CN103649040B - Four esters of tetramethylolmethane - Google Patents
Four esters of tetramethylolmethane Download PDFInfo
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- CN103649040B CN103649040B CN201280034710.5A CN201280034710A CN103649040B CN 103649040 B CN103649040 B CN 103649040B CN 201280034710 A CN201280034710 A CN 201280034710A CN 103649040 B CN103649040 B CN 103649040B
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- trimethylhexanoic
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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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- 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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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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
- 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
- C10N2020/071—Branched chain compounds
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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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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Abstract
The present invention provides four esters of a kind of tetramethylolmethane for refrigerator oil etc., it is the mixed ester of tetramethylolmethane and carboxylic acid, described carboxylic acid contains isopropylformic acid, 3,5, the straight-chain aliphatic monocarboxylic acid of 5-tri-methyl hexanoic acid and carbonatoms 4～7, four esters of described tetramethylolmethane balancedly have excellent low-temperature fluidity and excellent stability etc.
Description
Technical field
The present invention relates to four esters of the tetramethylolmethane for industrial lubricating oil etc. such as refrigerator oils.
Background technology
For the lubricating oil for industrial lubricating oil such as refrigerator oils, it is desired in order to the excellent low-temperature fluidity of use and the raising of various stability under the low temperature environment such as winter or cold district. As this stability, it is possible to enumerate: thermostability, oxidative stability, oxidation and stability to hydrolysis etc. In addition, in the equipment using this lubricating oil, it is desired to the various weather resistance such as wearability, anti-fatigability improves, the raising etc. of energy-efficient performance.
Patent documentation 1 describe containing making tetramethylolmethane and 3,5, the liquid composition of the ester that 5-tri-methyl hexanoic acid and isopropylformic acid and hexanodioic acid obtain using the molar ratio reaction of 1:1:2.5:0.25 is useful as the cooling liqs of refrigerator and air-conditioning, but the low-temperature fluidity of this ester and stability etc. cannot be satisfactory.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-25690 publication
Summary of the invention
Invent problem to be solved
It is an object of the present invention to provide four esters of the tetramethylolmethane for refrigerator oil etc. balancedly with excellent low-temperature fluidity and excellent stability etc.
For the method dealt with problems
The present invention provides following [1]～[5].
[1] four esters of tetramethylolmethane, it is the mixed ester of tetramethylolmethane and carboxylic acid, and above-mentioned carboxylic acid contains the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
[2] four esters of tetramethylolmethane as described in [1], wherein, above-mentioned carboxylic acid is made up of the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
[3] four esters of tetramethylolmethane as described in [1] or [2], wherein, the straight-chain aliphatic monocarboxylic acid of above-mentioned carbonatoms 4～7 is butyric acid.
[4] four esters of tetramethylolmethane as described in [1] or [2], wherein, the straight-chain aliphatic monocarboxylic acid of above-mentioned carbonatoms 4～7 is valeric acid.
[5] four esters of tetramethylolmethane as according to any one of [1]～[4], wherein, the kinematic viscosity of 100 DEG C is at 4.6～8.2mm2In the scope of/second.
Invention effect
According to the present invention, it may be possible to provide balancedly have four esters of the tetramethylolmethane for refrigerator oil etc. of excellent low-temperature fluidity and excellent stability etc.
Embodiment
Four esters of the tetramethylolmethane of the present invention are the mixed ester of tetramethylolmethane with the carboxylic acid of the straight-chain aliphatic monocarboxylic acid containing isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7. At this, four esters of tetramethylolmethane refer to the compound that tetramethylolmethane uses the carboxylic acid of multiple formation ester carry out esterification and obtain.
In addition, the each form of following (i)～(vi) is comprised (wherein in so-called " mixed ester " in the present invention, the carboxylic acid forming mixed ester contains the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7):
(i) formation carboxylic acid in same molecule contain the tetramethylolmethane of the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7 four esters,
(ii) the formation carboxylic acid in same molecule contain the tetramethylolmethane of two kinds in the group of the straight-chain aliphatic monocarboxylic acid being selected from isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7 four esters,
(iii) tetramethylolmethane with containing isobutyric carboxylic acid four esters,
(iv) tetramethylolmethane with containing 3,5,5 Trimethylhexanoic acid carboxylic acid four esters,
(v) tetramethylolmethane with containing carbonatoms 4～7 straight-chain aliphatic monocarboxylic acid carboxylic acid four esters,
(vi) mixture of the four two or more esters being selected from the group of above-mentioned (i)～(v).
Four esters of the tetramethylolmethane of the present invention can contain three esters etc. of the tetramethylolmethane as impurity.
The carboxylic acid forming mixed ester can also contain other carboxylic acids beyond the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7. As other carboxylic acids, it is possible to enumerate such as: acetic acid, propionic acid, sad, the straight-chain aliphatic monocarboxylic acid such as 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-ethylpentanoic, 2-ethyl-2-Methyl Butyric Acid, 2, the branched aliphatic monocarboxylic acids etc. such as 2-dimethyl valeric acid, 2-methyl enanthic acid, 2 ethyl hexanoic acid, 3-ethyl caproic acid, 2-ethyl-2 methyl valeric acid, 2-methyloctanoic acid, 2,2-dimethyl enanthic acid, different tridecanoic acid, Unimac 5680.
Isopropylformic acid, 3 is contained about above-mentioned, 5, the content of other carboxylic acids in the carboxylic acid of the straight-chain aliphatic monocarboxylic acid of 5-tri-methyl hexanoic acid and carbonatoms 4～7, as long as in the low-temperature fluidity of four esters of the tetramethylolmethane not damaging the present invention, stability or the scope to good characteristics such as the consistencies of methylene fluoride refrigeration agent etc. Other carboxylic acids are relative to isopropylformic acid and 3,5, mol ratio [other carboxylic acids/(isopropylformic acid, 3 of the straight-chain aliphatic monocarboxylic acid sum of 5-tri-methyl hexanoic acid and carbonatoms 4～7, the straight-chain aliphatic monocarboxylic acid of 5,5-tri-methyl hexanoic acid and carbonatoms 4～7) than] preferably in the scope of 0/100～5/100.
In the present invention, the carboxylic acid forming mixed ester is more preferably made up of the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
As the straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7 of four esters of the tetramethylolmethane forming the present invention, specifically, it is possible to enumerate butyric acid, valeric acid, caproic acid, enanthic acid, wherein, it is preferable to butyric acid or valeric acid. The straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7 is butyric acid or during valeric acid, four esters of the tetramethylolmethane of the present invention especially balancedly have excellent characteristics such as the consistency under the extensive concentration of methylene fluoride refrigeration agent, viscosity-temperature profile, low-temperature fluidity, cold property, stability.
The straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7 at four esters of the tetramethylolmethane forming the present invention is butyric acid or during valeric acid, butyric acid or valeric acid are relative to isopropylformic acid and 3,5, mol ratio [(butyric acid or the valeric acid)/(isopropylformic acid and 3 of 5-tri-methyl hexanoic acid sum, 5,5-tri-methyl hexanoic acid) than] be preferably 10/100～300/100 scope.
When the straight-chain aliphatic monocarboxylic acid of the carbonatoms 4～7 of four esters of the tetramethylolmethane forming the present invention is enanthic acid, enanthic acid is relative to isopropylformic acid and 3,5, mol ratio [enanthic acid/(the isopropylformic acid and 3 of 5-tri-methyl hexanoic acid sum, 5,5-tri-methyl hexanoic acid) than] be preferably 20/100～100/100 scope.
In cold property and stability, the isopropylformic acid forming four esters of the tetramethylolmethane of the present invention is preferably the scope of 5～55 moles of % relative to the ratio (mole %) of whole carboxylic acid sum, the scope being more preferably 9～40 moles of %, the more preferably scope of 15～40 moles of %.
Four esters of the tetramethylolmethane of the present invention such as can by make tetramethylolmethane and isopropylformic acid, 3,5,5 Trimethylhexanoic acid, carbonatoms 4～7 straight-chain aliphatic monocarboxylic acid and reacting at 120～250 DEG C according to other carboxylic acids expected within 5～60 hours, manufacture.
Above-mentioned reaction can use catalyzer, as catalyzer, it is possible to enumerate such as: mineral acid, organic acid, Lewis acid, organo-metallic, solid acid etc. As the concrete example of mineral acid, it is possible to enumerate such as: hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid etc. As organic acid concrete example, it is possible to enumerate such as: tosic acid, Phenylsulfonic acid, fourth sulfonic acid, propanesulfonic acid, ethyl sulfonic acid, methylsulfonic acid etc. As lewis acidic concrete example, it is possible to enumerate such as: boron trifluoride, aluminum chloride, tin tetrachloride, titanium tetrachloride etc. As the concrete example of organo-metallic, it is possible to enumerate such as: four titanium propanolates, four titanium butoxide, four (2-Ethylhexyl Alcohol) titanium etc. As the concrete example of solid acid, it is possible to enumerate such as Zeo-karb etc.
The usage quantity of the usage quantity of isobutyric usage quantity and 3,5,5 Trimethylhexanoic acid and the straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7 and the usage quantity sum of other carboxylic acids are relative to the hydroxyl of the tetramethylolmethane used, it is preferable to 1.1～1.4 times moles.
Above-mentioned reaction can use solvent, as solvent, it is possible to enumerate such as: the hydrocarbon series solvents etc. such as benzene, toluene, dimethylbenzene, hexane, heptane, isohexane, octane-iso, isononane, decane.
Preferably simultaneously reacting at the water generated except dereaction from reaction mixture. When removing the water that dereaction generates from reaction mixture, sometimes also can remove the straight-chain aliphatic monocarboxylic acid of isopropylformic acid and/or carbonatoms 4～7 from reaction mixture simultaneously.
In addition, from isopropylformic acid and 3,5, the straight-chain aliphatic monocarboxylic acid of 5-tri-methyl hexanoic acid and carbonatoms 4～7 sets out for reactive difference of tetramethylolmethane, form the isopropylformic acid and 3 of four esters obtained, 5,5-tri-methyl hexanoic acid is sometimes different with the mol ratio in the amount of the manufacture for four esters from the mol ratio of the straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7.
After the reaction, it is possible to by normally used method in Synthetic Organic Chemistry (using water and/or the cleaning of alkali aqueous solution, the process utilizing activated carbon, sorbent material etc., various chromatography, distillation method etc.), four esters of the tetramethylolmethane of the present invention are carried out purifying as required.
Four esters of the tetramethylolmethane of the present invention have excellent low-temperature fluidity, excellent stability, excellent cold property, excellent viscosity-temperature profile, the excellent consistency to methylene fluoride solvent, excellent oilness etc.
Viscosity-temperature profile refers to the change of the kinematic viscosity relative to temperature variation of the finishes such as lubricating oil. Viscosity-temperature profile well refers to little relative to temperature variation viscosity B coefficent, and on the other hand, the bad sharply increasing referred in low temperature range of viscosity-temperature profile is sticky, in high temperature range, kinematic viscosity reduces with exceeding imagination.Usually, this characteristic represents with viscosity index, it suffices to say that when numerical value is high, viscosity-temperature profile is good. In addition, the viscosity characteristics in low temperature range, also referred to as low-temperature fluidity, represents by yield point, zero pour, passage temperature etc.
Yield point refers to that the method cooling and lubricating oil based on Japanese Industrial Standards (JIS) K2269 waits the minimum temperature of finish flowing after finish. Even if the low finish of the yield point operating condition current downflow that under the environment of the low temperature such as winter or cold district or when using as refrigerator oil, the vaporizer etc. in refrigerator reaches low temperature also can not be deteriorated, therefore, use the equipment of finish work can not be occurred bad etc. in preferred.
In addition, by finishes such as lubricating oil when the place that temperature head is big preserves for a long time or uses, it is preferable that not there is volatility etc. in high temperature range, can not solidify in low temperature range or the finish of precipitation etc. As temperature range, it does not have be particularly limited to, it is preferable that about 150 DEG C, high temperature side, finish that use can be stablized at about-20 DEG C, low temperature side. Solidify not occurring in low temperature range or the feature definitions of precipitate is cold property. In the present invention, as carboxylic acid, with the use of the straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7, it is possible to suppress to produce precipitate when low temperature.
About stability, lubricating oil purposes such as, can enumerate thermostability, oxidative stability, oxidation and stability to hydrolysis, shear stability etc.
About oilness, it is possible to enumerate friction reduction property, reduce wear, extreme pressure property etc.
In addition, four esters of the tetramethylolmethane of the present invention are not only excellent to the consistency of conventional methylene fluoride mixed solvent (R-410A, R-407C), and the consistency of the independent solvent of methylene fluoride refrigeration agent is excellent. As refrigeration agent used for refrigerator, methylene fluoride refrigeration agent (HFC-32) is attracted attention in recent years. The ozone depleting potential of methylene fluoride refrigeration agent is zero, global warming potential (GWP) is low, for the refrigeration agent [R-410A (mixture of methylene fluoride and pentafluoride ethane), R-407C (methylene fluoride and the pentafluoride ethane and 1 that use at present, 1,1, the mixture of 2-Tetrafluoroethane) etc.] about 1/3～1/4, and coefficient of refrigerating performance (COP) also improves about 5～13% relative to R-410A, R-407C etc., therefore, also it is preferred refrigeration agent (" lubrication economy " from the viewpoint of energy-saving, in June, 2004 number (No.460), p.17). But, conventional lubricant base is insufficient to the consistency of methylene fluoride refrigeration agent, it is necessary to the lubricant base (Japanese Unexamined Patent Publication 2002-129177 publication) that consistency is excellent.
Usually double layer separation temperature is used to represent the consistency of methylene fluoride refrigeration agent. It may be said that double layer separation temperature is more low, the consistency in low temperature side is more good. In addition, the character of the consistency of refrigeration agent and this ester is had dependency by ester. In the present invention, use isopropylformic acid as carboxylic acid, therefore that the consistency of methylene fluoride solvent is good.
When four esters of the tetramethylolmethane of the present invention are used for refrigerator oil, the kinematic viscosity at 100 DEG C of this four ester is preferably 4.6～8.2mm2The scope of/second, it is more preferable to be 5.0～7.0mm2The scope of/second.
In addition, the viscosity index of this ester is preferably more than 89.
When four esters of the tetramethylolmethane of the present invention are used for refrigerator oil, when the remaining quantity of the hydroxyl of this four ester is many, there is gonorrhoea at low temperatures in refrigerator oil, the unsatisfactory phenomenon such as cause the capillary device making freeze cycle inaccessible, therefore, the hydroxyl value of this mixed ester is preferably below 10mgKOH/g, it is more preferable to be below 5mgKOH/g.
Four esters of the tetramethylolmethane of the present invention are except for refrigerator oil, it is also possible to for engine oil, gear oil, the machine oil utilized in hybrid electric vehicle or power truck, lubricating grease, the clean-out system of metal parts, softening agent etc.
As the refrigerator oil of four esters of the tetramethylolmethane employing the present invention, it is possible to enumerate such as: four esters containing tetramethylolmethane and the refrigerator oil etc. of additive for lubricant. In the refrigerator oil of four esters of the tetramethylolmethane employing the present invention, this four ester uses as lubricant base.
As additive for lubricant, it is possible to enumerate such as: the additive etc. that antioxidant, reduce wear agent (wear-resistant dose, anti-kill agent, extreme pressure agent etc.), friction modifier, acid-acceptor, metal passivator, defoamer etc. use usually used as lubricating oil additive. The content of these additives is preferably 0.001～5 weight % respectively in refrigerator oil.
Can also by four esters of the tetramethylolmethane of the present invention and other lubricant bases and use. As other lubricant bases, it is possible to enumerate such as mineral oil, synthetic base oil etc.
As mineral oil, it is possible to enumerate such as: paraffinic base system crude oil, intermediate base system crude oil, cycloalkyl system crude oil etc. In addition, it is possible to use these are carried out treated oil that is refining and that obtain by distillation etc.
As synthetic base oil, it is possible to enumerate such as: aliphatic ester beyond four esters of poly-alpha-olefin (alpha-olefin low polymers etc. of polybutene, polypropylene, carbonatoms 8～14), the present invention (fatty acid ester of fatty acid monoester, polyvalent alcohol, aliphatic polybasic acid esters etc.), aromatic ester (aromatic ester of aromatic series monoesters, polyvalent alcohol, aromatic series polybasic ester etc.), polyalkylene glycol, polyvingl ether, polyphenyl ether, alkylbenzene, carbonic ether, synthesis naphthenic hydrocarbon etc.
In addition, to dissolve the ability of the additive for lubricant such as metal passivator, silicon-type defoamer such as benzotriazoles excellent for four esters of the tetramethylolmethane of the present invention. This additive for lubricant is such as in order to extend lubricating oil, use the life-span of the equipment etc. of lubricating oil and be dissolved in lubricating oil and use. This additive for lubricant is the solvability in pentaerythritol ester low (Japanese Unexamined Patent Publication 10-259394 publication) usually. In addition, the solubleness low (Japanese Laid-Open Patent Publication 59-189195 publication) of benzotriazole in mineral oil and/or synthetic oil. But, such as solubleness (25 DEG C) as the benzotriazole in four esters 4 (embodiment 4 described later) of four esters of tetramethylolmethane of the present invention and four esters 10 (embodiment 10 described later) is 0.031g/g and 0.024g/g, in four esters of any one tetramethylolmethane, all demonstrate the high-dissolvability of benzotriazole. Four esters of the tetramethylolmethane of the present invention have excellent low-temperature fluidity, excellent wearability when being dissolved with benzotriazole.
Embodiment
Hereinafter, by embodiment, comparative example and test example, the present invention is more specifically described, but the present invention is not by the restriction of following examples.
NMR (Nuclear Magnetic Resonance) spectrum is measured by following metering equipment, measuring method.
Metering equipment; NEC Inc. GSX-400 (400MHz)
Measuring method;1H-NMR, standard substance (tetramethylsilane), solvent (CDCl3)
For four esters of each tetramethylolmethane manufactured in following embodiment 1～12, measure NMR (Nuclear Magnetic Resonance) spectrum, the mol ratio of the straight-chain aliphatic monocarboxylic acid of the isopropylformic acid in four esters of tetramethylolmethane and 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7 is calculated by following formula.
The integrated value of the integrated value/peak Y of the straight-chain aliphatic monocarboxylic acid=peak X of isopropylformic acid/3,5,5 Trimethylhexanoic acid/carbonatoms 4～7/(integrated value/2 of peak Z)
Wherein, peak X is equivalent to the peak of the hydrogen atom on the methyne in isopropylformic acid, and peak Y is equivalent to 3,5, the hydrogen atom on methyne in 5-tri-methyl hexanoic acid, peak Z is equivalent to the peak of the hydrogen atom on the methylene radical of the α position of the carbonyl in the straight-chain aliphatic monocarboxylic acid of carbonatoms 4～7.
For the ester of the tetramethylolmethane manufactured in following comparative example 1, measure NMR (Nuclear Magnetic Resonance) spectrum, calculated the isopropylformic acid in the ester of tetramethylolmethane and the mol ratio of 3,5,5 Trimethylhexanoic acid and hexanodioic acid by following formula.
The integrated value of the integrated value/peak Y of isopropylformic acid/3,5,5 Trimethylhexanoic acid/hexanodioic acid=peak X/(integrated value/4 of peak W)
Wherein, peak X and peak Y implication same as described above, peak W is equivalent to the peak of the hydrogen atom on the methylene radical of the α position of the carbonyl in hexanodioic acid.
[embodiment 1]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid is the manufacture of four esters (four esters 1) of the tetramethylolmethane of 71/29/33]
As sorbent material, it may also be useful to consonance chemical industry Inc. キ ョ ワ De 500.
As activated carbon, it may also be useful to Japan EnviroChemicals Inc. egression P.
The reactor of band Dean-Stark separator drops into tetramethylolmethane 327g (2.4 moles, extensively honor パ ス ト プ Inc.), isopropylformic acid 650g (7.4 moles, Tokyo chemical conversion Inc.), 3,5,5-tri-methyl hexanoic acid 365g (2.3 moles, consonance fermentation chemistry Inc.) and butyric acid 162g (1.8 moles and Guang Chun medicine Inc.), at room temperature carry out 30 minutes nitrogen bubbles while being uniformly mixed thing, thus make mixture degassed.
Then, while carrying out nitrogen bubble, mixture is stirred 30 hours at 138～230 DEG C. After reaction, reaction product being stirred 1 hour under the decompression of 0.7kPa, at 218 DEG C, thus, distillation removes the unreacted carboxylic acid in reaction product. By reaction product with comprise relative to the acid number of this reaction product be 2 times moles the alkali aqueous solution 400mL of sodium hydroxide clean 1 hour at 85 DEG C. Then, reaction product water 400mL is cleaned at 88 DEG C 1 hour, carry out 3 times. Then, while carrying out nitrogen bubble, reaction product is stirred 1 hour under the decompression of 1.1kPa, at 106 DEG C, thus dry reaction product.
Add sorbent material 5.0g (being equivalent to the weight 0.5% of reaction product) and activated carbon 9.9g (being equivalent to the weight 1.0% of reaction product) in the reaction product, while carrying out nitrogen bubble by reaction product under the decompression of 1.1kPa, stir 2 hours at 104 DEG C after, use filtration adjuvant to filter, thus obtain 822g tetra-ester 1.
[embodiment 2]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid is the manufacture of four esters (four esters 2) of the tetramethylolmethane of 62/38/57]
Except making mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of tetramethylolmethane, isopropylformic acid, 3,5,5 Trimethylhexanoic acid and butyric acid, 5,5-tri-methyl hexanoic acid/butyric acid ratio) for, beyond 1/1.80/1.20/1.80, operating similarly to Example 1, obtain four esters 2.
[embodiment 3]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid is the manufacture of four esters (four esters 3) of the tetramethylolmethane of 34/66/95]
Except making mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of tetramethylolmethane, isopropylformic acid, 3,5,5 Trimethylhexanoic acid and butyric acid, 5,5-tri-methyl hexanoic acid/butyric acid ratio) for, beyond 1/0.72/1.68/2.40, operating similarly to Example 1, obtain four esters 3.
[embodiment 4]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid is the manufacture of four esters (four esters 4) of the tetramethylolmethane of 34/66/41]
Except mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of tetramethylolmethane, isopropylformic acid, 3,5,5 Trimethylhexanoic acid and butyric acid, 5,5-tri-methyl hexanoic acid/butyric acid ratio) for, beyond 1/1.20/2.00/1.60, operating similarly to Example 1, obtain four esters 4.
[embodiment 5]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid is the manufacture of four esters (four esters 5) of the tetramethylolmethane of 24/76/42]
Except making mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of tetramethylolmethane, isopropylformic acid, 3,5,5 Trimethylhexanoic acid and butyric acid, 5,5-tri-methyl hexanoic acid/butyric acid ratio) for, beyond 1/0.90/3.00/0.90, operating similarly to Example 1, obtain four esters 5.
[embodiment 6]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid is the manufacture of four esters (four esters 6) of the tetramethylolmethane of 30/70/259]
Valeric acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and valeric acid, 5,5-tri-methyl hexanoic acid/valeric acid ratio) it is 1/0.38/0.96/3.46, in addition, operate similarly to Example 1, obtain four esters 6.
[embodiment 7]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid is the manufacture of four esters (four esters 7) of the tetramethylolmethane of 69/31/74]
Valeric acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and valeric acid, 5,5-tri-methyl hexanoic acid/valeric acid ratio) it is 1/1.92/0.96/1.92, in addition, operate similarly to Example 1, obtain four esters 7.
[embodiment 8]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid is the manufacture of four esters (four esters 8) of the tetramethylolmethane of 32/68/104]
Valeric acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and valeric acid, 5,5-tri-methyl hexanoic acid/valeric acid ratio) it is 1/0.72/1.68/2.40, in addition, operate similarly to Example 1, obtain four esters 8.
[embodiment 9]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid is the manufacture of four esters (four esters 9) of the tetramethylolmethane of 35/65/42]
Valeric acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and valeric acid, 5,5-tri-methyl hexanoic acid/valeric acid ratio) it is 1/1.20/2.00/1.60, in addition, operate similarly to Example 1, obtain four esters 9.
[embodiment 10]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid is the manufacture of four esters (four esters 10) of the tetramethylolmethane of 40/60/11]
Valeric acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and valeric acid, 5,5-tri-methyl hexanoic acid/valeric acid ratio) it is 1/1.73/2.59/0.48, in addition, operate similarly to Example 1, obtain four esters 10.
[embodiment 11]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid is the manufacture of four esters (four esters 11) of the tetramethylolmethane of 26/74/22]
Valeric acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and valeric acid, 5,5-tri-methyl hexanoic acid/valeric acid ratio) it is 1/0.90/3.00/0.90, in addition, operate similarly to Example 1, obtain four esters 11.
[embodiment 12]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/enanthic acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and enanthic acid is the manufacture of four esters (four esters 12) of the tetramethylolmethane of 65/35/72]
Enanthic acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and enanthic acid, 5,5-tri-methyl hexanoic acid/enanthic acid ratio) it is 1/1.92/0.96/1.92, in addition, operate similarly to Example 1, obtain four esters 12.
[comparative example 1]
[mol ratio (isopropylformic acid/3,5,5 Trimethylhexanoic acid/hexanodioic acid ratio) of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and hexanodioic acid is the manufacture of the ester (ester A) of the tetramethylolmethane of 69/31/7]
Hexanodioic acid is used to replace butyric acid, make tetramethylolmethane, isopropylformic acid, 3,5, mol ratio (tetramethylolmethane/isopropylformic acid/3 of the usage quantity of 5-tri-methyl hexanoic acid and hexanodioic acid, 5,5-tri-methyl hexanoic acid/hexanodioic acid ratio) it is 1/2.50/1.00/0.25, in addition, operate similarly to Example 1, obtain ester A.
The mensuration of (test example 1) yield point
Use automatic flowing point tester RPC-01CML (clutch Inc.), measure the yield point of four esters 1～12 and ester A based on the method for JISK2269-1987. Show the result in table 1～3.
The mensuration of (test example 2) kinematic viscosity
Use Cannon-Fenske viscometer, measure the kinematic viscosity at 40 DEG C and 100 DEG C of four esters 1～12 and ester A based on the method for JISK2283:2000. In addition, viscosity index is calculated based on same procedure. Show the result in table 1～3.
The mensuration of (test example 3) double layer separation temperature
The double layer separation temperature of four esters 1～4 and 6～8 is measured based on the method for JISK2211:2009. The four each 0.4g of ester 1～4 and 6～8 and methylene fluoride refrigeration agent 3.6g are loaded withstand voltage Glass tubing, by mixture from 30 DEG C with the cooling of every minute speed of 0.5 DEG C, using the temperature of mixture generation double layer separation or gonorrhoea as double layer separation temperature. Result is below shown.
(evaluation of cold property) is confirmed with presence or absence of solidification at (test example 4)-20 DEG C, precipitate
Four esters 2～12 are respectively charged in 1.0g Glass Containers, are being set in the thermostatted of-20 DEG C to leave standstill 96 hours. Visual confirm the solidification after leaving standstill, precipitate with or without. Result is below shown.
The mensuration (being oxidized and the evaluation of stability to hydrolysis, oxidative stability) in (test example 5) RBOT life-span
" condition 1 "
Using rotary bomb oxidation stability tester RBOT-02 (clutch Inc.), the method based on JISK2514-1996 carries out oxidation stability test. By four esters 1～12 and each 49.50g of ester A, 4,4'-methylene-bis (2,6-bis--tert.-butyl phenol) (Tokyo chemical conversion industrial system) 0.25g, IRGANOXL57 (Ciba Specialty Chemicals's system) 0.25g, water 5mL, drop in pressure vessel with the electrolysis copper cash (diameter 1.6mm, long 3m) after sand paper #400 rubs. Then, this pressure vessel is pressed into oxygen to 620kPa, this pressure vessel is loaded in the thermostatic bath of 150 DEG C, rotated with every minute 100 and turn.Until being reduced to the time required for the pressure of 175kPa (RBOT life-span) when mensuration reaches the highest from the pressure of this pressure vessel. Show the result in table 1～3.
In table 1～3, the RBOT life-span is more long, represents that the oxidation of four esters and stability to hydrolysis are more excellent.
" condition 2 "
4 are not loaded in pressure vessel, 4'-methylene-bis (2,6-bis--tert.-butyl phenol), IRGANOXL57 and water, in addition, carry out the operation same with condition 1, for four esters 3 and 8, until being reduced to the time required for the pressure of 175kPa (RBOT life-span) when mensuration reaches the highest from the pressure of this pressure vessel. At this, the RBOT life-span is more long, represents that the oxidative stability of four esters is more excellent.
(test example 6) weight reduces the mensuration (evaluation of thermostability) of temperature
Using thermogravimetric/differential calorimeter Tg-DTA6200 (SeikoInstruments Inc.), 5% weight measuring four esters 5,6 and 9～12 under the following conditions reduces temperature. Show the result in table 4.
Measure temperature; 40～420 DEG C, heat-up rate; 10 DEG C/min, atmosphere; Nitrogen ventilation (300mL/ minute), sample receiver; Aluminium system 15 μ l (opening), sample size; 3mg
Table 1
Table 2
Table 3
Table 4
By table 1～3 it will be seen that the kinematic viscosity at 100 DEG C of four esters 1～12 is 4.6～8.2mm2/ second, viscosity index is more than 89, there is excellent low-temperature fluidity, yield point is less than-42.5 DEG C, has excellent oxidation and stability to hydrolysis, and the RBOT life-span under condition 1 is more than 756 minutes.
As shown in Table 4, four esters 5,6 and 9～12,5% weight minimizing temperature in the mensuration of Tg-DTA is more than 221.8 DEG C. Four esters of the present invention have excellent thermostability.
In test example 3, the double layer separation temperature of four esters 1～4 and 6～8 is less than-32 DEG C, and wherein, four esters 1～3 and 7 are less than 50 DEG C. Four esters of the present invention have the excellent consistency to methylene fluoride refrigeration agent.
In test example 4, four esters 2～12 are solidification not, and does not observe precipitate. Four esters 2～12 are long-term in low temperature range to be preserved or under service condition, it is also possible to preferably use.
Under " condition 2 " of test example 5, the RBOT life-span of four esters 3 is 217 minutes, and the RBOT life-span of four esters 8 is 247 minutes. Four esters of known the present invention have high oxidation stability.
Utilizability in industry
According to the present invention, it may be possible to provide balancedly have four esters of the tetramethylolmethane for refrigerator oil etc. of excellent low-temperature fluidity and excellent stability etc.
Claims (4)
1. four esters of tetramethylolmethane, it is the mixed ester of tetramethylolmethane and carboxylic acid, and described carboxylic acid is made up of the straight-chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
2. four esters of tetramethylolmethane as claimed in claim 1, wherein, the straight-chain aliphatic monocarboxylic acid of described carbonatoms 4～7 is butyric acid.
3. four esters of tetramethylolmethane as claimed in claim 1, wherein, the straight-chain aliphatic monocarboxylic acid of described carbonatoms 4～7 is valeric acid.
4. four esters of tetramethylolmethane as according to any one of claims 1 to 3, its kinematic viscosity of 100 DEG C is at 4.6～8.2mm2In the scope of/second.
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| JP5990168B2 (en) | 2016-09-07 |
| TW201303005A (en) | 2013-01-16 |
| CN103649040A (en) | 2014-03-19 |
| JP2016193938A (en) | 2016-11-17 |
| TWI583783B (en) | 2017-05-21 |
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