acid in the first polyol ester and the second polyol ester and the mass fractions of the first polyol ester and the second polyol ester. Wherein in the first polyol ester, the ester synthesized by pentaerythritol and polybasic fatty acid has good viscosity index, keeps good lubricity at high temperature and high pressure, and is found by experiments that when the polybasic fatty acid is 0.2-0.5 mol relative to 1mol of pentaerythritol, the ester has carbon number of C4～C10The synthesized pentaerythritol mixed acid ester can give consideration to good compatibility and lubricity of the refrigerating machine oil. In the second polyol ester, dipentaerythritol and C4～C12The polyol ester synthesized from the monobasic fatty acid of (1) has a high viscosity and a low compatibility with R32, and thus can form a thick oil film on a metal surface. It has been found that when the first polyol ester and the second polyol ester are mixed at a mass ratio of (50:50) to (95:5), the resulting refrigerator oil has good compatibility and lubricating properties, and preferably, the first polyol ester has good compatibility and lubricating propertiesAnd the mass ratio of the second polyol ester is (60:40) - (70: 30). And the viscosity of the composite ester formed by mixing the first polyol ester and the second polyol ester is 50-150 mm at 40 DEG C2More preferably 55 to 140mm in terms of a mass fraction of the total mass fraction2A specific preferred thickness is 50 to 95mm2/s。
In the base oil of refrigerating machine oil, C4～C10The monobasic fatty acid of (1) includes, but is not limited to, straight or branched butyric acid, straight or branched valeric acid, straight or branched caproic acid, straight or branched heptanoic acid, straight or branched octanoic acid, and straight or branched nonanoic acid, and the like.
In the base oil of refrigerating machine oil, C4～C10The polybasic fatty acid(s) of (b) include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, trimellitic acid, and the like, and adipic acid and sebacic acid, among which adipic acid is more preferable, are preferred, which have an excellent balance of properties of synthesized esters and good availability.
In the base oil of refrigerating machine oil, C4～C12Include, but are not limited to, n-butyric acid, 2-methylpropionic acid, n-valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, n-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-dimethylbutyric acid, 2, 3-dimethylbutyric acid, 3, 3-dimethylbutyric acid, n-heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-dimethylpentanoic acid, 2, 3-dimethylpentanoic acid, 2, 4-dimethylpentanoic acid, 2,3, 3-trimethylbutanoic acid, n-octanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylhept, 3-ethylhexanoic acid, 4-ethylhexanoic acid, 2-dimethylhexanoic acid, 2, 3-dimethylhexanoic acid, 2, 4-dimethylhexanoic acid, 2, 5-dimethylhexanoic acid, 3-dimethylhexanoic acid, 3, 4-dimethylhexanoic acid, 3, 5-dimethylhexanoic acid, 4, 4-dimethylhexanoic acid, 4, 5-dimethylhexanoic acid, 5-dimethylhexanoic acid, 2,3, 4-trimethylpentanoic acid, 2, 3-trimethylpentanoic acid, 2, 4-trimethylpentanoic acid, 3, 4-trimethylpentanoic acid, 3,4, 4-trimethylpentanoic acid, 2-methyl-3-ethylpentanoic acid, 2-ethyl-3-methylpentanoic acid, 2-ethyl-4-methylpentanoic acid, 2, 3-methylpentanoic acid, 2-ethyl-4-, 2-Ethyl-3, 3-dimethylbutyric acid, 2-isopropyl-3-methyl esterPhenylbutyric acid, 2,3, 3-tetramethylbutyric acid, n-nonanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7-methyloctanoic acid, 2, 3-dimethylheptanoic acid, 2, 4-dimethylheptanoic acid, 2, 5-dimethylheptanoic acid, 2, 6-dimethylheptanoic acid, 3, 4-dimethylheptanoic acid, 3, 5-dimethylheptanoic acid, 3, 6-dimethylheptanoic acid, 4, 6-dimethylheptanoic acid, 5, 6-dimethylheptanoic acid, 6-dimethylheptanoic acid, 2,3, 4-trimethylhexanoic acid, 2, 4-trimethylpentanoic acid, 2,4, 4-trimethylpentanoic acid, 2,3, 5-trimethylhexanoic acid, 3,4, 5-trimethylhexanoic acid, 3,4, 4-trimethylhexanoic acid, 3,5, 5-trimethylhexanoic acid, 2-ethyl-3-methylhexanoic acid, 2-methyl-3-ethylhexanoic acid, 2-methyl-4-ethylhexanoic acid, n-decanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 4-methylnonanoic acid, 5-methylnonanoic acid, 6-methylnonanoic acid, 7-methylnonanoic acid, 8-methylnonanoic acid, 2-ethyloctanoic acid, 3-ethyloctanoic acid, 4-ethyloctanoic acid, 5-ethyloctanoic acid, 6-ethyloctanoic acid, 2, 3-dimethyloctanoic acid, 2, 4-dimethyloctanoic acid, 2, 5-dimethyloctanoic acid, 2, 6-dimethyloctanoic acid, 2, 7-dimethyloctanoic acid, 7, 7-dimethyloctanoic acid, 2,3, 4-trimethylheptanoic acid, 3,4, 5-trimethylheptanoic acid, 3,4, 6-trimethylheptanoic acid, n-undecanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 4-methyldecanoic acid, 5-methyldecanoic acid, 6-methyldecanoic acid, 7-methyldecanoic acid, 8-methyldecanoic acid, 9-methyldecanoic acid, 2-ethylnonanoic acid, 3-ethylnonanoic acid, 4-ethylnonanoic acid, 5-ethylnonanoic acid, 6-ethylnonanoic acid, 7-ethylnonanoic acid, 3,5, 7-trimethyloctanoic acid, 3,7, 7-trimethyloctanoic acid, n-dodecanoic acid, 2-methylundecanoic acid, 3-methylundecanoic acid, 4-methylundecanoic acid, 5-methylundecanoic acid, 2-methylundecanoic acid, 4-methylundecanoic acid, 6-methylundecanoic acid, 7-methylundecanoic acid, 8-methylundecanoic acid, 9-methylundecanoic acid, 10-methylundecanoic acid, 2-ethyldecanoic acid, 3-ethyldecanoic acid, 4-ethyldecanoic acid, 5-ethyldecanoic acid, 6-ethyldecanoic acid, 7-ethyldecanoic acid, 8-ethyldecanoic acid, 3,5, 7-trimethylnonanoic acid, 3,7, 8-trimethylnonanoic acid, 3,8, 8-trimethylnonanoic acid, and the like. From the viewpoint of low temperature characteristics, C is preferred5～C9More preferably branched valeric acid, 2-ethylhexanoic acid and 3,5, 5-trimethylhexanoic acid.
It is to be noted that the pentaerythritol ester and dipentaerythritol ester in the present invention may be a full ester in which all of the hydroxyl groups of pentaerythritol and dipentaerythritol ester are esterified, a partial ester in which a part of the hydroxyl groups of pentaerythritol and dipentaerythritol ester are not esterified, or a mixture of a full ester and a partial ester, and preferably a full ester.
In order to further improve the performance of the refrigerator oil, various known additives for refrigerator oils may be further added to the base oil as necessary. Examples of the additives include an extreme pressure anti-wear agent, an antioxidant, an anti-foaming agent, and an acid scavenger, 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 a composition of at least two of phosphate, sulfuric phosphate, a nitrogen-containing compound or nano metal particles and other compounds. 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 nitrogen-containing complex compound includes, but is not limited to, acetic acid diethanol amide phosphate, propionic acid diethanol amide phosphate, butyric acid diethanol amide phosphate, caproic acid diethanol amide phosphate or caproic acid dipropanol amide phosphate.
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. Preferably, phenolic antioxidants are used.
The acid trapping agent in the additive is used for further improving the thermo-chemical stability of the refrigerating machine oil and the working fluid composition for the refrigerating machine, and the acid trapping agent comprises any one or a composition of at least two of n-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, polyalkylene glycol glycidyl ether or carbodiimide. In this case, the acid scavenger according to the embodiment of the present invention slows down the metal corrosion due to the hydrolysis of the polyol ester, and improves the thermal stability and chemical stability of the refrigerator oil.
The defoaming agent is one or a composition of polyether modified silicone oil and polyalkylene glycol. The defoaming agent disclosed by the embodiment of the invention is used for reducing the foaming property of the refrigerating machine oil composition and further improving the lubricating property and stability of the refrigerating machine oil.
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. Wherein the refrigerant is 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 used in the respective examples and comparative examples and the respective index test methods are listed below. In examples 1 to 16 and comparative examples 1 to 16, sample oils were prepared by blending the base oils 1 to 8 shown below, respectively, in such a manner as to form the composition ratios shown in tables 1 to 5, and the properties of the sample oils obtained in examples 1 to 16 and comparative examples 1 to 16 and the indices measured by the following respective index test methods were recorded in tables 1 to 4, wherein the compounding ratios of the respective components in tables 1 to 4 were in the form of mass percentages.
(base oil)
Base oil 1: pentaerythritol ester synthesized by esterification of 1mol pentaerythritol with mixed fatty acids formed from 0.2mol adipic acid, 2mol n-butyric acid and 2mol 3,5, 5-trimethylhexanoic acid.
Base oil 2: pentaerythritol ester synthesized by esterification of 1mol pentaerythritol with mixed fatty acids formed from 0.3mol adipic acid, 2mol n-butyric acid and 2mol 3,5, 5-trimethylhexanoic acid.
Base oil 3: pentaerythritol ester synthesized by esterification of 1mol pentaerythritol with mixed fatty acids formed from 0.4mol adipic acid, 2mol n-butyric acid and 2mol 3,5, 5-trimethylhexanoic acid.
Base oil 4: pentaerythritol ester synthesized by esterification of 1mol pentaerythritol with mixed fatty acids formed from 0.5mol adipic acid, 2mol n-butyric acid and 2mol 3,5, 5-trimethylhexanoic acid.
Base oil 5: pentaerythritol ester synthesized by esterification of 1mol pentaerythritol with mixed fatty acids formed from 0.1mol adipic acid, 2mol n-butyric acid, 2mol 3,5, 5-trimethylhexanoic acid.
Base oil 6: pentaerythritol ester synthesized by esterification of 1mol pentaerythritol with mixed fatty acids formed from 0.6mol adipic acid, 2mol n-butyric acid and 2mol 3,5, 5-trimethylhexanoic acid.
7, 1mol of dipentaerythritol and dipentaerythritol ester synthesized by esterification of mixed fatty acid formed by 1.98mol of n-pentanoic acid, 0.66mol of isovaleric acid and 3.96mol of 3,5, 5-trimethylhexanoic acid are used as base oil.
8, 1mol of dipentaerythritol and dipentaerythritol ester synthesized by esterification of mixed fatty acid formed by 1.32mol of n-pentanoic acid, 0.66mol of isovaleric acid and 4.62mol of 3,5, 5-trimethylhexanoic acid are used as base oil.
It should be noted that the molar amounts of the respective raw materials in the base oils 1 to 8 are used to describe the relationship between the molar amounts of the alcohol and the respective fatty acids used for the synthesis of the ester, and do not represent the absolute amounts of the respective raw materials of the base oils.
(test for compatibility with refrigerant)
Referring to SH/T0699-.
(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.
(lubricity test)
Lubricity test the lubricity was evaluated by the Falex ring block test of a refrigerant oil and refrigerant composition, and the wear was evaluated by the wear scar width and wear volume size on the block specimen, the smaller the wear scar width and wear volume, the better the lubricity.
The test basis is as follows: ASTMD2714
Test materials: steel block and cast iron ring
Test start temperature: 25 deg.C
Test time: 1 hour
Rotating speed: 800rpm
Loading: 100lbf
TABLE 1 sample oils of examples 1-8 having compositions and property indices
Figure BDA0002789832060000111
TABLE 2 sample oils of examples 9 to 16, compositions and indexes of properties thereof
Figure BDA0002789832060000121
TABLE 3 sample oils of comparative examples 1 to 8, compositions and indexes of properties thereof
Figure BDA0002789832060000131
TABLE 4 sample oils of comparative examples 9 to 16, compositions and indexes of properties thereof
Figure BDA0002789832060000141
As is apparent from tables 1 to 4, the viscosity of the base oil was significantly improved as the ratio of the adipic acid raw material in the base oil was increased (comparative examples 1, 10 and 6), and the solubility viscosity of the base oil in the R32 refrigerant was gradually increased under the conditions of 110 ℃ and 4.2MPa abs. The experimental results show that under certain conditions, the addition of the adipic acid component can improve the viscosity of the base oil and also can improve the dissolution viscosity of the base oil. In addition, the viscosity of the polyol mixed ester of adipic acid with other fatty acids is more significantly affected by the addition amount of adipic acid, and the base oil product is easily made solid at ordinary temperature when the molar amount of adipic acid is more than 11% of the total molar amount of fatty acids esterified with pentaerythritol; when the molar ratio of adipic acid to pentaerythritol is more than 0.5, the solubility of the base oil to refrigerant R32 becomes poor and an incompatibility occurs, while when the molar ratio of adipic acid to pentaerythritol is less than 0.2, the solubility viscosity to R32 becomes low. Therefore, it is necessary to control the amount of adipic acid to adjust the balance between viscosity and compatibility.
As can be seen from the test data in tables 1-2, the invention can be used as a refrigerating machine oil working fluid composition in a refrigerating machine of hydrofluorocarbon R32 refrigerant.
The base oil and the composition thereof provided by the embodiment of the invention have good compatibility with hydrofluorocarbon R32 refrigerant, and the quaternary freezing base oil containing the base oil has good wear resistance, wear reduction and low-temperature fluidity; meanwhile, the dissolution viscosity is 2.0mm under the conditions of 110 ℃ and 4.2MPa of the actual operation working condition of the compressor2And/s or more, a sufficiently thick oil film is ensured between the friction pairs of the parts of the pump body of the compressor, so that the abrasion resistance of the working fluid composition is improved, and the operation reliability of the compressor is improved, therefore, the refrigerating machine oil has low-temperature fluidity, lubricating property and good compatibility with 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 comprising a first polyol ester and a second polyol ester, wherein the first polyol ester is composed of pentaerythritol and C4～C10A monobasic fatty acid of (1), C4～C10At least two fatty acids of the polybasic fatty acid are synthesized by esterification; the second polyol ester is prepared from dipentaerythritol and C4～C12At least one fatty acid of the monobasic fatty acid (c) is esterified and synthesized.
2. The refrigerator oil base of claim 1, wherein C is4～C10The polybasic fatty acid (b) is 0.2 to 0.5 mole per 1 mole of pentaerythritol.
3. The refrigerator oil base according to claim 1, wherein the mass ratio of the first polyol ester to the second polyol ester is (50:50) to (95: 5).
4. The refrigerator oil base of claim 1, wherein C is4～C10The monobasic fatty acid of (a) is at least one of n-butyric acid and 3,5, 5-trimethylhexanoic acid.
5. The refrigerator oil base of claim 1, wherein C is4～C10The polybasic fatty acid of (a) is adipic acid.
6. The refrigerator oil base of claim 1, wherein C is4～C12The monobasic fatty acid of (a) is at least one of n-pentanoic acid, isopentanoic acid, 3,5, 5-trimethylhexanoic acid and isooctanoic 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, and an acid trap.
9. A working fluid composition for refrigerators comprising the refrigerator oil according to claim 7 or 8 and R32 refrigerant.
10. The tool of claim 9The fluid composition is characterized in that the kinematic viscosity of the refrigerator oil at 40 ℃ is 50-150 mm2The pour point is below-35 ℃, the low-temperature two-phase separation temperature of the refrigerator oil and the R32 refrigerant is lower than 5 ℃, 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 the compressor is 110 ℃ and 4.2MPa2More than s.
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WO2024190539A1 (en) * 2023-03-10 2024-09-19 Ｅｎｅｏｓ株式会社 Ester for refrigerator oil, base oil for refrigerator oil, refrigerator oil, and working fluid composition

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