CN104093694A - Mixed ester of mixed polyhydric alcohol and carboxylic acid - Google Patents
Mixed ester of mixed polyhydric alcohol and carboxylic acid Download PDFInfo
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- CN104093694A CN104093694A CN201380007825.XA CN201380007825A CN104093694A CN 104093694 A CN104093694 A CN 104093694A CN 201380007825 A CN201380007825 A CN 201380007825A CN 104093694 A CN104093694 A CN 104093694A
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- acid
- mixed ester
- dipentaerythritol
- tetramethylolmethane
- isopropylformic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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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
- 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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- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/011—Cloud point
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Emergency Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The present invention provides a mixed ester of a mixed polyhydric alcohol comprising pentaerythritol and dipentaerythritol which is represented by formula (I), and a carboxylic acid that contains isobutyric acid. The molar ratio of the pentaerythritol and the dipentaerythritol (pentaerythritol/dipentaerythritol) in the mixed polyhydric alcohol is between 98/2 and 40/60, and the proportion of isobutyric acid in the carboxylic acid is 35 to 85 mol.%. The mixed ester, while maintaining a viscosity range required for a refrigerator oil, exhibits excellent lubricating properties and excellent compatibility with a difluoromethane refrigerant, and can be used as a refrigerator oil and the like.
Description
Technical field
The present invention relates to the mixed ester for refrigerator wet goods Industrial Oil etc.
Background technology
In recent years, ozone layer destroying coefficient be zero and the lower HFC compound (HFC) of global greenhouse effect coefficient (GWP) as used for refrigerator refrigeration agent, use.The GWP of methylene fluoride refrigeration agent (HFC-32) is lower, refrigeration agent [R-410A (mixture of methylene fluoride and pentafluoride ethane), R-407C (methylene fluoride and the pentafluoride ethane and 1 using at present, 1,1, the mixture of 2-Tetrafluoroethane) etc.] approximately 1/3～1/4, and its coefficient of performance (COP) has also improved approximately 5～13% with respect to R-410A, R-407C etc.,, from the viewpoint of energy-saving, be therefore preferred refrigeration agent (non-patent literature 1).
In the refrigerant circulation loop (サ イ Network Le) of refrigerator, conventionally form together with the refrigeration agent of refrigerator oil and lubricated coolant compressor the structure at loop internal recycle.Therefore, require refrigerator oil to there is the consistency with refrigeration agent, and because the object of the working portion for lubricated refrigerator is used, so lubricity is also important certainly.If refrigerator oil is separated, from coolant compressor, refrigerator oil out becomes and is easily trapped in loop, as a result, the refrigerator oil mass in coolant compressor declines, and produces and causes insufficient lubrication or block the problems such as expansion mechanism such as kapillary.For the lubricity in refrigerator, the particularly importantly maintenance of the oil film in the compressor reaching a high temperature, in order to keep oil film, refrigerator oil viscosity is very important.If viscosity is low, oil film attenuation, easily causes insufficient lubrication, if viscosity is high, and the decrease in efficiency of heat exchange (patent documentation 1, patent documentation 2, patent documentation 3).
Patent documentation 2 discloses for the tetramethylolmethane of refrigerator oil and the ester of lipid acid for methylene fluoride refrigeration agent, but the consistency of this ester and methylene fluoride refrigeration agent etc. are insufficient.
Patent documentation 3 has been recorded as the useful multiple carboxylicesters of the cooling liqs of refrigerator and air-conditioning, wherein, disclose a kind of liquid composition, this liquid composition contains the ester obtaining by the carboxylic acid reaction that makes tetramethylolmethane and Dipentaerythritol and contain isobutyric anhydride.But, do not record the consistency of this ester and methylene fluoride refrigeration agent, and the viscosity of this ester is not in as the necessary range of viscosities of refrigerator oil.
Prior art document
Patent documentation
Patent documentation 1: No. 3429031 communique of Japanese Patent
Patent documentation 2: TOHKEMY 2002-129177 communique
Patent documentation 3: Japanese kokai publication hei 6-41575 communique
Non-patent literature
The sliding Longitude Economic of non-patent literature 1:< < Run > >, phase in June, 2004 (No.460), the 17th page
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of mixed ester for refrigerator wet goods, it is guaranteeing as refrigerator oil in necessary range of viscosities also have good consistency with methylene fluoride refrigeration agent etc.
For the method for dealing with problems
The invention provides following [1]～[4].
[1] mixed ester, it is the polyol blend consisting of the Dipentaerythritol shown in tetramethylolmethane and formula (I) and the mixed ester that contains isobutyric carboxylic acid,
The scope that tetramethylolmethane in described polyol blend and the mol ratio of Dipentaerythritol [tetramethylolmethane/Dipentaerythritol] are 98/2～40/60, isopropylformic acid shared ratio in described carboxylic acid is the scope of 35～85 % by mole.
[2] mixed ester as described in [1], wherein, described carboxylic acid contains isopropylformic acid and 3,5,5 Trimethylhexanoic acid and/or 2 ethyl hexanoic acid.
[3] mixed ester as described in [1], wherein, described carboxylic acid consists of isopropylformic acid and 3,5,5 Trimethylhexanoic acid.
[4] mixed ester as described in [1], wherein, described carboxylic acid consists of isopropylformic acid and 2 ethyl hexanoic acid.
Invention effect
According to the present invention, a kind of mixed ester for refrigerator wet goods is provided, it is guaranteeing as refrigerator oil in necessary range of viscosities also have good consistency with methylene fluoride refrigeration agent etc.
Embodiment
Mixed ester of the present invention is the polyol blend consisting of the Dipentaerythritol shown in tetramethylolmethane and formula (I) and the mixed ester that contains isobutyric carboxylic acid,
The scope that tetramethylolmethane in described polyol blend and the mol ratio of Dipentaerythritol [tetramethylolmethane/Dipentaerythritol] are 98/2～40/60, isopropylformic acid shared ratio in described carboxylic acid is the scope of 35～85 % by mole.At this, mixed ester refers to the compound that uses multiple polyvalent alcohol to carry out esterification and obtain.
Below, the Dipentaerythritol shown in described formula (I) is called to Dipentaerythritol.
In the present invention, alleged " mixed ester " comprises each mode of following (i)～(iii):
(i) with the formation carboxylic acid in a part comprise other carboxylic acids beyond isopropylformic acid and isopropylformic acid the two tetramethylolmethane ester, with the formation carboxylic acid in a part, comprise the two the mixture of ester of Dipentaerythritol of other carboxylic acids beyond isopropylformic acid and isopropylformic acid;
(ii) mixture of tetramethylolmethane and the ester that contains isobutyric carboxylic acid, the ester, the Dipentaerythritol that are formed by tetramethylolmethane and other carboxylic acids beyond isopropylformic acid and the ester that contains isobutyric carboxylic acid and the ester that formed by Dipentaerythritol and isopropylformic acid other carboxylic acids in addition;
(iii) above-mentioned (i) and mixture (ii).
It should be noted that, in mixed ester of the present invention, can not contain part of hydroxyl as the polyol blend of impurity esterified and with residual part ester of the form of hydroxyl etc.
Owing to forming the polyol blend of mixed ester of the present invention, tetramethylolmethane and Dipentaerythritol, consist of, therefore mixed ester of the present invention has and the good consistency of methylene fluoride refrigeration agent, good oilness, viscosity-temperature profile, the characteristic such as cold property fully fully with good balance.
In forming the polyol blend of mixed ester of the present invention, the mol ratio of tetramethylolmethane and Dipentaerythritol [ratio of tetramethylolmethane/Dipentaerythritol] is 98/2～40/60 scope, is preferably 97/3～70/30 scope.This mol ratio of tetramethylolmethane and Dipentaerythritol is 98/2 when following, mixed ester can when guaranteeing essential range of viscosities, improve cold property, with the consistency of methylene fluoride refrigeration agent.On the other hand, this mol ratio is 40/60 when above, and mixed ester can keep good oilness when guaranteeing essential range of viscosities.
Owing to forming the carboxylic acid of mixed ester of the present invention, contain isopropylformic acid, therefore mixed ester of the present invention has and the good consistency of methylene fluoride refrigeration agent, good oilness, viscosity-temperature profile, the characteristic such as cold property fully fully with good balance.
Isopropylformic acid shared ratio in forming the carboxylic acid of mixed ester of the present invention is the scope of 35～85 % by mole, is preferably the scope of 40～80 % by mole, the scope of 60～80 % by mole more preferably.When isopropylformic acid this shared ratio in forming the carboxylic acid of mixed ester departs from the scope of 35～85 % by mole, cannot obtain above-mentioned characteristic.When isobutyric this ratio surpasses 85 % by mole, the cold property variation of mixed ester.
In forming the carboxylic acid of mixed ester of the present invention, as other carboxylic acids beyond isopropylformic acid, can enumerate straight chain aliphatic monocarboxylic acids such as: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2, 2,-neopentanoic acid, 2 Ethylbutanoic acid, 2 methyl valeric acid, 4-methylvaleric acid, 2 methyl caproic acid, 2-ethyl valeric acid, 2-Ethyl-2-Methyl butyric acid, 2, 2-dimethyl valeric acid, 2-methyl enanthic acid, 2 ethyl hexanoic acid, 3-thylhexoic acid, 3, 5, 5-tri-methyl hexanoic acid, 2-Ethyl-2-Methyl valeric acid, 2-methyloctanoic acid, 2, 2-dimethyl enanthic acid, different tridecanoic acid, a chain aliphatic monocarboxylic acid such as Unimac 5680 etc., wherein, preferred butyric acid, valeric acid, caproic acid, enanthic acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2, 2,-neopentanoic acid, 2 Ethylbutanoic acid, 2 methyl valeric acid, 4-methylvaleric acid, 2 methyl caproic acid, 2-ethyl valeric acid, 2 ethyl hexanoic acid, or 3, 5, 5-tri-methyl hexanoic acid, more preferably butyric acid, valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2 ethyl hexanoic acid, or 3, 5, 5-tri-methyl hexanoic acid, further preferred 2 ethyl hexanoic acid, or 3, 5, 5-tri-methyl hexanoic acid.In addition, can combine two or more these preferred carboxylic acid.
Form the carboxylic acid of mixed ester of the present invention for containing isopropylformic acid and 3,5, during the carboxylic acid of 5-tri-methyl hexanoic acid and/or 2 ethyl hexanoic acid, mixed ester of the present invention can contain other carboxylic acids at the content range not damaging with the good characteristics such as consistency of methylene fluoride refrigeration agent etc.
Other carboxylic acids are with respect to isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid and/or 2 ethyl hexanoic acid sum [ratio of other carboxylic acids/(isopropylformic acid and 3,5,5 Trimethylhexanoic acid and/or 2 ethyl hexanoic acid)] is preferably 0/100～50/50 scope, more preferably 0/100.
The carboxylic acid that forms mixed ester of the present invention is by isopropylformic acid and 3,5,5-tri-methyl hexanoic acid or by isopropylformic acid and 2 ethyl hexanoic acid, formed carboxylic acid time, mixed ester of the present invention has and the good consistency of methylene fluoride refrigeration agent, good oilness, viscosity-temperature profile, the characteristic such as cold property fully fully with good balance.
The carboxylic acid that forms mixed ester of the present invention for by isopropylformic acid and 3,5,5 Trimethylhexanoic acid, formed carboxylic acid time, the scope of the mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid [ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid] in 35/65～85/15.
The carboxylic acid that forms mixed ester of the present invention for by isopropylformic acid and 2 ethyl hexanoic acid, formed carboxylic acid time, the scope of the mol ratio of isopropylformic acid and 2 ethyl hexanoic acid [ratio of isopropylformic acid/2 ethyl hexanoic acid] in 35/65～85/15.
The polyol blend consisting of tetramethylolmethane and Dipentaerythritol that forms mixed ester of the present invention can be bought with the commercially available product of the form of mixture, maybe the tetramethylolmethane of buying with the form of commercially available product respectively be mixed to obtain with Dipentaerythritol.
Mixed ester of the present invention for example can be by reacting tetramethylolmethane and Dipentaerythritol and manufacture for 5～60 hours with isopropylformic acid and other carboxylic acids as required at 120～300 ℃.
In described reaction, can use catalyzer, as catalyzer, can enumerate such as mineral acid, organic acid, Lewis acid, organo-metallic, solid acid etc.As the concrete example of mineral acid, can enumerate such as hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid etc.As organic acid concrete example, can enumerate such as tosic acid, Phenylsulfonic acid, fourth sulfonic acid, propanesulfonic acid, ethyl sulfonic acid, methylsulfonic acid etc.As lewis acidic concrete example, can enumerate such as boron trifluoride, aluminum chloride, tin tetrachloride, titanium tetrachloride etc.As organometallic concrete example, can enumerate such as four titanium propanolates, four titanium butoxide, four (2-ethyl hexyl oxy) titanium etc.As the concrete example of solid acid, can enumerate such as Zeo-karb etc.
The usage quantity sum of isobutyric usage quantity and other carboxylic acids is preferably 1.1～1.4 times moles with respect to the hydroxyl sum of used tetramethylolmethane and Dipentaerythritol.
Can in described reaction, use solvent, as solvent, can enumerate such as hydrocarbon system solvents such as benzene,toluene,xylene, hexane, heptane, isohexane, octane-iso, isononane, decane etc.
Preferably react removing limit by the water of reaction generation from reaction mixture on limit.When the water being generated by reaction is removed from reaction mixture, sometimes also can isopropylformic acid and other carboxylic acids be removed from reaction mixture simultaneously.
In addition, due to isopropylformic acid and other carboxylic acids reactive difference for tetramethylolmethane and/or Dipentaerythritol, the mol ratio that forms the tetramethylolmethane of resulting mixed ester and mol ratio, isopropylformic acid and other carboxylic acids of Dipentaerythritol sometimes with the manufacture of mixed ester in the mol ratio of the amount used different.
In addition, the carboxylic acid that forms mixed ester of the present invention also can derive from carboxylic acid anhydride or carboxylic acid halide, by use them in reaction, can effectively make unreacted hydroxy esterification.Carboxylic acid anhydride refers to that 2 carboxylic acids lose 1 molecular water and carry out the compound that condensation forms.Carboxylic acid halide refer to the hydroxyl that contains in the carboxyl with halogen displacement carboxylic acid and material, according to the kind of halogen, have sour fluorochemical, sour muriate, sour bromide, sour iodide etc.
Can be as required with normally used method in Synthetic Organic Chemistry (making the washing of water and/or alkali aqueous solution, the processing based on activated carbon, sorbent material etc., various chromatogram, distillation etc.) purifying mixed ester of the present invention after reaction.
Mixed ester of the present invention has and the good consistency of methylene fluoride solvent, good oilness, sufficient viscosity-temperature profile, sufficient cold property etc.
The kinematic viscosity that viscosity-temperature profile is lubricated wet goods finish is with respect to the variation of temperature variation.It is little with respect to temperature variation that the good finish of viscosity-temperature profile refers to that viscosity changes, and on the other hand, bad finish refers at the rapid tackify of low temperature range, at the also low finish of high temperature range kinematic viscosity ratio anticipation.Viscosity-temperature profile represents with the form of viscosity index conventionally, can say that when numerical value is high, viscosity-temperature profile is good.In addition, the viscosity characteristics under low temperature range is also referred to as low-temperature fluidity, by expressions such as yield point, zero pour, channel points (チ ャ Application ネ Le point).
Yield point refer to according to the method for the K2269 of Japanese Industrial Standards (JIS) will lubricate wet goods finish cooling after, the minimum temperature that finish is mobile.For the low finish of yield point, even if vaporizer while in the winter time or coldlyly etc. under low temperature environment, using as refrigerator oil in refrigerator etc. is the operational conditions of low temperature, therefore mobility does not worsen yet, and it is preferred never producing that the viewpoints such as the work of the equipment that uses finish is bad set out.
In addition, the large place of temperature contrast is long-term when preserving or using lubricated wet goods finish, preferably in high temperature range non-volatility etc. and in low temperature range without the finish that solidifies, separates out etc.As temperature range, be not particularly limited, but preferably high temperature side at approximately 150 ℃, low temperature side at approximately-20 ℃ of finishes that can stably use.To in low temperature range, without characteristic curing, precipitate, be defined as cold property.Mixed ester of the present invention and used tetramethylolmethane and Dipentaerythritol as the polyol blend that forms mixed ester, in the time of therefore can being suppressed at low temperature, produce precipitate.
Stability can be enumerated such as the thermostability in lubricating oil purposes, oxidative stability, stability to hydrolysis, shear stability etc.
Oilness can be enumerated: friction lowering, wearing and tearing lowering, extreme pressure property etc.Can be by adding additive in lubricant base, improving oilness with the ester etc. with the range of viscosities that is suitable for purposes, lubricating condition as lubricant base.
In addition, mixed ester of the present invention is not only excellent with the consistency of existing methylene fluoride mixed solvent (R-410A, R-407C), and the consistency independent with methylene fluoride refrigeration agent is also excellent.
Generally by two separate temperature, represent with the consistency of methylene fluoride refrigeration agent.The consistency of low temperature side can say that two separate temperature is more low better.But as mentioned above, from the viewpoint of oilness, ester requires to have suitable range of viscosities.Be difficult to when guaranteeing suitable viscosity, keep or improve consistency.Mixed ester of the present invention and used tetramethylolmethane and Dipentaerythritol as the polyol blend that forms mixed ester, therefore can when guaranteeing essential range of viscosities, have the consistency with methylene fluoride solvent concurrently.In addition, refrigeration agent is relevant with the character of this ester to the consistency of mixed ester.
When mixed ester of the present invention is used for to refrigerator oil, the kinematic viscosity of this mixed ester at 40 ℃ is preferably 20～100mm
2/ second scope, 30～95mm more preferably
2the scope of/second.
When mixed ester of the present invention is used for to refrigerator oil, if the residual quantity of the hydroxyl of this mixed ester is many, can cause that thereby the less desirable phenomenons such as capillary device obstruction that gonorrhoea makes freezing loop occur refrigerator oil at low temperatures, so the hydroxyl value of this mixed ester is preferably below 10mgKOH/g, more preferably below 5mgKOH/g.
Mixed ester of the present invention is except for refrigerator oil, the washing composition of the electric motor oil that can also use for engine oil, gear oil, hybrid electric vehicle and power truck, lubricating grease, metal parts, softening agent etc.
As the refrigerator oil that has used mixed ester of the present invention, for example can enumerate: the refrigerator wet goods that contains mixed ester and additive for lubricant.In having used the refrigerator oil of mixed ester of the present invention, this mixed ester is used as lubricant base.
As additive for lubricant, can enumerate such as: detergent dispersant, antioxidant, wearing and tearing depressant (wear-resistant dose, antiseize lubricant, extreme pressure agent etc.), friction modifier, oiliness improver, acid scavenger, metal passivator, rust-preventive agent, yield point depressant, viscosity index improving agent, thickening material, defoamer etc.The content of these additives is preferably respectively 0.001～5 % by weight in refrigerator oil.
Can be used in combination mixed ester of the present invention and other lubricant bases.As other lubricant bases, can enumerate such as: mineral oil, synthetic base oil etc.
As mineral oil, can enumerate such as paraffin base system crude oil, middle base system crude oil, naphthenic hydrocarbon base system crude oil etc.In addition, also can use by distillation and wait the treated oil after they are refined.
As synthetic base oil, can enumerate such as the aliphatic ester (fatty acid ester of fatty acid monoester, polyvalent alcohol, aliphatics polybasic ester etc.) beyond: poly-alpha-olefin (alpha-olefin low polymers of polybutene, polypropylene, carbonatoms 8～14 etc.), four esters of the present invention, aromatic ester (aromatic ester of aromatic series monoesters, polyvalent alcohol, aromatic series polybasic ester etc.), polyalkylene glycol, polyvinyl ether, polyphenylene oxide, alkylbenzene, polycarbonate, synthetic naphthenic hydrocarbon etc.
In addition, to dissolve the ability of the additive for lubricant such as metal passivator, silicone based defoamer such as benzotriazole good for mixed ester of the present invention.Such as in order to make lubricating oil, use lubricating oil equipment etc. life and in lubricating oil, dissolve this additive for lubricant and use.This additive for lubricant is the solvability in mixed ester low (Japanese kokai publication hei 10-259394 communique) conventionally.In addition, the solubleness of benzotriazole in mineral oil and/or synthetic oil low (Japanese kokai publication sho 59-189195 communique).But, for example, as the solubleness (25 ℃) of benzotriazole in the mixed ester 15 (aftermentioned embodiment 15) of mixed ester of the present invention, be 0.04g/g, demonstrate the high-dissolvability of benzotriazole.On the other hand, in mixed ester A (aftermentioned comparative example 1), the solubleness (25 ℃) of benzotriazole is 0.02g/g.Mixed ester of the present invention, when benzotriazole is dissolved, has good low-temperature fluidity, good wearability.
Embodiment
By the following examples, comparative example, reference example and test example be described more specifically the present invention, but the present invention is not defined as following embodiment.
NMR (Nuclear Magnetic Resonance) spectrum is measured by following metering equipment, measuring method.
Metering equipment: the GSX-400 processed of NEC company (400MHz)
Measuring method:
1h-NMR, standard substance (tetramethylsilane), solvent (CDCl
3)
The mixed ester of manufacturing in following embodiment 1～24, comparative example 1 and reference example 1～2 is measured respectively to NMR (Nuclear Magnetic Resonance) spectrum, and calculate tetramethylolmethane in mixed ester and the mol ratio of Dipentaerythritol by following formula.
Tetramethylolmethane/Dipentaerythritol=(integrated value/8 of peak R)/(integrated value/4 of peak S)
Wherein, peak R is equivalent to the peak of the hydrogen atom on the methylene radical in tetramethylolmethane, peak S be equivalent to Dipentaerythritol in the methylene radical that closes of ether-oxygen bond on hydrogen atom.
The mixed ester of manufacturing in following embodiment 1～16, comparative example 1 and reference example 1～2 is measured respectively to NMR (Nuclear Magnetic Resonance) spectrum, and calculate isopropylformic acid in mixed ester and the mol ratio of 3,5,5 Trimethylhexanoic acid by following formula.
The integrated value of integrated value/peak U of isopropylformic acid/3,5,5 Trimethylhexanoic acid=peak T
Wherein, peak T is equivalent to the peak of the hydrogen atom on the methyne in isopropylformic acid, and peak U is equivalent to the peak of the hydrogen atom on the methyne in 3,5,5 Trimethylhexanoic acid.
The mixed ester of manufacturing in following embodiment 17～19 is measured respectively to NMR (Nuclear Magnetic Resonance) spectrum, and calculate isopropylformic acid in mixed ester and the mol ratio of 2 ethyl hexanoic acid by following formula.
The integrated value of integrated value/peak V of isopropylformic acid/2 ethyl hexanoic acid=peak T
Wherein, peak T is identical with above-mentioned implication, and peak V is equivalent to the peak of the hydrogen atom on the methyne in 2 ethyl hexanoic acid.
The mixed ester of manufacturing in following embodiment 20 is measured to NMR (Nuclear Magnetic Resonance) spectrum, and calculate isopropylformic acid in mixed ester and the mol ratio of 3,5,5 Trimethylhexanoic acid and 2 ethyl hexanoic acid by following formula.
The integrated value of integrated value/peak V of integrated value/peak U of isopropylformic acid/3,5,5 Trimethylhexanoic acid/2 ethyl hexanoic acid=peak T
Wherein, peak T, peak U are identical with above-mentioned implication with peak V.
The mixed ester of manufacturing in following embodiment 21 is measured to NMR (Nuclear Magnetic Resonance) spectrum, and calculate isopropylformic acid in mixed ester and the mol ratio of 3,5,5 Trimethylhexanoic acid and butyric acid by following formula.
The integrated value of integrated value/peak U of isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid=peak T/(integrated value/2 of peak W)
Wherein, peak T is identical with above-mentioned implication with peak U, and peak W is equivalent to the peak of the hydrogen atom on the α position methylene radical of the carbonyl in butyric acid.
The mixed ester of manufacturing in following embodiment 22 and 23 is measured respectively to NMR (Nuclear Magnetic Resonance) spectrum, and calculate isopropylformic acid in mixed ester and the mol ratio of 3,5,5 Trimethylhexanoic acid and valeric acid by following formula.
The integrated value of integrated value/peak U of isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid=peak T/(integrated value/2 of peak X)
Wherein, peak T is identical with above-mentioned implication with peak U, and peak X is equivalent to the peak of the hydrogen atom on the α position methylene radical of the carbonyl in valeric acid.
The mixed ester of manufacturing in following embodiment 24 is measured to NMR (Nuclear Magnetic Resonance) spectrum, and calculate isopropylformic acid in mixed ester and the mol ratio of 3,5,5 Trimethylhexanoic acid and 2-Methyl Butyric Acid by following formula.
The integrated value of integrated value/peak Y of integrated value/peak U of isopropylformic acid/3,5,5 Trimethylhexanoic acid/2-Methyl Butyric Acid=peak T
Wherein, peak T is identical with above-mentioned implication with peak U, and peak Y is equivalent to the peak of the hydrogen atom on the methyne in 2-Methyl Butyric Acid.
[embodiment 1]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 97/3, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 81/19 mixed ester (mixed ester 1)]
As sorbent material, use the consonance キ ョ processed ー ワ ー of chemical industrial company De 500.
As activated carbon, use the Japanese Enviro Chemicals egression P processed of company.
In the reactor with Dean-Stark separator, add tetramethylolmethane 153g (1.1 moles, Koei-Perstorp company system), Dipentaerythritol 9g (0.04 mole, Koei-Perstorp company system), isopropylformic acid 398g (4.5 moles, Tokyo change into company's system) and 3,5,5-tri-methyl hexanoic acid 177g (1.1 moles, consonance fermentation chemistry company system), while stirring the mixture, at room temperature carry out 30 minutes bell nitrogen, thus that mixture is degassed.
Then, limit is roused nitrogen limit mixture is stirred 23 hours at 155～232 ℃.After reaction, resultant of reaction under the decompression of 0.7kPa, stir 1 hour at 210 ℃, is removed the unreacted carboxylic acid distillation in resultant of reaction thus.The alkali aqueous solution 300mL of the sodium hydroxide that is 2 times moles with the acid number containing with respect to this resultant of reaction, at 90 ℃, washing reaction resultant is 1 hour.Then, resultant of reaction is washed at 90 ℃ with 300mL water 1 hour, carry out 3 times.Then, limit rouse nitrogen limit by resultant of reaction under the decompression of 0.7kPa, stir 1 hour at 110 ℃, thus that resultant of reaction is dry.
In resultant of reaction, add sorbent material 5.5g (be equivalent to resultant of reaction weight 1.0%) and activated carbon 5.5g (be equivalent to resultant of reaction weight 1.0%), limit rouse nitrogen limit by resultant of reaction under the decompression of 0.7kPa, stir 2 hours at 110 ℃, then use filtration adjuvant to filter, obtain thus the mixed ester 1 of 370g.
[embodiment 2]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 97/3, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 64/36 mixed ester (mixed ester 2)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.03/3.01/2.01, operation obtains mixed ester 2 similarly to Example 1 in addition.
[embodiment 3]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 97/3, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 40/60 mixed ester (mixed ester 3)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.03/2.01/3.01, operation obtains mixed ester 3 similarly to Example 1 in addition.
[embodiment 4]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 90/10, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 82/18 mixed ester (mixed ester 4)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.11/4.48/1.12, operation obtains mixed ester 4 similarly to Example 1 in addition.
[embodiment 5]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 90/10, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 72/28 mixed ester (mixed ester 5)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.11/3.92/1.68, operation obtains mixed ester 5 similarly to Example 1 in addition.
[embodiment 6]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 90/10, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 51/49 mixed ester (mixed ester 6)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.11/2.80/2.80, operation obtains mixed ester 6 similarly to Example 1 in addition.
[embodiment 7]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 81/19 mixed ester (mixed ester 7)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.18/4.86/1.21, operation obtains mixed ester 7 similarly to Example 1 in addition.
[embodiment 8]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 58/42 mixed ester (mixed ester 8)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.18/3.49/2.58, operation obtains mixed ester 8 similarly to Example 1 in addition.
[embodiment 9]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 50/50 mixed ester (mixed ester 9)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.18/3.04/3.04, operation obtains mixed ester 9 similarly to Example 1 in addition.
[embodiment 10]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 40/60 mixed ester (mixed ester 10)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.18/2.43/3.64, operation obtains mixed ester 10 similarly to Example 1 in addition.
[embodiment 11]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 80/20, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 82/18 mixed ester (mixed ester 11)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.25/5.28/1.32, operation obtains mixed ester 11 similarly to Example 1 in addition.
[embodiment 12]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 80/20, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 72/28 mixed ester (mixed ester 12)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.25/4.62/1.98, operation obtains mixed ester 12 similarly to Example 1 in addition.
[embodiment 13]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 70/30, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 82/18 mixed ester (mixed ester 13)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.43/6.31/1.58, operation obtains mixed ester 13 similarly to Example 1 in addition.
[embodiment 14]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 70/30, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 60/40 mixed ester (mixed ester 14)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.43/4.73/3.15, operation obtains mixed ester 14 similarly to Example 1 in addition.
[embodiment 15]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 60/40, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 82/18 mixed ester (mixed ester 15)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.67/7.68/1.92, operation obtains mixed ester 15 similarly to Example 1 in addition.
[embodiment 16]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 50/50, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 81/19 mixed ester (mixed ester 16)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/1.00/9.60/2.40, operation obtains mixed ester 16 similarly to Example 1 in addition.
[embodiment 17]
[manufacture that the mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, the mol ratio (ratio of isopropylformic acid/2 ethyl hexanoic acid) of isopropylformic acid and 2 ethyl hexanoic acid is 64/36 mixed ester (mixed ester 17)]
Use 2 ethyl hexanoic acid to replace 3,5,5-tri-methyl hexanoic acid, the mol ratio (ratio of tetramethylolmethane/Dipentaerythritol/isopropylformic acid/2 ethyl hexanoic acid) that makes the usage quantity of tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 2 ethyl hexanoic acid is 1/0.18/3.64/2.43, and operation obtains mixed ester 17 similarly to Example 1 in addition.
[embodiment 18]
[manufacture that the mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, the mol ratio (ratio of isopropylformic acid/2 ethyl hexanoic acid) of isopropylformic acid and 2 ethyl hexanoic acid is 47/53 mixed ester (mixed ester 18)]
Use 2 ethyl hexanoic acid to replace 3,5,5-tri-methyl hexanoic acid, the mol ratio (ratio of tetramethylolmethane/Dipentaerythritol/isopropylformic acid/2 ethyl hexanoic acid) that makes the usage quantity of tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 2 ethyl hexanoic acid is 1/0.18/2.43/3.64, and operation obtains mixed ester 18 similarly to Example 1 in addition.
[embodiment 19]
[manufacture that the mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 70/30, the mol ratio (ratio of isopropylformic acid/2 ethyl hexanoic acid) of isopropylformic acid and 2 ethyl hexanoic acid is 62/38 mixed ester (mixed ester 19)]
Use 2 ethyl hexanoic acid to replace 3,5,5-tri-methyl hexanoic acid, the mol ratio (ratio of tetramethylolmethane/Dipentaerythritol/isopropylformic acid/2 ethyl hexanoic acid) that makes the usage quantity of tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 2 ethyl hexanoic acid is 1/0.43/4.73/3.15, and operation obtains mixed ester 19 similarly to Example 1 in addition.
[embodiment 20]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, mol ratio (isopropylformic acid/3 of 5-tri-methyl hexanoic acid and 2 ethyl hexanoic acid, the ratio of 5,5-tri-methyl hexanoic acid/2 ethyl hexanoic acid) be the manufacture of 61/19/20 mixed ester (mixed ester 20)]
Use 3,5, the mixed carboxylic acid of 5-tri-methyl hexanoic acid and 2 ethyl hexanoic acid replaces 3,5,5 Trimethylhexanoic acid, make tetramethylolmethane, Dipentaerythritol, isopropylformic acid, 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid and 2 ethyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid/2 ethyl hexanoic acid) be 1/0.18/3.64/1.21/1.21, operation obtains mixed ester 20 similarly to Example 1 in addition.
[embodiment 21]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, mol ratio (isopropylformic acid/3 of 5-tri-methyl hexanoic acid and butyric acid, the ratio of 5,5-tri-methyl hexanoic acid/butyric acid) be the manufacture of 39/18/43 mixed ester (mixed ester 21)]
Use 3,5, the mixed carboxylic acid of 5-tri-methyl hexanoic acid and butyric acid replaces 3,5,5 Trimethylhexanoic acid, make tetramethylolmethane, Dipentaerythritol, isopropylformic acid, 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid and butyric acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid/butyric acid) be 1/0.18/2.43/1.21/2.43, operation obtains mixed ester 21 similarly to Example 1 in addition.
[embodiment 22]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, mol ratio (isopropylformic acid/3 of 5-tri-methyl hexanoic acid and valeric acid, the ratio of 5,5-tri-methyl hexanoic acid/valeric acid) be the manufacture of 40/17/43 mixed ester (mixed ester 22)]
Use 3,5, the mixed carboxylic acid of 5-tri-methyl hexanoic acid and valeric acid replaces 3,5,5 Trimethylhexanoic acid, make tetramethylolmethane, Dipentaerythritol, isopropylformic acid, 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid and valeric acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid/valeric acid) be 1/0.18/2.43/1.21/2.43, operation obtains mixed ester 22 similarly to Example 1 in addition.
[embodiment 23]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, mol ratio (isopropylformic acid/3 of 5-tri-methyl hexanoic acid and valeric acid, the ratio of 5,5-tri-methyl hexanoic acid/valeric acid) be the manufacture of 38/39/23 mixed ester (mixed ester 23)]
Use 3,5, the mixed carboxylic acid of 5-tri-methyl hexanoic acid and valeric acid replaces 3,5,5 Trimethylhexanoic acid, make tetramethylolmethane, Dipentaerythritol, isopropylformic acid, 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid and valeric acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid/valeric acid) be 1/0.18/2.43/2.43/1.21, operation obtains mixed ester 23 similarly to Example 1 in addition.
[embodiment 24]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, mol ratio (isopropylformic acid/3 of 5-tri-methyl hexanoic acid and 2-Methyl Butyric Acid, the ratio of 5,5-tri-methyl hexanoic acid/2-Methyl Butyric Acid) be the manufacture of 43/20/37 mixed ester (mixed ester 24)]
Use 3,5, the mixed carboxylic acid of 5-tri-methyl hexanoic acid and 2-Methyl Butyric Acid replaces 3,5,5 Trimethylhexanoic acid, make tetramethylolmethane, Dipentaerythritol, isopropylformic acid, 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid and 2-Methyl Butyric Acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid/2-Methyl Butyric Acid) be 1/0.18/2.43/1.21/2.43, operation obtains mixed ester 24 similarly to Example 1 in addition.
[comparative example 1]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 60/40, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of the mixed ester (mixed ester A) of 12.5/87.5]
Use isobutyric anhydride to replace isopropylformic acid, make tetramethylolmethane, Dipentaerythritol, isobutyric anhydride and 3,5, mol ratio (tetramethylolmethane/Dipentaerythritol/isobutyric anhydride/3 of the usage quantity of 5-tri-methyl hexanoic acid, 5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.67/0.60/8.40, operation obtains mixed ester A similarly to Example 1 in addition.
[reference example 1]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 85/15, isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid (ratio of isopropylformic acid/3,5,5 Trimethylhexanoic acid) is the manufacture of 86/14 mixed ester (mixed ester B)]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/0.18/5.30/0.79, operation obtains mixed ester B similarly to Example 1 in addition.Therefore mixed ester B is at room temperature solid, is unsuitable for as refrigerator oil the purposes of using under temperature range widely.
[reference example 2]
[mol ratio of tetramethylolmethane and Dipentaerythritol (ratio of tetramethylolmethane/Dipentaerythritol) is 35/65, isopropylformic acid and 3,5, the manufacture of the mixed ester (mixed ester C) of the mol ratio of 5-tri-methyl hexanoic acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid) Ga 81/19]
Make tetramethylolmethane, Dipentaerythritol, isopropylformic acid and 3, the mol ratio of the usage quantity of 5,5-tri-methyl hexanoic acid (tetramethylolmethane/Dipentaerythritol/isopropylformic acid/3,5, the ratio of 5-tri-methyl hexanoic acid) be 1/1.87/14.62/3.65, operation obtains mixed ester C similarly to Example 1 in addition.Therefore mixed ester C is at room temperature solid, is unsuitable for as refrigerator oil the purposes of using under temperature range widely.
The mensuration of (test example 1) kinematic viscosity
Use Cannon-Fenske viscometer, the method based on JIS K2283:2000 is measured mixed ester 1～24 and the kinematic viscosity of mixed ester A at 40 ℃ and 100 ℃.In addition, according to the method, calculate viscosity index.Result is as shown in table 1～6.
The mensuration of (test example 2) hydroxyl value
According to the method for JIS K-2501, measure the hydroxyl value of mixed ester 1～24 and mixed ester A～C.Result is as shown in table 1～6.
The mensuration of (test example 3) yield point
Use automatic flowing point tester RPC-01CML (clutch company system), according to the method for JISK2269-1987, measure the yield point of mixed ester 1～24 and mixed ester A.Result is as shown in table 1～6.
The mensuration of (test example 4) two separate temperature
According to the method for JIS K2211:2009, measure the two separate temperature of mixed ester 1～24 and mixed ester A.Mixed ester 1～24 and each 0.4g of mixed ester A and methylene fluoride refrigeration agent 3.6g being enclosed to withstand voltage Glass tubing, mixture is begun to cool down from 30 ℃ with the speed of 0.5 ℃ of per minute, is two separate temperature by the Temperature Setting of mixture generation two separate or gonorrhoea.Result is as shown in table 1～6.But the situation that mixture has been occurred at 30 ℃ to for two separate or gonorrhoea is labeled as " separation ".
The mensuration of (test example 5) frictional coefficient
Use shell-type four ball frictional testing machiness (Shen Gangzao machine company system), under the condition of load 100N, rotating speed 300rpm, 25 ℃ of temperature, test materials [test ball (SUJ-2)], test, measure the frictional coefficient of mixed ester 1～24 and mixed ester A.Frictional coefficient is the mean value of the frictional coefficient of 10 minute of trial trip under these conditions after 20 minutes.Result is as shown in table 1～6.
At (test example 6)-20 ℃, have or not confirmation (evaluation of cold property) curing, precipitate
Mixed ester 1～24 each 10g is put into Glass Containers, in being set as the thermostatted of-20 ℃ standing 10 hours.After Visual Confirmation 10 hours is standing, have or not curing, precipitate.Result is as follows.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
*) owing to being at room temperature solid, so undetermined
From table 1～5, the kinematic viscosity of mixed ester 1～24 at 40 ℃ is 31.2～93.6mm
2/ second, two separate temperature is below-22 ℃.Mixed ester 1～24 is in the good consistency of guaranteeing as refrigerator oil to have in necessary range of viscosities with methylene fluoride refrigeration agent.
From table 1～5, the frictional coefficient of mixed ester 1～24 is below 0.10.Mixed ester 1～24 has good oilness.
From table 1～5, the viscosity index of mixed ester 1～24 is more than 69, yield point is for below-30 ℃.Mixed ester 1～24 has sufficient viscosity-temperature profile, sufficient low-temperature fluidity.
In the evaluation of cold property, mixed ester 1～24 does not solidify and is also unconfirmed to precipitate.Mixed ester 1～24 also can preferably be used when preserving for a long time in low temperature range or using.
The mensuration of the solubleness of the benzotriazole at (test example 7) 5 ℃
In mixed ester 7～10,13,15 and each 4.85g of mixed ester A, mix benzotriazole 0.15g, at 60 ℃, heat, obtain respectively 3 % by weight mixed ester solution of benzotriazole.Respectively this mixed ester solution was placed after 40 hours at 5 ℃, by the visual confirmation of carrying out precipitate.
For this mixed ester solution of not observing precipitate, more than the solubleness of the benzotriazole at 5 ℃ [benzotriazole is with respect to the meltage (g) of 1g mixed ester] is designated as to 0.030g/g.For this mixed ester solution of observing precipitate, by filtering (filter paper; No.5A, paulownia mountain make made) remove after precipitate, resulting filtrate is used to high performance liquid chromatography (1200SERIES processed of AGILENT company, chromatographic column: YMC Pack Ph A-414
moving phase: tetrahydrofuran (THF)/0.1% phosphate aqueous solution=7/3, column temperature: 40 ℃, flow velocity: 0.7mL/ minute, detect: UV (220nm), sample concentration: 50g/L, sample size: 5 μ L) measure, obtain the solubleness [benzotriazole is with respect to the meltage (g) of 1g mixed ester] of the benzotriazole at 5 ℃ by absolute calibration curve method.Result as shown in Table 7 and 8.
The mensuration of the yield point of (test example 8) mixed ester solution
In mixed ester 7～10,13,15 and each 43.65g of mixed ester A, mix benzotriazole 1.35g, at 60 ℃, heat, obtain respectively 3 % by weight mixed ester solution of benzotriazole.Use automatic flowing point tester RPP-01CML (clutch company system), according to the method for JIS K2269-1987, measure respectively the yield point of this 3 % by weight mixed ester solution.Result as shown in Table 7 and 8.In table 7 and 8, BZT represents benzotriazole.
The mensuration of the wear scar diameter of (test example 9) mixed ester solution
In mixed ester 7～10,13 and 15 each 19.80g, mix benzotriazole 0.20g, at 60 ℃, heat, obtain respectively 1 % by weight mixed ester solution of benzotriazole.Use shell-type four ball frictional testing machiness (Shen Gangzao machine company system), under the condition of load 200N, rotating speed 1200rpm, 30 minutes time, 75 ℃ of temperature, test materials [test ball (SUJ-2)], respectively resulting this 1 % by weight mixed ester solution is tested the wear scar diameter after determination test.By wear scar diameter be made as 3 fixedly the vertical direction of ball, whole mean values of horizontal direction.Result is as follows.The wearability of the less expression mixed ester of the value solution of wear scar diameter is better.
[table 7]
[table 8]
From table 7 and 8, the solubleness of the benzotriazole at mixed ester 7～10,13 and 15 5 ℃ is more than 0.030g/g, and the ability of dissolving benzotriazole is good.In addition, the yield point of 3 % by weight mixed ester solution of mixed ester 7～10,13 and 15 benzotriazole is below-30.0 ℃, therefore when dissolving benzotriazole, has good low-temperature fluidity.
In test example 9, about the wear scar diameter of mixed ester solution, mixed ester 7 is that 0.51mm, mixed ester 8 are that 0.54mm, mixed ester 9 are that 0.55mm, mixed ester 10 are that 0.49mm, mixed ester 13 are that 0.55mm, mixed ester 15 are 0.58mm.Known, mixed ester of the present invention has sufficient wearability when dissolving benzotriazole.
Utilizability in industry
According to the present invention, can provide at the mixed ester for refrigerator wet goods of guaranteeing as refrigerator oil to have in necessary range of viscosities good consistency with methylene fluoride refrigeration agent etc.
Claims (4)
1. a mixed ester, it is the polyol blend consisting of the Dipentaerythritol shown in tetramethylolmethane and formula (I) and the mixed ester that contains isobutyric carboxylic acid,
The scope that tetramethylolmethane in described polyol blend and the mol ratio of Dipentaerythritol [tetramethylolmethane/Dipentaerythritol] are 98/2～40/60, isopropylformic acid shared ratio in described carboxylic acid is the scope of 35～85 % by mole.
2. mixed ester as claimed in claim 1, wherein, described carboxylic acid contains isopropylformic acid and 3,5,5 Trimethylhexanoic acid and/or 2 ethyl hexanoic acid.
3. mixed ester as claimed in claim 1, wherein, described carboxylic acid consists of isopropylformic acid and 3,5,5 Trimethylhexanoic acid.
4. mixed ester as claimed in claim 1, wherein, described carboxylic acid consists of isopropylformic acid and 2 ethyl hexanoic acid.
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| PCT/JP2013/051848 WO2013115160A1 (en) | 2012-02-01 | 2013-01-29 | Mixed ester of mixed polyhydric alcohol and carboxylic acid |
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| EP3109304B1 (en) * | 2014-02-20 | 2021-01-13 | AGC Inc. | Composition for heat cycle system, and heat cycle system |
| WO2015125881A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
| CN106062159B (en) | 2014-02-20 | 2019-04-16 | Ａｇｃ株式会社 | Heat circulating system composition and heat circulating system |
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| JPH03227397A (en) * | 1989-11-29 | 1991-10-08 | Asahi Denka Kogyo Kk | Lubricant for freezer |
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| JP4936656B2 (en) * | 2003-11-21 | 2012-05-23 | 日油株式会社 | Lubricating oil composition for refrigerator |
| WO2010029704A1 (en) * | 2008-09-09 | 2010-03-18 | 株式会社ジャパンエナジー | Refrigerator oil for refrigerant 2,3,3,3-tetrafluoro-1-propene |
| KR101800168B1 (en) * | 2010-08-24 | 2017-11-22 | 제이엑스티지 에네루기 가부시키가이샤 | Refrigerating machine oil and working fluid composition for refrigerating machines |
| JP5089826B2 (en) * | 2010-08-24 | 2012-12-05 | Ｋｈネオケム株式会社 | Pentaerythritol tetraester |
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| EP0430657A1 (en) * | 1989-11-29 | 1991-06-05 | Asahi Denka Kogyo Kabushiki Kaisha | Lubricant for refrigerators |
| CN1202880A (en) * | 1995-09-25 | 1998-12-23 | 花王株式会社 | Ester compounds and lubricating oil composition |
| JP2002356694A (en) * | 2001-05-29 | 2002-12-13 | Nof Corp | Lubricating oil composition for operating fluid composition refrigerator and |
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| CN114657010A (en) * | 2022-03-17 | 2022-06-24 | 苏州铱诺化学材料有限公司 | Lubricating oil for refrigerator and preparation method and application thereof |
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| JP6083873B2 (en) | 2017-02-22 |
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