CN108431190A - Refrigerator oil and composition for refrigerator - Google Patents

Refrigerator oil and composition for refrigerator Download PDF

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Publication number
CN108431190A
CN108431190A CN201780006501.2A CN201780006501A CN108431190A CN 108431190 A CN108431190 A CN 108431190A CN 201780006501 A CN201780006501 A CN 201780006501A CN 108431190 A CN108431190 A CN 108431190A
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CN
China
Prior art keywords
acid
refrigerator
carbon atom
refrigerator oil
various
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Pending
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CN201780006501.2A
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Chinese (zh)
Inventor
松本知也
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Publication of CN108431190A publication Critical patent/CN108431190A/en
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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
    • 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
    • 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
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/92—Carboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/92—Carboxylic acids
    • C10M129/93—Carboxylic acids having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
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    • C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
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    • 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
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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    • C10M2223/04—Phosphate esters
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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    • C10N2020/097—Refrigerants
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
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    • 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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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

A refrigerator oil according to one embodiment of the present invention includes a base oil containing an oxygen-containing organic compound, a polyphosphate compound, and a metal salt of an organic carboxylic acid having 6 to 60 carbon atoms.

Description

Refrigerator oil and composition used for refrigerator
Technical field
The present invention relates to the compositions used for refrigerator of refrigerator oil and the use refrigerator oil.
Background technology
In refrigerator, the mixture (hereinafter also referred to " composition used for refrigerator ") of refrigerant and refrigerator oil is formed close The structure recycled in the system of envelope, to refrigerator oil, it is desirable that compatibility, stability and greasy property with refrigerant.In order to hold Easily meet these requirements performance, most use is made as main component cold comprising oxygen-containing organic compounds such as vinyl ether compounds Freeze machine oil (referring for example to patent document 1).
On the other hand, as refrigerant, in recent years, the high hydrochlorofluorocarbons of alternative environment load (HCFC) gradually uses hydrogen Fluorohydrocarbon (HFC).Among HFC, use R32 (Difluoroethane), R410A (mixture of Difluoroethane and pentafluoroethane) etc. full mostly With hydrofluorocarbon (saturation HFC).
As the skill improved with greasy properties such as compatibility, abrasion performance, the resistance to seizures of such saturation HFC refrigerant Art, it is known that the phosphorus with 1 phosphorus atoms such as tricresyl phosphate (TCP) is added into the base oil comprising oxygen-containing organic compound Ester compound (referring for example to patent document 2).
In addition, in such as patent document 3 ~ 5, in order to improve abrasion performance etc., discloses and coordinate fatty acid alkali metal salt In refrigerator oil.Further, it in these patent documents 3 ~ 5, also discloses other than fatty acid alkali metal salt, also coordinates TCP etc. has the phosphate compound of 1 phosphorus atoms.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 6-128578 bulletins
Patent document 2：Japanese Unexamined Patent Publication 10-130683 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2001-3072 bulletins
Patent document 4：Japanese Unexamined Patent Publication 4-300996 bulletins
Patent document 5：No. WO2008/041549.
Invention content
The subject that the invention solves
However, in recent years, various refrigerators have been gradually increased with the requirement for saving energy, it is desirable that improve the coefficient of performance (COP： Coefficient of Performance).Therefore, it to refrigerator oil, other than abrasion performance, in order to improve COP, also wants Seek the friction coefficient further decreased at the slipper of refrigerator.
However, as shown in patent document 2 ~ 5, even if TCP etc. to be had to phosphate compound, the fat of 1 phosphorus atoms Fat acid alkali metal salt or both be matched in refrigerator oil, it is also difficult to it is abundant while so that abrasion performance is reached good Reduce friction coefficient.
The present invention puts and carries out in view of the above problems, and project is, is using comprising oxygen-containing organic compound as base When the refrigerator oil of plinth oil, friction coefficient is reduced while so that abrasion performance is reached good.
Means for solving the problems
It is that the inventors of the present invention are furtherd investigate as a result, it has been found that, by the base oil comprising oxygen-containing organic compound containing Both specific phosphorus series compound and metal salt of organic carboxylic acid with phosphorus atoms more than at least two in one molecule, can solve Certainly the above subject, so as to complete the present invention.The present invention provides refrigerator oil, composition used for refrigerator and refrigerator below The manufacturing method of oil.
(1) refrigerator oil, it includes the organic carboxyl acids that base oil, polyphosphate based compound and carbon atom number are 6 ~ 60 Metal salt, the base oil include oxygen-containing organic compound.
(2) composition used for refrigerator, it includes the refrigerator oils described in refrigerant and above-mentioned (1).
(3) manufacturing method of refrigerator oil, wherein into the base oil comprising oxygen-containing organic compound, at least coordinate more The metal salt for the organic carboxyl acid that phosphate based compound and carbon atom number are 6 ~ 60, to obtain refrigerator oil.
The effect of invention
According to the present invention, by containing the metal salt of specific phosphorus series compound and organic carboxyl acid in base oil, providing can The refrigerator oil of friction coefficient is reduced while so that abrasion performance is reached good.
Specific implementation mode
Hereinafter, for the present invention, illustrated using embodiment.
Refrigerator oil involved by an embodiment of the invention includes base oil, polyphosphate based compound and has The metal salt of machine carboxylic acid.Hereinafter, being described in detail for each ingredient contained in refrigerator oil.
[base oil]
Base oil in present embodiment includes oxygen-containing organic compound.As oxygen-containing organic compound, can enumerate in molecule In the synthetic oil containing ether, ketone group, ester group, carbonate group etc. and together with these groups containing hetero atom (sulphur atom, Fluorine atom, chlorine atom, silicon atom, nitrogen-atoms etc.) synthetic oil.More specifically, can enumerate polyvinyl ether (PVE), The copolymer (ECP) of polyether polyols class (PAG), poly- (oxygen) aklylene glycol or its monoether and polyvingl ether and more First alkoxide (POE).Oxygen-containing organic compound can be used singly or in combination of two or more.
Among these, be preferably selected from a kind in polyvinyl ether (PVE) and polyether polyols class (PAG) with On, wherein more preferably it is selected from one or more of polyvinyl ether (PVE).It should be noted that PVE is especially to aftermentioned general formula (1) shown and R9Make for polyphosphate compound shown in the polyphosphate compound of group, general formula (5) shown in general formula (2) In the case of, it is easy that friction coefficient, abrasion performance is made to reach good.
Oxygen-containing organic compound becomes the main component of refrigerator oil, and oxygen-containing organic compound is relative to refrigerator oil total amount Preferably comprise 70 ~ 99.98 mass %, further preferably 90 ~ 99.5 mass %, further preferably 93.0 ~ 99.3 mass %.
Hereinafter, for use as PVE, PAG, ECP, POE of base oil, it is described in detail.
＜ polyvinyl ethers (PVE) ＞
Polyvinyl ether (PVE) is the polymer with the structural unit from vinyl ethers, specifically, tool can be enumerated There is the polyvinyl based compound of structural unit shown in the following general formula (A-1).
[chemical formula 1]
。
R in above-mentioned general formula (A-1)1a、R2aAnd R3aThe alkyl that hydrogen atom or carbon atom number are 1 ~ 8 is each independently represented, They each other can be identical or different.Here, as alkyl, can specifically enumerate methyl, ethyl, n-propyl, isopropyl, The alkyl such as normal-butyl, isobutyl group, sec-butyl, tertiary butyl, various amyls, various hexyls, various heptyl, various octyls；Cyclopenta, The naphthenic base such as cyclohexyl, various methylcyclohexyls, various ethylcyclohexyls, various Dimethylcyclohexyls；Phenyl, various methylbenzenes The aryl such as base, various ethylphenyls, various 3,5-dimethylphenyls；The aryl such as benzyl, various phenylethyls, various methylbenzyls Alkyl, preferably alkyl.
R1a、R2aAnd R3aMore preferably hydrogen atom or carbon atom number are 3 alkyl below, are further preferably hydrogen original Son.It should be noted that the r expression number of repeat unit in general formula (A-1), the number for the range that average value is 0 ~ 10, preferably 0.
R4aIndicate that carbon atom number is 2 ~ 10 bivalent hydrocarbon radical, here, the bivalent hydrocarbon radical for being 2 ~ 10 as carbon atom number, specifically For have ethylidene, phenyl-ethylene, 1,2- propylidene, 2- phenyl -1,2- propylidene, 1,3- propylidene, various butylidenes, each The bivalent aliphatics hydrocarbon such as kind pentylidene, various hexylidenes, various heptamethylenes, various octamethylenes, various nonylenes, various decylenes Base；There are 2 in the ester ring type hydrocarbons such as hexamethylene, hexahydrotoluene, ethyl cyclohexane, dimethyl cyclohexane, propyl cyclohexane It is bonded the alicyclic type hydrocarbon at position；Various phenylenes, various methylphenylenes, various ethylphenylenes, various dimethyl Asias benzene The divalent aromatic hydrocarbon groups such as base, various naphthylenes；It is each at the moieties and aromatic fractions of the alkylaromatic hydrocarbons such as toluene, ethylo benzene Alkyl aromatic alkyl from the bonding position with monovalence；In the moieties of more alkylaromatic hydrocarbons such as dimethylbenzene, diethylbenzene Locate the alkyl aromatic alkyl etc. with bonding position.Among these, more preferably carbon atom number be 2 ~ 4 aliphatic alkyl.This Outside, multiple R4aO may be the same or different.
Further, the R in general formula (A-1)5aIndicate that carbon atom number is 1 ~ 10 alkyl, which specifically indicates first Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, various amyls, various hexyls, various heptyl, The alkyl such as various octyls, various nonyls, various decyls；Cyclopenta, cyclohexyl, various methylcyclohexyls, various ethylcyclohexyls, The naphthenic base such as various propylcyclohexyls, various Dimethylcyclohexyls；Phenyl, various aminomethyl phenyls, various ethylphenyls, various two The aryl such as aminomethyl phenyl, various propyl phenyl, various trimethylphenyls, various butyl phenyls, various naphthalenes；It is benzyl, various The aryl alkyls such as phenylethyl, various methylbenzyls, various phenyl propyls, various phenyl butyls.Wherein, preferably carbon atom Number is 1 ~ 8 alkyl, the alkyl that more preferably carbon atom number is 1 ~ 6.It should be noted that alkyl can be straight-chain, branched, ring Any one in shape.
Among the polyvinyl based compound of structural unit shown in above-mentioned general formula (A-1), preferably R1a、R2aWith R3aIt is hydrogen atom, r 0, the R for including 50 ~ 100 moles of %5aFor the structural unit of ethyl, the R of 0 ~ 50 mole of %5aFor carbon atom The polymer or copolymer of the structural unit for the alkyl that number is 3 or 4.More preferable R5aRatio for the structural unit of ethyl is 70 ~ 100 moles of % and R5aThe ratio of structural unit of alkyl for being 3 or 4 for carbon atom number is 0 ~ 30 mole of %, further preferably the former For 80 ~ 95% and the latter be 5 ~ 20 moles of %.
In addition, as aforementioned R5aCarbon atom number be 3 or 4 alkyl, n-propyl, isopropyl, normal-butyl, different can be used Butyl, sec-butyl, tertiary butyl, particularly preferably isobutyl group.
Polyvingl ether based compound has structural unit shown in above-mentioned general formula (A-1), and number of repeat unit is according to the phase The kinematic viscosity of prestige suitably selects.In addition, above-mentioned polyvingl ether based compound can pass through corresponding vinyl ethers system The polymerization of monomer and manufacture.The vinyl ether monomer that can be used herein is shown in general formula below (A-2).
[chemical formula 2]
(in formula, R1a、R2a、R3a、R4aAnd R5aAs hereinbefore with r).
As the vinyl ether monomer, there are various monomers corresponding with above-mentioned polyvingl ether based compound, Ke Yiju Go out for example vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, Vinyl isobutyl ether, vinyl sec-butyl ether, vinyl tertbutyl ether, vinyl n-pentyl ether, vinyl n-hexyl ether, second Alkenyl -2- methoxy ethyls ether, vinyl -2- ethoxyethyl groups ether, vinyl -2- methoxyl group -1- methyl ethyl ethers, ethylene Base -2- methoxy-propyl esters, vinyl -3,6- dioxaheptyls ether, vinyl -3,6,9- trioxas decyl ethers, vinyl - 1,4- dimethyl -3,6- dioxaheptyls ether, vinyl -1,4,7- trimethyl -3,6,9- trioxas decyl ethers, vinyl -2, 6- dioxa -4- heptyl ether, vinyl -2,6,9- trioxa -4- decyl ethers, 1- methoxyl groups propylene, 1- ethoxy propylenes, 1- are just Propoxyl group propylene, 1- isopropoxies propylene, 1- n-butoxies propylene, 1- isobutoxies propylene, 1- sec-butoxies propylene, the tertiary fourths of 1- Oxygroup propylene, 2- methoxyl groups propylene, 2- ethoxy propylenes, 2- positive propoxies propylene, 2- isopropoxies propylene, 2- n-butoxies third Alkene, 2- isobutoxies propylene, 2- sec-butoxies propylene, 2- tert-butoxies propylene, 1- methoxyl group -1- butylene, 1- ethyoxyl -1- fourths Alkene, 1- positive propoxy -1- butylene, 1- isopropoxy -1- butylene, 1- n-butoxy -1- butylene, 1- isobutoxy -1- butylene, 1- Sec-butoxy -1- butylene, 1- tert-butoxy -1- butylene, 2- methoxyl group -1- butylene, 2- ethyoxyl -1- butylene, 2- positive propoxies - 1- butylene, 2- isopropoxy -1- butylene, 2- n-butoxy -1- butylene, 2- isobutoxy -1- butylene, 2- sec-butoxy -1- fourths Alkene, 2- tert-butoxy -1- butylene, 2- methoxyl group -2- butylene, 2- ethyoxyl -2- butylene, 2- positive propoxy -2- butylene, 2- isopropyls Oxygroup -2- butylene, 2- n-butoxy -2- butylene, 2- isobutoxy -2- butylene, 2- sec-butoxy -2- butylene, 2- tert-butoxies - 2- butylene etc..These vinyl ether monomers can be manufactured by well known method.
At the end section of polymer shown in general formula (A-1), it can be imported from saturation by well known method Hydrocarbon, ether, alcohol, ketone, amide, nitrile etc. univalent perssad.
Wherein, as polyvingl ether based compound, it is suitble to the end structure with following (1) ~ (4).
(1) its 1 end is shown in the following general formula (A-1-i) and remaining end is shown in the following general formula (A-1-ii) Substance
[chemical formula 3]
(in formula, R6a、R7aAnd R8aHydrogen atom or carbon atom number are each independently represented as 1 ~ 8 alkyl, they each other can phase It is same or different；R9aIndicate that carbon atom number is 2 ~ 10 bivalent hydrocarbon radical, R10aIndicate that carbon atom number is 1 ~ 10 alkyl, r1 indicates it The number that average value is 0 ~ 10, R9aO there are it is multiple when, multiple R9aO can be identical or different).
[chemical formula 4]
(in formula, R11a、R12aAnd R13aHydrogen atom or carbon atom number are each independently represented as 1 ~ 8 alkyl, they can be each other It is identical or different, R14aIndicate that carbon atom number is 2 ~ 10 bivalent hydrocarbon radical, R15aIndicate that carbon atom number is 1 ~ 10 alkyl, r2 is indicated The number that its average value is 0 ~ 10, R14aO there are it is multiple when, multiple R14aO can be identical or different).
(2) one end is shown in above-mentioned general formula (A-1-i) and remaining end is shown in general formula (A-1-iii) Substance
[chemical formula 5]
(in formula, R16a、R17aAnd R18aThe alkyl that hydrogen atom or carbon atom number are 1 ~ 8 is each independently represented, they each other can be with It is identical or different；R19aAnd R21aEach independently represent carbon atom number be 2 ~ 10 bivalent hydrocarbon radical, they can it is mutually the same or Difference, R20aAnd R22aThe alkyl that carbon atom number is 1 ~ 10 is each independently represented, they can be the same or different from each other, r3 and r4 Respectively indicate that its average value is 0 ~ 10 number, they can be the same or different from each other, and there are multiple R in addition19aWhen O, multiple R19aO Can be identical or different, there are multiple R21aWhen O, multiple R21aO can be identical or different).
(3) one end is shown in above-mentioned general formula (A-1-i) and remaining end has the object of ethylenic unsaturated bond Matter.
(4) one end is shown in above-mentioned general formula (A-1-i) and remaining end is object shown in general formula (A-1-iv) Matter
[chemical formula 6]
(in formula, R23a、R24aAnd R25aRespectively indicate that hydrogen atom or carbon atom number are 1 ~ 8 alkyl, they each other can it is identical or It is different).
Polyvingl ether system mixture can be the substance selected from the end structure with aforementioned (1) ~ (4) in two kinds with On mixture.As such mixture, the mixing of the substance of for example aforementioned (1) and the substance of (4) can be preferably enumerated The mixture of object and the substance of aforementioned (2) and the substance of (3).
Polyvingl ether the based compound preferably selected degree of polymerization, end structure etc. are to reach the viscous of aftermentioned preferred base oil Spend range.In addition, polyvingl ether based compound can be used singly or in combination of two or more.
Among the polyvinyl based compound of structural unit shown in above-mentioned general formula (A-1), particularly preferred 1 end It is substance shown in above-mentioned general formula (A-1-ii) for shown in above-mentioned general formula (A-1-i) and remaining end.
Wherein, in formula (A-1-i) and formula (A-1-ii), more preferable R6a、R7a、R8a、R11a、R12aAnd R13aFor hydrogen atom, and R1 and r2 is 0, R10a、R15aThe alkyl for being 1 ~ 4 for carbon atom number.
＜ polyether polyols class (PAG) ＞
As polyether polyols class (PAG), the following general formula (B-1) compound represented can be enumerated.It should be noted that basic When in oil including PAG, which may be used singly or in combin two or more.
R1b-[(OR2b)m-OR3b]n (B-1)
(in formula, R1bIt indicates hydrogen atom, 1 valency alkyl that carbon atom number is 1 ~ 10, the acyl group that carbon atom number is 2 ~ 10, have 2 ~ 6 The oxygen-containing alkyl that the alkyl or carbon atom number that the carbon atom number at a bonding position is 1 ~ 10 are 1 ~ 10, R2bIndicate that carbon atom number is 2 ~ 4 alkylidene, R3bIndicate hydrogen atom, the alkyl that carbon atom number is 1 ~ 10 or acyl group or carbon atom that carbon atom number is 2 ~ 10 The oxygen-containing alkyl that number is 1 ~ 10, n indicate that 1 ~ 6 integer, m expressions make the number that the average value of m × n reaches 6 ~ 80).
In above-mentioned general formula (B-1), R1bAnd R3bEach of in carbon atom number be 1 ~ 10 1 valency alkyl can be straight Any one of chain, branched, ring-type.The alkyl is preferably alkyl, as its concrete example, can enumerate methyl, ethyl, just Propyl, isopropyl, various butyl, various amyls, various hexyls, various heptyl, various octyls, various nonyls, various decyls, ring Amyl, cyclohexyl etc..Above-mentioned 1 valency alkyl is by making carbon atom number for 10 hereinafter, to become good with the compatibility of refrigerant. From such a viewpoint, the carbon atom number of 1 valency alkyl is more preferably 1 ~ 4.
In addition, R1bAnd R3bEach of in carbon atom number be 2 ~ 10 acyl group possessed by hydrocarbyl portion can be Any one of straight-chain, branched, ring-type.The hydrocarbyl portion of the acyl group is preferably alkyl, as its concrete example, can be enumerated Above-mentioned R can be elected to be1bAnd R3bAlkyl among carbon atom number be 1 ~ 9 group.By make the acyl group carbon atom number be 10 with Under, become good with the compatibility of refrigerant.The carbon atom number of preferred acyl group is 2 ~ 4.
R1bAnd R3bWhen being alkyl or acyl group, R1bAnd R3bCan be identical, it can also be different from each other.
Further, when n is 2 or more, multiple R in 1 molecule3bIt may be the same or different.
R1bFor have 2 ~ 6 bonding positions carbon atom numbers be 1 ~ 10 alkyl when, the alkyl can be chain, can also For ring-type.As the alkyl with 2 bonding positions, preferably aliphatic alkyl, it can be cited for example that ethylidene, propylidene, Butylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, decylene, cyclopentylene, cyclohexylidene etc..As other Alkyl can be enumerated and remove residue obtained from hydroxyl-removal from the bisphenols such as xenol, Bisphenol F, bisphenol-A.In addition, as with The alkyl at 3 ~ 6 bonding positions, preferably aliphatic alkyl, it can be cited for example that from trimethylolpropane, glycerine, Ji Wusi It is gone in the polyalcohols such as alcohol, D-sorbite, 1,2,3- trihydroxies hexamethylene, 1,3,5- trihydroxy hexamethylenes residual obtained from hydroxyl-removal Base.
By making the carbon atom number of the aliphatic alkyl for 10 hereinafter, the compatibility with refrigerant becomes good.The fat The preferred carbon atom number of race's alkyl is 2 ~ 6.
Further, as R1bAnd R3bEach of in carbon atom number be 1 ~ 10 oxygen-containing alkyl, can enumerate has The aliphatic group of the chain of ehter bond, cricoid aliphatic group (such as tetrahydrofurfuryl) etc..
It is preferred that above-mentioned R1bAnd R3bAt least one of be alkyl that alkyl, especially carbon atom number are 1 ~ 4.
R in aforementioned formula (B-1)2bThe alkylidene for being 2 ~ 4 for carbon atom number can as the oxyalkylene of repetitive unit To enumerate oxygen ethylidene, oxygen propylidene, oxygen butylidene.Oxyalkylene in 1 molecule can be identical, can also include 2 kinds with On oxyalkylene, preferably in 1 molecule include at least oxygen propylene unit, more preferably in oxygen alkylidene unit include 50 The oxygen propylene unit of mole % or more.
The integer that n in aforementioned formula (B-1) is 1 ~ 6, and according to R1bBonding position quantity and determine.For example, R1b For alkyl, acyl group when, n 1, R1bFor with 2,3,4,5 and 6 bonding position aliphatic alkyl when, n is respectively 2,3,4,5 With 6.In addition, m is the number for making the average value of m × n reach 6 ~ 80.By making the average value reach 80 hereinafter, compatibility becomes good It is good.In addition, n be preferably 1 ~ 3 integer, more preferably 1.Wherein, the average value of m × n is preferably suitably set to reach aftermentioned excellent The range of viscosities of the base oil of choosing.
Polyether polyols class shown in aforementioned formula (B-1) is included in the polyoxy alkylidene two that end has hydroxyl Alcohol, as long as the content of the hydroxyl is to reach 50 moles of % ratios below relative to whole end groups, then containing It is suitble to use.
Copolymer (ECP) ＞ of poly- (oxygen) aklylene glycols of ＜ or its monoether and polyvingl ether
In the refrigerator oil of present embodiment, as poly- (oxygen) aklylene glycol or its monoether that can be used as base oil and poly- second The copolymer of alkene ether, can enumerate copolymer shown in copolymer and general formula (C-2) shown in general formula below (C-1) (with Under be referred to as polyvingl ether based copolymer I and polyvingl ether based copolymer II).It should be noted that poly- (oxygen) alkylidene two Alcohol refers to both polyalkylene glycol and polyether polyols.
[chemical formula 7]
。
R in above-mentioned general formula (C-1)1c、R2cAnd R3cThe alkyl that hydrogen atom or carbon atom number are 1 ~ 8 is each independently represented, They can be the same or different from each other, R5cIndicate that carbon atom number is 2 ~ 4 bivalent hydrocarbon radical, R6cIndicate that carbon atom number is 1 ~ 20 Aliphatic or alicyclic type hydrocarbon, the aromatic hydrocarbyl that carbon atom number is 1 ~ 20, the acyl group that carbon atom number is 2 ~ 20 or carbon atom number are 2 ~ 50 oxygen-containing alkyl, R4cIndicate that carbon atom number is 1 ~ 10 alkyl, R1c~R6cThey there are it is multiple when, respectively can be identical Or it is different.
Here, R1c~R3cAmong carbon atom number be 1 ~ 8 alkyl refer to specifically indicate methyl, ethyl, n-propyl, The alkyl such as isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, various amyls, various hexyls, various heptyl, various octyls； The naphthenic base such as cyclopenta, cyclohexyl, various methylcyclohexyls, various ethylcyclohexyls, various Dimethylcyclohexyls；Various diformazans The aryl such as base phenyl；The aryl alkyls such as benzyl, various phenylethyls, various methylbenzyls.It should be noted that as these R1c、R2cAnd R3cEach of, particularly preferably hydrogen atom.
On the other hand, as R5cShown in carbon atom number be 2 ~ 4 bivalent hydrocarbon radical, specifically have methylene, ethylidene, The divalent alkyls such as various propylidene, various butylidenes.
It should be noted that the v in general formula (C-1) indicates R5cThe number of repeat unit of O, be its average value be 1 ~ 50, preferably 1 ~ 20, the number of further preferably 1 ~ 10, particularly preferably 1 ~ 5 range.R5cO there are it is multiple when, multiple R5cO can it is identical or It is different.V can be identical or different for each structural unit.
In addition, w expressions 1 ~ 50, preferably 1 ~ 10, further preferred 1 ~ 2, particularly preferred 1 number, u expressions 0 ~ 50, preferably 2 ~ 25, further preferred 5 ~ 15 number, w and u they there are it is multiple when, can be respectively block or random.
Further, the R in general formula (C-1)6cIt is preferred that indicating the alkyl that carbon atom number is 1 ~ 10, the acyl that carbon atom number is 2 ~ 10 The oxygen-containing alkyl that base or carbon atom number are 2 ~ 50.
The carbon atom number be 1 ~ 10 alkyl refer to specifically indicate methyl, ethyl, n-propyl, isopropyl, normal-butyl, Isobutyl group, sec-butyl, tertiary butyl, various amyls, various hexyls, various heptyl, various octyls, various nonyls, various decyls, ring Amyl, cyclohexyl, various methylcyclohexyls, various ethylcyclohexyls, various propylcyclohexyls, various Dimethylcyclohexyls etc..
In addition, as carbon atom number be 2 ~ 10 acyl group, can enumerate acetyl group, propiono, bytyry, isobutyryl, Valeryl, isovaleryl, pivaloyl group, benzoyl, toluyl groups etc..
Further, as carbon atom number be 2 ~ 50 oxygen-containing alkyl concrete example, can preferably enumerate methoxy, Methoxy ethyl, methoxy-propyl, 1,1- bi-methoxies propyl, 1,2- bi-methoxies propyl, ethoxycarbonyl propyl, (2- methoxyl groups Ethyoxyl) propyl, (1- methyl -2- methoxyl groups) propyl etc..
In general formula (C-1), R4cShown in carbon atom number be 1 ~ 10 alkyl refer to specifically indicating methyl, ethyl, just Propyl, isopropyl, normal-butyl, isobutyl group, various amyls, various hexyls, various heptyl, various octyls, various nonyls, the various last of the ten Heavenly stems The alkyl such as base；Cyclopenta, cyclohexyl, various methylcyclohexyls, various ethylcyclohexyls, various propylcyclohexyls, various diformazans The naphthenic base such as butylcyclohexyl；Phenyl, various aminomethyl phenyls, various ethylphenyls, various 3,5-dimethylphenyls, various propyl phenyl, The aryl such as various trimethylphenyls, various butyl phenyls, various naphthalenes；Benzyl, various phenylethyls, various methylbenzene first Aryl alkyls such as base, various phenyl propyls, various phenyl butyls etc..
By will have the polyvingl ether based copolymer I of structural unit shown in aforementioned formula (C-1) that copolymer is made, Lubricity, insulating properties, hygroscopicity etc. can be improved while meeting compatibility.
On the other hand, in polyvingl ether based copolymer II shown in aforementioned formula (C-2), R1c~R5cAnd v and aforementioned phase Together.R4c、R5cThey there are it is multiple when, respectively can be identical or different.X and y respectively indicates 1 ~ 50 number, and x and y are at them There are it is multiple when, can be respectively block or random.Xc、YcEach independently represent hydrogen atom, hydroxyl or carbon atom number be 1 ~ 20 alkyl.
It should be noted that number of repeat unit u, w, x, y in general formula (C-1), (C-2) are preferably suitably selected to reach the aftermentioned phase The viscosity of prestige.In addition, for the manufacturing method of polyvingl ether based copolymer I, II, as long as the method for obtaining it, then do not have There is special limitation.
Vinyl ethers based copolymer I shown in general formula (C-1) can be made one end be general formula below (C-3) or (C-4) shown in and remaining end has the polyvingl ether system of structure shown in general formula below (C-5) or general formula (C-6) Copolymer I.
[chemical formula 8]
(in above-mentioned (C-3), (C-4), R1c~R6cAs hereinbefore with v).
[chemical formula 9]
(in above-mentioned (C-5), (C-6), R1c~R6cAs hereinbefore with v).
＜ polyalcohols esters (POE) ＞
In refrigerator oil, as the polyalcohol esters that can be used as base oil, it is preferable to use glycol or have 3 ~ 20 hydroxyls Polyalcohol and carbon atom number be 1 ~ 24 the ester that is formed of aliphatic acid.Here, as glycol, it can be cited for example that ethylene glycol, 1, 3-propanediol, propylene glycol, 1,4- butanediols, 1,2- butanediols, 2- methyl-1,3-propanediols, 1,5- pentanediols, neopentyl glycol, 1,6-HD, 2- Ethyl-2-Methyl -1,3- propylene glycol, 1,7- heptandiols, 2- methyl-2-propyl -1,3- propylene glycol, 2,2- Diethyl -1,3- propylene glycol, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 1,11- undecanes, 1,12- 12 Alkane glycol etc..As polyalcohol, it can be cited for example that trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, two (three Hydroxymethyl-propane), three (trimethylolpropanes), pentaerythrite, two (pentaerythrites), three (pentaerythrites), glycerine, poly- the third three Alcohol (2 ~ 20 aggressiveness of glycerine), penta triols of 1,3,5-, D-sorbite, sorbitan, D-sorbite glycerine condensation product, The polyalcohols such as ribitol, arabite, xylitol, mannitol；Xylose, arabinose, ribose, rhamnose, glucose, fruit Sugar, galactolipin, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, melitriose, gentianose, The carbohydrates such as melezitose；And their partial etherification and methyl glucosamine (glycocide) etc..Among these, as polyalcohol, Preferably neopentyl glycol, trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, two (trimethylolpropanes), three (three Hydroxymethyl-propane), pentaerythrite, two (pentaerythrites), the hindered alcohols such as three (pentaerythrites).
As aliphatic acid, especially carbon atom number, there is no limit it is 1 ~ 24 aliphatic acid that can usually use carbon atom number. Among the aliphatic acid that carbon atom number is 1 ~ 24, from the viewpoint of lubricity, the aliphatic acid that preferably carbon atom number is 3 or more, The aliphatic acid that the aliphatic acid that more preferably carbon atom number is 4 or more, further preferably carbon atom number are 5 or more.In addition, from From the perspective of the compatibility of refrigerant, preferably carbon atom number is 18 aliphatic acid below, and more preferably carbon atom number is 12 Aliphatic acid below is even more preferably 9 aliphatic acid below for carbon atom number.
Furthermore, it is possible to for any one in straight-chain aliphatic acid, branched aliphatic acid, from the viewpoint of lubricity, preferably For straight-chain aliphatic acid, from the viewpoint of hydrolytic stability, preferably branched aliphatic acid.Further, it is possible to be saturated fat Any one in fat acid, unsaturated fatty acid.
As aliphatic acid, it can be cited for example that isobutyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, Dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, octadecanoid acid, nonadecylic acid, 20 The aliphatic acid or alpha-carbon atom of the linear chain or branched chains such as alkanoic acid, oleic acid are the so-called eo-acid etc. of quaternary carbon.More specifically, excellent Be selected as isobutyric acid, valeric acid (positive valeric acid), caproic acid (n-caproic acid), enanthic acid (positive enanthic acid), sad (caprylic acid), n-nonanoic acid (pelargonic acid), Capric acid (n-capric acid), oleic acid (elaidic acid), isovaleric acid (3 Methylbutanoic acid), 2 methyl caproic acid, 2- ethyls penta Acid, 2 ethyl hexanoic acid, 3,5,5 Trimethylhexanoic acid etc..
Can be that whole hydroxyls not in polyalcohol are esterified and remaining partial ester it should be noted that as polyol ester, Can also be full ester obtained from whole hydroxyls are esterified, in addition it is also possible to be the mixture of partial ester and full ester, preferably entirely Ester.
Among the polyol ester, from the viewpoint of hydrolytic stability is better, more preferably neopentyl glycol, trihydroxy methyl Ethane, trimethylolpropane, tri hydroxy methyl butane, two (trimethylolpropanes), three (trimethylolpropanes), pentaerythrite, two The ester of the hindered alcohols such as (pentaerythrite), three (pentaerythrites) is even more preferably neopentyl glycol, trimethylolethane, three hydroxyls The ester of methylpropane, tri hydroxy methyl butane and pentaerythrite, from especially excellent with the compatibility and hydrolytic stability of refrigerant Viewpoint is set out, most preferably the ester of pentaerythrite.
As the concrete example of preferred polyol ester, neopentyl glycol can be enumerated and be selected from isobutyric acid, valeric acid, caproic acid, heptan Acid, octanoic acid, n-nonanoic acid, capric acid, oleic acid, isovaleric acid, 2 methyl caproic acid, 2- ethylpentanoics, 2 ethyl hexanoic acid, 3,5,5- trimethyls oneself The diester that one or two or more kinds of aliphatic acid in acid are formed；Trimethylolethane with selected from isobutyric acid, valeric acid, caproic acid, heptan Acid, octanoic acid, n-nonanoic acid, capric acid, oleic acid, isovaleric acid, 2 methyl caproic acid, 2- ethylpentanoics, 2 ethyl hexanoic acid, 3,5,5- trimethyls oneself Three esters that one or two or more kinds of aliphatic acid in acid are formed；Trimethylolpropane with selected from isobutyric acid, valeric acid, caproic acid, heptan Acid, octanoic acid, n-nonanoic acid, capric acid, oleic acid, isovaleric acid, 2 methyl caproic acid, 2- ethylpentanoics, 2 ethyl hexanoic acid, 3,5,5- trimethyls oneself Three esters that one or two or more kinds of aliphatic acid in acid are formed；Tri hydroxy methyl butane with selected from isobutyric acid, valeric acid, caproic acid, heptan Acid, octanoic acid, n-nonanoic acid, capric acid, oleic acid, isovaleric acid, 2 methyl caproic acid, 2- ethylpentanoics, 2 ethyl hexanoic acid, 3,5,5- trimethyls oneself Three esters that one or two or more kinds of aliphatic acid in acid are formed；Pentaerythrite with selected from isobutyric acid, valeric acid, caproic acid, enanthic acid, pungent In acid, n-nonanoic acid, capric acid, oleic acid, isovaleric acid, 2 methyl caproic acid, 2- ethylpentanoics, 2 ethyl hexanoic acid, 3,5,5 Trimethylhexanoic acid Four esters that are formed of one or two or more kinds of aliphatic acid.
It should be noted that can mix two kinds or more of a kind of aliphatic acid and more with the ester that two kinds or more of aliphatic acid is formed Substance obtained from the ester that first alcohol is formed can also be the ester of two kinds or more of fatty acid mixed and polyalcohol formation, particularly, It is the low-temperature characteristics for the ester that fatty acid mixed is formed with polyalcohol, excellent in compatibility with refrigerant.
100 DEG C of kinematic viscosity of the oxygen-containing organic compound contained in refrigerator oil are preferably 1 ~ 30mm2/s.The movement is viscous As long as degree is 1mm2/ s or more then plays good greasy property, while leakproofness also becomes good.In addition, if being 30mm2/ s hereinafter, then refrigerant and refrigerator oil it is excellent in compatibility, saving the energy becomes good.From the viewpoint of above, 100 DEG C of kinematic viscosity of oxygen-containing organic compound are more preferably 2 ~ 20mm2/ s, further preferably 3 ~ 15mm2/s。
It should be noted that base oil can be only made of above-mentioned oxygen-containing organic compound, but do not hindering the purpose of the present invention In the range of, other than oxygen-containing organic compound, conjunction that can be containing mineral oil, other than above-mentioned oxygen-containing organic compound At oil or the two.It should be noted that the base oil other than above-mentioned oxygen-containing organic compound is excellent relative to refrigerator oil total amount Choosing is less than 10 mass %, more preferably less than 5 mass %, even more preferably below 1 mass %.Other than oxygen-containing organic compound For base oil also in the same manner as oxygen-containing organic compound, 100 DEG C of kinematic viscosity are preferably 1 ~ 30mm2/ s, more preferably 2 ~ 20mm2/s、 Further preferably 3 ~ 15mm2/s。
[polyphosphate based compound]
The polyphosphate based compound contained in the refrigerator oil of present embodiment is that have at least two phosphoric acid in a molecule The phosphate compound of skeleton.Polyphosphate based compound general formula (1) compound represented specifically below.
[chemical formula 10]
(wherein, in formula (1), n indicates 1 ~ 10 integer, R1~R8It is 1 ~ 20 to each independently represent hydrogen atom or carbon atom number Alkyl, R9Indicate that carbon atom number is 2 ~ 20 bivalent hydrocarbon radical).
The refrigerator oil of present embodiment passes through the metal containing above-mentioned polyphosphate based compound and aftermentioned organic carboxyl acid Salt can reduce the friction coefficient at the slipper of refrigerator, and abrasion performance is made to reach good.
It should be noted that polyphosphate based compound can be used singly or in combination of two or more.
In general formula (1), R1~R8In alkyl can be straight-chain, branched, it is cyclic annular in any one, can enumerate methyl, It is ethyl, n-propyl, isopropyl, various butyl, various amyls, various hexyls, various heptyl, various octyls, various nonyls, various Decyl, various undecyls, various dodecyls, various tridecyls, various myristyls, various pentadecyls, various ten Six alkyl, various heptadecyls, various octadecyls etc..
R1~R8The alkyl that preferably hydrogen atom or carbon atom number are 1 ~ 4, more preferably hydrogen atom or methyl, most preferably hydrogen Atom.
R in general formula (1)9Preferably alkylidene, arlydene or the alkyl formed by arlydene and alkylidene, in addition, excellent Choosing includes arlydene.Here, R9For alkylidene when, the alkylidene it can be cited for example that ethylidene, propylidene, butylidene, Asia penta Base, hexylidene, heptamethylene, octamethylene, nonylene, decylene, alkylene undecyl, sub-dodecyl, sub- myristyl, Asia 16 Alkyl, alkylene octadecyl, alkylene eicosyl etc., they can be the group of straight-chain or the base of various branched Group.In addition, as alkylidene, or cyclopropylidene, sub- cyclobutyl, cyclopentylene, cyclohexylidene, cycloheptylidene, sub- ring Octyl, sub- bicyclopentyl, the isothrausmatic alkylidene of sub- three cyclopenta.
In addition, as arlydene, any one in being substitution or being unsubstituted, specifically, substitution or not can be enumerated Substituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted xenyl etc., as arlydene, preferably not Substitution.In addition, among these, preferably phenylene.
Further, R9When being formed by arlydene and alkylidene, arlydene is same as described above, and as alkylidene, can be with Enumerate straight-chain, branched or cricoid carbon atom number be 1 ~ 14 alkylidene, can use such as methylene, with above-mentioned phase Same group.Furthermore it is preferred that the alkylidene that the carbon atom number for being straight-chain or branched is 1 ~ 5, specifically, Asia can be enumerated The various ethylidene such as methyl, 1,1- ethylidene, 1,2- ethylidene, 1,3- propylidene, 1,2- propylidene, 2,2- propylidene etc. are various Propylidene, various butylidenes, various pentylidene, among these, more preferably 2,2- propylidene (- C (CH3)2-)。
In addition, in general formula (1), n is preferably 1 ~ 8, can be n by a kind of specific monomer formed, or n is by spy The mixture of two kinds of fixed composition described above.N is more preferably 1 ~ 3, wherein n is particularly preferably 1.By reducing n, molecular weight becomes smaller, Therefore the solubility for being easy to improve relative to base oil further easily reduces friction coefficient.
In addition, as R9Suitable concrete example, group shown in general formula (2) ~ (4) preferably below is more preferably logical Group shown in formula (2) or (3), more preferably group shown in general formula (2).It should be noted that general formula (2) can be ortho position body, Any one in meta position body, contraposition body, preferably meta position body.
[chemical formula 11]
。
In addition, the concrete example as preferred polyphosphate based compound, it can be cited for example that general formula below (5) and (6) compound represented.Among these, general formula (5) compound represented more preferably below.
[chemical formula 12]
。
In formula (5), the integer of n expressions 1 ~ 10, preferably 1 ~ 8, more preferably 1 ~ 5.It should be noted that shown in general formula (5) Polyphosphate based compound base oil include PVE as above-mentioned oxygen-containing organic compound when, easy performance is sent as an envoy to abrasion performance Achieve the effect that good and reduce friction coefficient, when n is 1 ~ 3, particularly when n is 1, is easy to play the effect.
[chemical formula 13]
。
The content of polyphosphate based compound is preferably 0.01 ~ 5.0 mass % relative to refrigerator oil total amount.This embodiment party It, can be by the stability of refrigerator oil, abrasion performance by the polyphosphate based compound containing 0.01 mass % or more in formula While property is maintained good, the friction coefficient at slipper is efficiently reduced.In addition, by being set as 5.0 mass % hereinafter, Polyphosphate based compound is easy to be dissolved in base oil, and is easy to play effect corresponding with content.
In addition, while in view of the stability and abrasion performance of refrigerator oil, in order to efficiently reduce at sliding part Friction coefficient, the content of above-mentioned polyphosphate based compound is more preferably 0.5 ~ 5.0 mass %, further preferably 1.0 ~ 5.0 Quality %, particularly preferably 1.0 ~ 3.0 mass %.
[metal salt of organic carboxylic acid]
The carbon atom number of the organic carboxyl acid used in the metal salt of organic carboxylic acid of present embodiment is 6 ~ 60.In addition, as organic The organic carboxyl acid that the organic carboxyl acid that carboxylic acid, preferably carbon atom number are 6 ~ 24, more preferably carbon atom number are 16 ~ 20.
As organic carboxyl acid, aliphatic saturation monocarboxylic acid, aliphatic unsaturated monocarboxylic, aliphatic dicarboxyl can be enumerated Acid, aromatic carboxylic acid, ester ring type carboxylic acid etc..
If further enumerating concrete example, it is saturated monocarboxylic acid as aliphatic, caproic acid, octanoic acid, capric acid, the moon can be enumerated The straight chain fatties such as cinnamic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, cerinic acid (cerotic acid), lacceroic acid Acid；2 methyl valeric acid, 2,2-dimethylbutyric acid, 2 methyl caproic acid, 5- methylhexanoic acids, 2,2- dimethyl enanthic acid, 2- ethyl -2- first Base butyric acid, 2 ethyl hexanoic acid, dimethylhexanoic acid, 2- n-propyls-valeric acid, 3,5,5 Trimethylhexanoic acid, dimethyl octanoic acid, different 13 The branched chain fatty acids such as alkanoic acid, different myristic acid, isostearic acid, different arachidic acid, isocaproic acid.
In addition, as aliphatic unsaturated monocarboxylic, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, flax can be enumerated Acid etc. and the hydroxy unsaturated acids such as ricinoleic acid.In addition, as aliphatic dicarboxylic acid, can enumerate adipic acid, azelaic acid, Decanedioic acid can enumerate benzoic acid, phthalic acid, trimellitic acid, Pyromellitic Acid etc. as aromatic carboxylic acid.In addition, making For ester ring type carboxylic acid, aphthenic acids etc. can be enumerated.
Furthermore, it is possible to for dimeric dibasic acid, the trimer acid etc. of various aliphatic acid.
These organic carboxyl acids can be used alone, and can also be applied in combination 2 kinds.
Among those, the aliphatic that preferably carbon atom number is 16 ~ 20 is saturated monocarboxylic acid to organic carboxyl acid, carbon atom number is 16 ~ 20 aliphatic unsaturated monocarboxylic, wherein the more preferably aliphatic unsaturated monocarboxylic such as oleic acid.
The metal of metal salt of organic carboxylic acid is constituted specifically, the alkali metal such as lithium, potassium, sodium, magnesium, calcium, strontium etc. can be enumerated Alkaline-earth metal, zinc, nickel, aluminium etc. as other metals.Preferred metal is alkali and alkaline earth metal ions, more preferably alkali gold Belong to, particularly preferably potassium.These metals are not limited to a kind, two or more can be applied in combination.
The concrete example of metal salt of organic carboxylic acid more preferably, among above-mentioned, particularly preferably potassium oleate.
The content of metal salt of organic carboxylic acid in refrigerator oil is dense with metal component relative to refrigerator oil total amount (quality) Degree meter is preferably 1ppm or more.In present embodiment, by by content be set as with metal component densimeter 1ppm or more and with it is upper It states polyphosphate based compound to be applied in combination, friction coefficient can be reduced while so that abrasion performance is reached good.Organic carboxylic The content of acid metal salt is in order to suitably obtain these effects, more with the metal component densimeter for refrigerator oil total amount Preferably 1 ~ 20ppm, further preferably 1 ~ 10ppm, particularly preferably 1 ~ 5ppm.
It can be any means as fitting method of the metal salt of organic carboxylic acid in refrigerator oil, preferably make molten in advance The solvent for solving or being dispersed with metal salt of organic carboxylic acid is matched in refrigerator oil, it should be noted that being dissolved or being dispersed with organic The method of the solvent of carboxylic metallic salt is not particularly limited, and can be obtained to make organic carboxyl acid and reacting metal salt in a solvent It arrives, but metal salt of organic carboxylic acid obtained from reacting in advance can also be made to be dissolved or dispersed in solvent and obtain.
As solvent, as long as the solvent of metal salt of organic carboxylic acid can be dissolved or be disperseed, various alcohol can be enumerated Class, ethers, wherein preferably ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, Isosorbide-5-Nitrae-fourth two The polyalcohols such as alcohol, 2,3-butanediol, hexylene glycol, ethohexadiol, glycerine, wherein more preferably dipropylene glycol.The usage amount of solvent It is usually 5 ~ 50 times in terms of using carboxylic metallic salt as benchmark (quality).
[other additives]
Refrigerator oil involved by present embodiment other than above-mentioned polyphosphate based compound, metal salt of organic carboxylic acid, into One step, can also contain antioxidant, sour agent for capturing, antifoaming agent, extreme pressure agent, oiliness improver, oxygen agent for capturing, metal inerting agent and It is arbitrary one kind or two or more in the various additives such as antirust agent.That is, refrigerator oil can be by base oil, above-mentioned polyphosphate system Compound and above-mentioned metal salt of organic carboxylic acid are formed, can also be by base oil, above-mentioned polyphosphate based compound, above-mentioned organic Carboxylic metallic salt and above-mentioned solvent are formed, can also be by base oil, above-mentioned polyphosphate based compound, above-mentioned organic carboxyl acid gold Belong to salt, additive in addition to this to be formed, it can also be by above-mentioned polyphosphate based compound, above-mentioned metal salt of organic carboxylic acid, molten Agent and additive in addition to this are formed.At this point, base oil can include as described above, other than oxygen-containing organic compound Mineral oil, the synthetic oil other than above-mentioned oxygen-containing organic compound, are preferably formed by oxygen-containing organic compound.
In addition, as above-mentioned various additives, among above-mentioned, preferably comprise in antioxidant, sour agent for capturing and antifoaming agent It is arbitrary one kind or two or more.The above-mentioned additive other than polyphosphate based compound and metal salt of organic carboxylic acid relative to Refrigerator oil total amount preferably comprises 15 mass % or less, further preferably 0 ~ 5 mass %.
As antioxidant, can enumerate 2,6- di-tert-butyl-4-methy phenols, 2,6- di-t-butyl -4- ethyl -phenols, Phenol systems, phenyl-α-naphthylamine, the N such as 2,2' methylene bis (4- methyl-6-tert-butylphenols), N'- diphenyl-p-phenylenediamines etc. The antioxidant of amine system, the preferably antioxidant of phenol system.The content of antioxidant is from the viewpoints such as effect and economy, phase It is usually 0.01 ~ 5 mass %, preferably 0.05 ~ 3 mass % for refrigerator oil total amount.
As sour agent for capturing, it can be cited for example that phenylglycidyl ether, alkyl glycidyl base ether, aklylene glycol The epoxides such as glycidyl ether, cyclohexene oxide, oxidation alpha-olefin, epoxidised soybean oil.Wherein, compatibility this Aspect, preferably phenylglycidyl ether, alkyl glycidyl base ether, aklylene glycol glycidyl ether, oxidation hexamethylene Alkene, oxidation alpha-olefin.
The alkyl of the alkyl glycidyl base ether and the alkylidene of aklylene glycol glycidyl ether can have branch Chain, carbon atom number are usually 3 ~ 30, preferably 4 ~ 24, particularly preferably 6 ~ 16.In addition, oxidation alpha-olefin uses total carbon atom number Generally 4 ~ 50, be preferably 4 ~ 24, specifically for 6 ~ 16 substance.In present embodiment, above-mentioned acid agent for capturing can use a kind, Two or more can also be applied in combination.In addition, its content from the viewpoint of effect and inhibit sludge generate, relative to refrigerator Oily total amount is usually 0.005 ~ 5 mass %, preferably 0.05 ~ 3 mass %.
In present embodiment, by containing sour agent for capturing, the stability of refrigerator oil can be improved.
In addition, as antifoaming agent, it can be cited for example that silicone-based antifoaming agent, fluorinated silicone system antifoaming agent etc..Antifoaming agent Content is usually 0.005 ~ 2 mass %, preferably 0.01 ~ 1 mass % relative to refrigerator oil total amount.
As extreme pressure agent, phosphate, phosphate ester acid, phosphite ester, acid phosphite ester and their amine can be enumerated The phosphorus extreme pressure agents such as salt.
These phosphorus extreme pressure agents are the substances for having in the molecule thereof 1 phosphorus atoms, can enumerate tricresyl phosphate, phosphorus Sour three thio phenyl esters, phosphorous acid three (nonyl phenyl) ester, two oleyl ester of hydrogen phosphite, phosphorous acid 2- ethylhexyl diphenyl phosphates Deng.
Further, as extreme pressure agent in addition to that mentioned above, it can be cited for example that vulcanization grease, sulfide aliphatic acid, vulcanization Ester, olefine sulfide, dihydrocarbyl polysulfide, thiocarbamates, thio terpenes, dialkyl dipropionic acid esters etc. Sulphur system extreme pressure agent.
The content of above-mentioned extreme pressure agent is usually from the viewpoint of lubricity and stability, relative to refrigerator oil total amount 0.001 ~ 5 mass %, particularly preferably 0.005 ~ 3 mass %.
These extreme pressure agents can be used singly or in combination of two or more.
As the example of oiliness improver, the aliphatic such as stearic acid, oleic acid saturation and unsaturated monocarboxylic can be enumerated；Dimerization The polymerized fatty acids such as acid, hydrogenated dimer acids；The hydroxy fatty acids such as ricinoleic acid, 12- hydroxy stearic acids；The fat such as laruyl alcohol, oleyl alcohol Fat race is saturated and unsaturated single methanol；The aliphatic such as stearic amine, oleyl amine are saturated and unsaturated monoamine；Lauramide, The aliphatic such as oleamide are saturated and unsaturated single carboxylic acid amides；The polyalcohols such as glycerine, D-sorbite and aliphatic saturation or not It is saturated the partial ester etc. that monocarboxylic acid is formed.
These can be used singly or in combination of two or more.In addition, its content is total relative to refrigerator oil Amount is usually selected in the range of 0.01 ~ 10 mass %, preferably 0.1 ~ 5 mass %.
As oxygen agent for capturing, 4,4'- thiobis (3 methy 6 tert butyl phenol), diphenyl sulfide, dioctyl can be enumerated Diphenyl sulfide, dialkyl group diphenylene sulfide, benzothiophene, dibenzothiophenes, phenthazine, benzothiopyran derivative, thiapyran, thianthrene, The aliphatic such as the sulfur containing aromatic compounds such as dibenzothiopyrans, diphenylene disulphide, various alkene, diene, triolefin are unsaturated Compound, the terpenes etc. for having double bond.
As metal inerting agent, it can be cited for example that N- [N, N'- dialkyl group (alkyl that carbon atom number is 3 ~ 12) amino first Base] triazole etc..
As antirust agent, it can be cited for example that metal sulfonate, aliphatic amine, organic phosphite, organophosphorus ester, Metal organic sulfonate, organic phosphoric acid metal salt, alkenyl succinic acid ester, polyol ester etc..
It, can be with further in the range of not hindering the purpose of the present invention in refrigerator oil involved by present embodiment Contain other well known various additives.
[refrigerant]
Refrigerator oil involved by present embodiment is the substance used under refrigerant environment, specifically, being and refrigerant The substance for mixing and being used in refrigerator.That is, in present embodiment, with used for refrigerator group containing refrigerator oil and refrigerant The form of object is closed in refrigerator.In composition used for refrigerator, for the usage amount of refrigerant and refrigerator oil, with refrigeration The mass ratio meter of agent/refrigerator oil is preferably in 99/1 ~ 10/90, further 95/5 ~ 30/70 range.If by the quality Than being set as in above range, then refrigerating capacity and lubricity in refrigerator can be made to reach suitable.
As used refrigerant, can enumerate selected from fluorohydrocarbon, the carbon dioxide as natural series coolant, hydrocarbon, With it is one kind or two or more in ammonia.
＜ fluorohydrocarbons ＞
As fluorohydrocarbon, saturated fluorohydrocarbons compound (saturation HFC), unsaturated fluorinated hydrocarbon compound (HFO) can be enumerated.
As saturated fluorohydrocarbons compound, the fluoro object for the alkane that usually carbon atom number is 1 ~ 4, preferably carbon atom number For the fluoro object of 1 ~ 3 alkane, the fluoro object for the alkane (methane or ethane) that more preferably carbon atom number is 1 ~ 2.As specific Methane or ethane fluoro object, can enumerate fluoroform (R23), difluoromethane (R32), 1,1- Difluoroethanes (R152a), 1,1,1- trifluoroethane (R143a), 1,1,2- trifluoroethane (R143), 1,1,1,2- tetrafluoroethane (R134a), 1,1,2,2- tetra- Fluoroethane (R134), 1,1,1,2,2- pentafluoroethane (R125), among these, preferably fluoromethane, 1,1,1,2,2- five fluorine second Alkane.
These saturated fluorohydrocarbons compounds can be used singly or in combination of two or more.Here, as group The example using situation of more than two kinds is closed, can enumerate and mix the saturated fluorohydrocarbons chemical combination that carbon atom number of more than two kinds is 1 ~ 3 It is mixed obtained from the saturated fluorohydrocarbons compound that mix refrigerant obtained from object, mixing carbon atom number of more than two kinds are 1 ~ 2 Refrigerant.
As specific mix refrigerant, the mixture (R410A) of R32 and R125 can be enumerated；R125, R143a with The mixture (R404A) of R134a；The mixture (R407A, R407C, R407E etc.) of R32, R125 and R134a；R125 and R143a Mixture (R507A) etc..
As unsaturated fluorinated hydrocarbon compound, the carbon atom number of straight-chain or branched can be enumerated as 2 ~ 6 chain alkene The substances with carbon-to-carbon double bond such as hydrocarbon, the fluoro object of cyclic olefin that carbon atom number is 4 ~ 6.
More specifically, it can enumerate and import the ethylene of 1 ~ 3 fluorine atom, the propylene that has imported 1 ~ 5 fluorine atom, lead The butylene of 1 ~ 7 fluorine atom is entered, the amylene for having imported 1 ~ 9 fluorine atom, the hexene for having imported 1 ~ 11 fluorine atom, has imported The cyclobutane of 1 ~ 5 fluorine atom, the cyclopentene for having imported 1 ~ 7 fluorine atom, the cyclohexene etc. for having imported 1 ~ 9 fluorine atom.
Among these unsaturated fluorinated hydrocarbon compounds, the preferably fluoro object of propylene has more preferably imported 3 ~ 5 fluorine originals The propylene of son, has most preferably imported the propylene of 4 fluorine atoms.Specifically, as preferred compound, 1,3 can be enumerated, 3,3- tetrafluoropropenes (HFO1234ze), 2,3,3,3- tetrafluoropropenes (HFO1234yf).
These unsaturated fluorinated hydrocarbon compounds can be used singly or in combination of two or more, can also be with Refrigerant compositions other than unsaturated fluorinated hydrocarbon compound use.Here, as in addition to unsaturated fluorinated hydrocarbon compound Except refrigerant compositions the case where using example, saturated fluorohydrocarbons compound and unsaturated fluorinated hydrocarbon compound can be enumerated Mix refrigerant.As specific mix refrigerant, the mix refrigerant of R-32, HFO1234ze and R152a can be enumerated (AC5, mixing ratio 13.23:76.20:9.96) etc..
The natural series coolant ＞ of ＜
As natural series coolant, carbon dioxide (carbonic acid gas) can be enumerated；Propane, normal butane, iso-butane, 2- methyl fourths The hydrocarbon such as alkane, pentane, pentamethylene, iso-butane, normal butane；Ammonia, they can be used alone, can also be applied in combination 2 kinds with On, it can also be with the refrigerant compositions other than natural series coolant.Here, as with other than natural series coolant The example of the case where refrigerant compositions can be enumerated and saturated fluorohydrocarbons compound, unsaturated fluorinated hydrocarbon compound or the two Mix refrigerant.As specific mix refrigerant, the hybrid refrigeration of carbon dioxide, HFO1234ze and R134a can be enumerated Agent (AC6, match ratio 5.15:79.02:15.41) etc..
In present embodiment, among these refrigerants, preferably fluorohydrocarbon, more preferably saturated fluorohydrocarbons compound.System Cryogen can be the mixture of saturated fluorohydrocarbons compound and other refrigerants, but feelings being only made of saturated fluorohydrocarbons compound Condition is preferred.Wherein, further preferably R32, R125, as the R410A of their mixture.In addition, particularly preferred refrigerant Including R32, at this point, the ratio of the R32 in refrigerant totality counted on the basis of refrigerant total amount preferably 50 mass % or more, into One step is preferably 70 mass % or more, is most preferably the 100 individual refrigerants of mass %, i.e. R32.
[refrigerator]
Refrigerator oil or composition used for refrigerator involved by present embodiment are the substances filled and used inside refrigerator. Here, refrigerator refers to freeze cycle, the freeze cycle includes with compressor, condenser, expansion mechanism (expansion valve Deng) and evaporator or compressor, condenser, expansion mechanism, drier and evaporator as necessary structure.Refrigerator oil For being lubricated to the slipper being arranged in such as compressor etc..
It should be noted that the slipper of refrigerator is preferably between metal-metal, as the metal of slipper, Ke Yiju It taps a blast furnace, steel.The refrigerator oil of present embodiment can be while improving the abrasion performance between iron or steel, reduction friction system Number.
In addition, above-mentioned refrigerator oil and composition used for refrigerator are more specifically, it can be used for such as air conditioning for automobiles, combustion gas The various refrigerator systems such as heat pump (GHP), air-conditioning, refrigerator, vending machine, showcase, water heater, floor heating, hot-water supply system, And heating system.
[manufacturing method of refrigerator oil]
In the manufacturing method of refrigerator oil involved by an embodiment of the invention, to above-mentioned comprising oxygen-containing organic compound Base oil in, at least coordinate above-mentioned polyphosphate based compound and metal salt of organic carboxylic acid, to manufacture refrigerator oil.This Outside, in this method, other than polyphosphate based compound and metal salt of organic carboxylic acid, above-mentioned various additives can also be coordinated In it is arbitrary one kind or two or more.Base oil, polyphosphate based compound, metal salt of organic carboxylic acid and various additives it is detailed Describe in detail it is bright same as described above, so the description thereof will be omitted.
Embodiment
Hereinafter, be further elaborated with the present invention by embodiment, but the present invention not due to these examples by any limit It is fixed.It should be noted that each characteristic of the character of base oil, refrigerator oil and composition used for refrigerator is asked according to main points described below Go out.
(1) kinematic viscosity
According to JIS K2283：2000, it is measured using glass system capillary viscosimeter.
(2) lubricity test
Using block (block-on-ring) frictional testing machine (LFW-1) on closed ring is made, made at R32 (difluoromethane) Under cryogen environment, the friction coefficient and ring abrasion loss of the slipper of each composition used for refrigerator are measured under the following conditions.
Ring：FC250 blocks：SKH51 rotating speeds：1000rpm
Break-in：The load-carrying of load-carrying 300N × 1 minute：The 500N times：30 minutes oil temperatures：80℃
Refrigerant pressure：0.4Mpa.
Embodiment 1 ~ 14, comparative example 1 ~ 14
The refrigerator oil of each embodiment, comparative example shown in table 1 and the combination used for refrigerator using the refrigerator oil are prepared respectively Object implements lubricity test.The results are shown in tables 1.
[table 1]
。
In each embodiments of ※, comparative example, base oil, additive are as described below.
[base oil]
PVE：Copolymer (the molar ratio 9 of ethyl vinyl ether and isobutyl vinyl ether:1,100 DEG C of kinematic viscosity is 7.8mm2/ S), two ends are respectively R shown in general formula (A-1-i) and general formula (A-1-ii)6a~R8a、R11a~R13aFor hydrogen atom, and r1 It is 0, R with r210aAnd R15aFor ethyl or isobutyl group.
PAG：(100 DEG C of kinematic viscosity are 9.8mm to polyoxypropylene glycol2/s)
ECP：(5/5, the 100 DEG C of movements of PPG/PEV molar ratios are viscous for polypropylene glycol (PPG)/poly- ethyl vinyl ether (PEV) copolymer Degree is 11.2mm2/s)
POE：(C8 acid/1/1.1,100 DEG C of C9 acid molar ratio kinematic viscosity is pentaerythrite octanoic acid (C8 acid) n-nonanoic acid (C9 acid) ester 8.6mm2/s)。
[additive]
Polyphosphate based compound 1：The compound for the mixture that n is 1 ~ 3 in above-mentioned general formula (5)
Polyphosphate based compound 2：The compound for the mixture that n is 1 ~ 8 in above-mentioned general formula (5)
Polyphosphate based compound 3：Above-mentioned general formula (6) compound represented
Polyphosphate based compound 4：Above-mentioned general formula (1) compound represented, wherein R1、R3、R5、R7For hydrogen atom, R2、R4、 R6、R8The alkyl for being 1 ~ 20 for carbon atom number, R9The bivalent hydrocarbon radical for being 2 ~ 20 for carbon atom number, the mixture that n is 1 ~ 8.
Metal salt of organic carboxylic acid dilution：Dipropylene glycol dilution (the dilution ratio of potassium oleate：30 times, the potassium in dilution is dense Degree：4000ppm)
Antioxidant：2,6 di tert butyl 4 methyl phenol (DBPC)
Sour agent for capturing：2- ethylhexyl glycidyl ethers
Antifoaming agent：Silicone-based antifoaming agent.
By the result of the lubricity test of embodiment 1 ~ 14 it is found that by containing polyphosphate system chemical combination in refrigerator oil Both object and metal salt of organic carboxylic acid can reduce the friction coefficient at the slipper of refrigerator.In addition, few by ring abrasion loss It is found that abrasion performance also becomes good.
In contrast, as shown in comparative example 1 ~ 14, polyphosphate based compound and organic carboxylic are free of in refrigerator oil In the case of either or both of acid metal salt, both abrasion performance and friction coefficient can not be made to reach good.

Claims (14)

1. refrigerator oil, it includes the metals for the organic carboxyl acid that base oil, polyphosphate based compound and carbon atom number are 6 ~ 60 Salt, the base oil include oxygen-containing organic compound.
2. refrigerator oil according to claim 1, wherein the content of the polyphosphate based compound is relative to refrigerator Oily total amount is 0.01 ~ 5.0 mass %.
3. refrigerator oil according to claim 1 or 2, wherein the content of the metal salt of the organic carboxyl acid is relative to cold Freeze machine oil total amount and 1ppm or more is calculated as with metal component concentration.
4. according to refrigerator oil as claimed in any one of claims 1 to 3, wherein the oxygen-containing organic compound is to be selected from poly- second The copolymer of alkenyl ethers, polyether polyols class, poly- (oxygen) aklylene glycol or its monoether and polyvingl ether and polynary It is at least one kind of in alkoxide.
5. the refrigerator oil according to any one of claim 1 ~ 4, wherein the polyphosphate based compound is following logical Formula (1) compound represented,
[chemical formula 1]
Wherein, in formula (1), n indicates 1 ~ 10 integer, R1~R8Hydrogen atom or carbon atom number are each independently represented as 1 ~ 20 alkane Base, R9Indicate that carbon atom number is 2 ~ 20 bivalent hydrocarbon radical.
6. refrigerator oil according to claim 5, wherein in general formula (1), R9Including arlydene.
7. refrigerator oil according to claim 5 or 6, wherein in general formula (1), R9For the following general formula (2) or general formula (3) institute Any one shown,
[chemical formula 2]
。
8. the refrigerator oil according to any one of claim 1 ~ 7, wherein the polyphosphate compound is selected from following It is at least one kind of in general formula (5) and (6) compound represented,
[chemical formula 3]
Wherein, in formula (5), n indicates 1 ~ 10 integer；
[chemical formula 4]
。
9. according to refrigerator oil any one of claims 1 to 8, wherein the metal salt of the organic carboxyl acid is organic carboxylic The alkali metal salt of acid.
10. according to refrigerator oil any one of claims 1 to 9, wherein the metal salt of the organic carboxyl acid is carbon original The metal salt for the organic carboxyl acid that subnumber is 16 ~ 20.
11. the refrigerator oil according to any one of claim 1 ~ 10, wherein the metal salt of the organic carboxyl acid is oleic acid Potassium.
12. composition used for refrigerator, it includes the refrigerator oils described in any one of refrigerant and claim 1 ~ 11.
13. composition used for refrigerator according to claim 12, wherein the refrigerant includes selected from fluorohydrocarbon, dioxy Change one kind or two or more in carbon, hydrocarbon and ammonia.
14. the manufacturing method of refrigerator oil, wherein into the base oil comprising oxygen-containing organic compound, at least coordinate polyphosphoric acid The metal salt for the organic carboxyl acid that ester based compound and carbon atom number are 6 ~ 60, to obtain refrigerator oil.
CN201780006501.2A 2016-01-15 2017-01-13 Refrigerator oil and composition for refrigerator Pending CN108431190A (en)

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PCT/JP2017/001045 WO2017122788A1 (en) 2016-01-15 2017-01-13 Refrigeration oil, and composition for use in refrigerating machine

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JP2911629B2 (en) 1991-03-29 1999-06-23 出光興産株式会社 Refrigeration oil composition
JP3173684B2 (en) 1992-06-04 2001-06-04 出光興産株式会社 Lubricating oil for compression refrigerators
JP2859253B2 (en) 1997-12-08 1999-02-17 出光興産株式会社 Refrigeration oil for fluorinated alkane refrigerant
JP4184544B2 (en) * 1999-06-21 2008-11-19 出光興産株式会社 Refrigerating machine oil composition for carbon dioxide refrigerant
US8409464B2 (en) 2006-09-29 2013-04-02 Idemitsu Kosan Co., Ltd. Lubricant for compression refrigerating machine and refrigerating apparatus using the same
KR101871696B1 (en) * 2010-03-26 2018-06-27 가부시키가이샤 아데카 Lubricant Additive and Lubricant Composition containing Lubricant Additive
JP2012107108A (en) * 2010-11-17 2012-06-07 Adeka Corp Abrasion preventing agent composition, and lubricant composition containing the abrasion preventing agent composition

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Application publication date: 20180821