CN103649040A - Tetraester of pentaerythritol - Google Patents
Tetraester of pentaerythritol Download PDFInfo
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- CN103649040A CN103649040A CN201280034710.5A CN201280034710A CN103649040A CN 103649040 A CN103649040 A CN 103649040A CN 201280034710 A CN201280034710 A CN 201280034710A CN 103649040 A CN103649040 A CN 103649040A
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- acid
- esters
- tetramethylolmethane
- isopropylformic
- 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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- 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
- C10M2207/02—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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- 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
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a tetraester of pentaerythritol, the tetraester being a mixed ester of pentaerythritol and carboxylic acid, and being used in refrigerant oils and the like having excellent low-temperature fluidity, excellent stability, and the like in a balanced manner. The carboxylic acid contains isobutyric acid, 3,5,5-trimethylhexanoic acid, and C4-7 linear aliphatic monocarboxylic acid.
Description
Technical field
The present invention relates to four esters for the tetramethylolmethane of refrigerator wet goods Industrial Oil etc.
Background technology
For the lubricating oil for refrigerator wet goods Industrial Oil, require in the winter time or the good low-temperature fluidity using under the low temperature environment such as cold district and the raising of various stability.As this stability, can enumerate: thermostability, oxidative stability, oxidation and stability to hydrolysis etc.In addition, in using the equipment of this lubricating oil, require the raising of the various weather resistance raisings such as wearability, anti-fatigability, energy-efficient performance etc.
In patent documentation 1, recorded to contain and made tetramethylolmethane and 3,5,5-tri-methyl hexanoic acid and isopropylformic acid and hexanodioic acid using 1:1:2.5:0.25 molar ratio reaction and the liquid composition of the ester that obtains 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 document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 6-25690 communique
Summary of the invention
Invent problem to be solved
The object of the invention is to, four esters of the tetramethylolmethane for refrigerator wet goods balancedly with good low-temperature fluidity and good stability etc. are provided.
For the method for dealing with problems
The invention provides following [1]～[5].
[1] four esters of tetramethylolmethane, it is the mixed ester of tetramethylolmethane and carboxylic acid, the straight chain aliphatic monocarboxylic acid that above-mentioned carboxylic acid contains isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
[2] four esters of the tetramethylolmethane as described in [1], wherein, above-mentioned carboxylic acid consists of the straight chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
[3] four esters of the 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 the 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 the tetramethylolmethane as described in any one in [1]～[4], wherein, the kinematic viscosity of 100 ℃ is at 4.6～8.2mm
2in the scope of/second.
Invention effect
According to the present invention, can provide four esters of the tetramethylolmethane for refrigerator wet goods balancedly with good low-temperature fluidity and good stability etc.
Embodiment
Four esters of tetramethylolmethane of the present invention are tetramethylolmethanes and the mixed ester of the carboxylic acid of the straight chain aliphatic monocarboxylic acid that contains isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.At this, four esters of tetramethylolmethane refer to and use the carboxylic acid of multiple formation ester to carry out esterification and the compound that obtains to tetramethylolmethane.
In addition, comprise in the present invention following (i)～(vi) each form (wherein, forming the straight chain aliphatic monocarboxylic acid that the carboxylic acid of mixed ester contains isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7) in so-called " mixed ester ":
Four esters of the tetramethylolmethane of the straight chain aliphatic monocarboxylic acid that (i) the formation carboxylic acid in same a part contains isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7,
Four esters of the tetramethylolmethane of two kinds in the group that (ii) the formation carboxylic acid in same a part contains the straight chain aliphatic monocarboxylic acid that is selected from isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7,
(iii) tetramethylolmethane and four esters that contain isobutyric carboxylic acid,
(iv) four esters of tetramethylolmethane and the carboxylic acid that contains 3,5,5 Trimethylhexanoic acid,
(v) four esters of tetramethylolmethane and the carboxylic acid of the straight chain aliphatic monocarboxylic acid that contains carbonatoms 4～7,
(vi) be selected from the mixture of the four two or more esters in the group of above-mentioned (i)～(v).
In four esters of tetramethylolmethane of the present invention, can contain three esters as the tetramethylolmethane of impurity etc.
In forming the carboxylic acid of 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, can enumerate such as straight chain aliphatic monocarboxylic acids such as: acetic acid, propionic acid, sad, n-nonanoic acid, capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acids; 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, 2-Ethyl-2-Methyl valeric acid, 2-methyloctanoic acid, 2, a chain aliphatic monocarboxylic acid such as 2-dimethyl enanthic acid, different tridecanoic acid, Unimac 5680 etc.
About the above-mentioned isopropylformic acid, 3 that contains, 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, if do not damage the low-temperature fluidity of four esters of tetramethylolmethane of the present invention, stability or to the scope of the good characteristics such as consistency of methylene fluoride refrigeration agent etc. in.Other carboxylic acids are with respect 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) ratio] preferably in 0/100～5/100 scope.
In the present invention, the carboxylic acid that forms mixed ester more preferably consists 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 that forms four esters of tetramethylolmethane of the present invention, particularly, can enumerate butyric acid, valeric acid, caproic acid, enanthic acid, wherein, be preferably butyric acid or valeric acid.When the straight chain aliphatic monocarboxylic acid of carbonatoms 4～7 is butyric acid or valeric acid, four esters of tetramethylolmethane of the present invention especially balancedly have good characteristics such as the consistency under the extensive concentration of methylene fluoride refrigeration agent, viscosity-temperature profile, low-temperature fluidity, cold property, stability.
When the straight chain aliphatic monocarboxylic acid of carbonatoms 4～7 that forms four esters of tetramethylolmethane of the present invention is butyric acid or valeric acid, butyric acid or valeric acid are with respect to isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid sum [(butyric acid or valeric acid)/(isopropylformic acid and 3,5,5-tri-methyl hexanoic acid) than] be preferably 10/100～300/100 scope.
When the straight chain aliphatic monocarboxylic acid of carbonatoms 4～7 that forms four esters of tetramethylolmethane of the present invention is enanthic acid, enanthic acid is with respect to isopropylformic acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid sum [enanthic acid/(isopropylformic acid and 3,5,5-tri-methyl hexanoic acid) than] be preferably 20/100～100/100 scope.
Aspect cold property and stability, form tetramethylolmethane of the present invention four esters isopropylformic acid with respect to the ratio of whole carboxylic acid sums (% by mole) be preferably the scope of 5～55 % by mole, the more preferably scope of 9～40 % by mole, the more preferably scope of 15～40 % by mole.
Four esters of tetramethylolmethane of the present invention for example can be by making tetramethylolmethane with the straight chain aliphatic monocarboxylic acid of isopropylformic acid, 3,5,5 Trimethylhexanoic acid, carbonatoms 4～7 and reacting at 120～250 ℃ and manufacture for 5～60 hours according to other carboxylic acids of expectation.
In above-mentioned 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-Ethylhexyl Alcohol) titanium etc.As the concrete example of solid acid, can enumerate such as Zeo-karb etc.
The usage quantity of the straight chain aliphatic monocarboxylic acid of the usage quantity of isobutyric usage quantity and 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7 and the usage quantity sum of other carboxylic acids, with respect to the hydroxyl of the tetramethylolmethane using, are preferably 1.1～1.4 times moles.
In above-mentioned reaction, can 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 in the water generating except dereaction from reaction mixture, react.When the water generating except dereaction, sometimes also can from reaction mixture, remove the straight chain aliphatic monocarboxylic acid of isopropylformic acid and/or carbonatoms 4～7 simultaneously from reaction mixture.
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 resulting four esters, the mol ratio of 5,5-tri-methyl hexanoic acid and the straight chain aliphatic monocarboxylic acid of carbonatoms 4～7 is sometimes different with the mol ratio of the amount of manufacture for four esters.
After reaction, can by normally used method in Synthetic Organic Chemistry (making the cleaning of water and/or alkali aqueous solution, the processing that utilizes activated carbon, sorbent material etc., various chromatography, distillation method etc.), to four esters of tetramethylolmethane of the present invention, carry out purifying as required.
Four esters of tetramethylolmethane of the present invention have good low-temperature fluidity, good stability, good cold property, good viscosity-temperature profile, good in the consistency of methylene fluoride solvent, good oilness etc.
Viscosity-temperature profile refers to the variation of the kinematic viscosity with respect to temperature variation of lubricated wet goods finish.Viscosity-temperature profile well refers to and with respect to temperature variation viscosity, changes littlely, and on the other hand, viscosity-temperature profile is bad refers to sharply tackify in low temperature range, in high temperature range, kinematic viscosity exceeds imagination and reduces.Conventionally, this characteristic represents with viscosity index, can say that in the situation that 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 with yield point, zero pour, channel temperature etc.
Yield point refers to the mobile minimum temperature of finish after the method cooling and lubricating wet goods finish based on the K2269 of Japanese Industrial Standards (JIS).Even if the low finish of the yield point operating condition current downflow that in the winter time or under the environment of the low temperature such as cold district or while using as refrigerator oil, vaporizer in refrigerator etc. reaches low temperature can variation yet, therefore, at the equipment that uses finish, can there is not the aspects such as work is bad preferred.
In addition, will lubricated wet goods finish in the situation that the large place of temperature head is long-term preserves or use, the finish that preferably do not there is volatility etc. in high temperature range, can not solidify or separate out etc. in low temperature range.As temperature range, be not particularly limited, preferably approximately 150 ℃ of high temperature sides, at approximately-20 ℃ of low temperature sides, can stablize the finish of use.The characteristic that does not occur curing or precipitate in low temperature range is defined as to cold property.In the present invention, as carboxylic acid, by using the straight chain aliphatic monocarboxylic acid of carbonatoms 4～7, in the time that low temperature can being suppressed at, produce precipitate.
About stability, such as enumerating thermostability, oxidative stability, oxidation and stability to hydrolysis, shear stability etc. in lubricating oil purposes.
About oilness, can enumerate friction lowering, wearing and tearing lowering, extreme pressure property etc.
In addition, four esters of tetramethylolmethane of the present invention are not only good to the consistency of methylene fluoride mixed solvent (R-410A, R-407C) in the past, and good to the consistency of methylene fluoride refrigeration agent separate solvent.As used for refrigerator refrigeration agent, methylene fluoride refrigeration agent (HFC-32) is attracted attention in recent years.The ozone depleting potential of methylene fluoride refrigeration agent is zero, (GWP) is low for global warming potential, for the refrigeration agent [R-410A (mixture of methylene fluoride and pentafluoride ethane) using at present, R-407C (methylene fluoride and pentafluoride ethane and 1, 1, 1, the mixture of 2-Tetrafluoroethane) etc.] approximately 1/3～1/4, and coefficient of refrigerating performance (COP) is with respect to R-410A, R-407C etc. also improve approximately 5～13%, therefore, from the viewpoint of energy-saving, be also preferred refrigeration agent (< < lubrication economy > >, in June, 2004 number (No.460), p.17).But lubricant base is in the past insufficient to the consistency of methylene fluoride refrigeration agent, need the lubricant base that consistency is good (TOHKEMY 2002-129177 communique).
To the consistency of methylene fluoride refrigeration agent, conventionally use double layer separation temperature to represent.Can say that double layer separation temperature is lower, better in the consistency of low temperature side.In addition, ester has dependency to the character of the consistency of refrigeration agent and this ester.In the present invention, as carboxylic acid, use isopropylformic acid, therefore good to the consistency of methylene fluoride solvent.
By four esters of tetramethylolmethane of the present invention, when the refrigerator oil, the kinematic viscosity at 100 ℃ of this four ester is preferably 4.6～8.2mm
2the scope of/second, more preferably 5.0～7.0mm
2the scope of/second.
In addition, the viscosity index of this ester is preferably more than 89.
When four esters of tetramethylolmethane of the present invention are used for to refrigerator oil, when the remaining quantity of the hydroxyl of this four ester is many, there is at low temperatures gonorrhoea in refrigerator oil, cause the not satisfied phenomenons such as capillary device obturation that make freeze cycle, therefore, the hydroxyl value of this mixed ester is preferably below 10mgKOH/g, more preferably below 5mgKOH/g.
Four esters of tetramethylolmethane of the present invention are except for refrigerator oil, can also be for the clean-out system of engine oil, gear oil, the machine oil utilizing in hybrid electric vehicle or power truck, lubricating grease, metal parts, softening agent etc.
As the refrigerator oil that has used four esters of tetramethylolmethane of the present invention, for example can enumerate: four esters that contain tetramethylolmethane and the refrigerator wet goods of additive for lubricant.In the refrigerator oil of four esters that has used tetramethylolmethane of the present invention, this four ester is used as lubricant base.
As additive for lubricant, can enumerate additive that such as: antioxidant, wearing and tearing depressant (wear-resistant dose, anti-agent, the extreme pressure agent etc. of killing), friction modifier, acid-acceptor, metal passivator, defoamer etc. used usually used as lubricating oil additive etc.The content of these additives is preferably respectively 0.001～5 % by weight in refrigerator oil.
Also can and use four esters of tetramethylolmethane 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, cycloalkanes base system crude oil etc.In addition, also can use these are waited and refined the treated oil obtaining by distillation.
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, polyvingl ether, polyphenylene ether, alkylbenzene, carbonic ether, synthetic naphthenic hydrocarbon etc.
In addition, the ability of the additive for lubricant such as metal passivator, silicon-type defoamer such as four esters dissolving benzotriazoles of tetramethylolmethane of the present invention is good.This additive for lubricant such as in order to extend lubricating oil, use life-span and being dissolved in lubricating oil of the equipment etc. of lubricating oil to use.This additive for lubricant is the solvability in pentaerythritol 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 four esters 4 (embodiment 4 described later) of four esters and the solubleness (25 ℃) of the benzotriazole in four esters 10 (embodiment 10 described later) as tetramethylolmethane of the present invention 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 tetramethylolmethane of the present invention have good low-temperature fluidity, good wearability when being dissolved with benzotriazole.
Embodiment
Below, by embodiment, comparative example and test example, the present invention is more specifically described, but the present invention is not subject to the restriction of following examples.
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)
Four esters for each tetramethylolmethane of manufacturing in the embodiment 1～12 following, measure NMR (Nuclear Magnetic Resonance) spectrum, by following formula, calculate the mol ratio of the straight chain aliphatic monocarboxylic acid of isopropylformic acid in four esters of tetramethylolmethane and 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
Integrated value/(integrated value/2 of peak Z) of integrated value/peak Y of straight chain aliphatic monocarboxylic acid=peak X of isopropylformic acid/3,5,5 Trimethylhexanoic acid/carbonatoms 4～7
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, 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 α position of the carbonyl in the straight chain aliphatic monocarboxylic acid of carbonatoms 4～7.
For the ester of the tetramethylolmethane of manufacturing in following comparative example 1, measure NMR (Nuclear Magnetic Resonance) spectrum, by following formula, calculate isopropylformic acid in the ester of tetramethylolmethane and the mol ratio of 3,5,5 Trimethylhexanoic acid and hexanodioic acid.
The integrated value of 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 α position of the carbonyl in hexanodioic acid.
[embodiment 1]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) is the manufacture of four esters (four esters 1) of 71/29/33 tetramethylolmethane]
As sorbent material, use the consonance キ ョ processed ー ワ ー of chemical industrial company De 500.
As activated carbon, use the Japanese EnviroChemicals egression P processed of company.
In the reactor with Dean-Stark separator, drop into tetramethylolmethane 327g (2.4 moles, wide flourish パ ー ス トー プ company system), isopropylformic acid 650g (7.4 moles, Tokyo change into company's system), 3,5,5-tri-methyl hexanoic acid 365g (2.3 moles, consonance fermentation chemistry company system) and butyric acid 162g (1.8 moles, He Guangchun medicine company system), when stirring the mixture, at room temperature carry out 30 minutes nitrogen bubbles, make thus mixture degassed.
When then, carrying out nitrogen bubble, mixture is stirred 30 hours at 138～230 ℃.After reaction, by reaction product, under the decompression of 0.7kPa, stir 1 hour at 218 ℃, thus, the unreacted carboxylic acid in reaction product is removed in distillation.The alkali aqueous solution 400mL of the sodium hydroxide that is 2 times moles with the acid number comprising with respect to this reaction product by reaction product cleans 1 hour at 85 ℃.Then, reaction product water 400mL is cleaned at 88 ℃ 1 hour, carry out 3 times.Then, when carrying out nitrogen bubble by reaction product under the decompression of 1.1kPa, stir 1 hour at 106 ℃, dry reaction product thus.
In reaction product, add sorbent material 5.0g (weight 0.5% that is equivalent to reaction product) and activated carbon 9.9g (weight 1.0% that is equivalent to reaction product), when carrying out nitrogen bubble by reaction product under the decompression of 1.1kPa, stir after 2 hours at 104 ℃, use filtration adjuvant to filter, obtain thus 822g tetra-esters 1.
[embodiment 2]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) is the manufacture of four esters (four esters 2) of 62/38/57 tetramethylolmethane]
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) be beyond 1/1.80/1.20/1.80, operation, obtains four esters 2 similarly to Example 1.
[embodiment 3]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) is the manufacture of four esters (four esters 3) of 34/66/95 tetramethylolmethane]
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) be beyond 1/0.72/1.68/2.40, operation, obtains four esters 3 similarly to Example 1.
[embodiment 4]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) is the manufacture of four esters (four esters 4) of 34/66/41 tetramethylolmethane]
Mol ratio (tetramethylolmethane/isopropylformic acid/3 except the usage quantity of tetramethylolmethane, isopropylformic acid, 3,5,5 Trimethylhexanoic acid and butyric acid, 5,5-tri-methyl hexanoic acid/butyric acid ratio) be beyond 1/1.20/2.00/1.60, operation, obtains four esters 4 similarly to Example 1.
[embodiment 5]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and butyric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/butyric acid ratio) is the manufacture of four esters (four esters 5) of 24/76/42 tetramethylolmethane]
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) be beyond 1/0.90/3.00/0.90, operation, obtains four esters 5 similarly to Example 1.
[embodiment 6]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) is the manufacture of four esters (four esters 6) of 30/70/259 tetramethylolmethane]
Use valeric acid 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) be 1/0.38/0.96/3.46, in addition, operation, obtains four esters 6 similarly to Example 1.
[embodiment 7]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) is the manufacture of four esters (four esters 7) of 69/31/74 tetramethylolmethane]
Use valeric acid 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) be 1/1.92/0.96/1.92, in addition, operation, obtains four esters 7 similarly to Example 1.
[embodiment 8]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) is the manufacture of four esters (four esters 8) of 32/68/104 tetramethylolmethane]
Use valeric acid 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) be 1/0.72/1.68/2.40, in addition, operation, obtains four esters 8 similarly to Example 1.
[embodiment 9]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) is the manufacture of four esters (four esters 9) of 35/65/42 tetramethylolmethane]
Use valeric acid 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) be 1/1.20/2.00/1.60, in addition, operation, obtains four esters 9 similarly to Example 1.
[embodiment 10]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) is the manufacture of four esters (four esters 10) of 40/60/11 tetramethylolmethane]
Use valeric acid 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) be 1/1.73/2.59/0.48, in addition, operation, obtains four esters 10 similarly to Example 1.
[embodiment 11]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and valeric acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/valeric acid ratio) is the manufacture of four esters (four esters 11) of 26/74/22 tetramethylolmethane]
Use valeric acid 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) be 1/0.90/3.00/0.90, in addition, operation, obtains four esters 11 similarly to Example 1.
[embodiment 12]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and enanthic acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/enanthic acid ratio) is the manufacture of four esters (four esters 12) of 65/35/72 tetramethylolmethane]
Use enanthic acid 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) be 1/1.92/0.96/1.92, in addition, operation, obtains four esters 12 similarly to Example 1.
[comparative example 1]
[mol ratio of isopropylformic acid and 3,5,5 Trimethylhexanoic acid and hexanodioic acid (isopropylformic acid/3,5,5 Trimethylhexanoic acid/hexanodioic acid ratio) is the manufacture of the ester (ester A) of 69/31/7 tetramethylolmethane]
Use hexanodioic acid 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) be 1/2.50/1.00/0.25, in addition, operation, obtains ester A similarly to Example 1.
The mensuration of (test example 1) yield point
Use automatic flowing point tester RPC-01CML (clutch company system), the method based on JISK2269-1987 is measured the yield point of four esters 1～12 and ester A.Show the result in table 1～3.
The mensuration of (test example 2) kinematic viscosity
Use Cannon-Fenske viscometer, the method based on JIS K2283:2000 is measured the kinematic viscosity at four esters 1～12 and ester A 40 ℃ and 100 ℃.In addition, based on same procedure, calculate viscosity index.Show the result in table 1～3.
The mensuration of (test example 3) double layer separation temperature
Method based on JIS K2211:2009 is measured the double layer separation temperature of four esters 1～4 and 6～8.Pack four esters 1～4 and 6～8 each 0.4g and methylene fluoride refrigeration agent 3.6g into withstand voltage Glass tubing, mixture is cooling from 30 ℃ of speed with 0.5 ℃ of per minute, using the temperature of mixture generation double layer separation or gonorrhoea as double layer separation temperature.Result is below shown.
Solidifying at (test example 4)-20 ℃, the confirmation (evaluation of cold property) that precipitate has or not
Four esters 2～12 are respectively charged in 1.0g Glass Containers in setting the thermostatted of-20 ℃ for standing 96 hours.Curing, precipitate after Visual Confirmation is standing have or not.Result is below shown.
The mensuration in (test example 5) RBOT life-span (evaluation of oxidation and stability to hydrolysis, oxidative stability)
" condition 1 "
Use rotary bomb oxidation stability tester RBOT-02 (clutch company system), the method based on JIS K2514-1996 is carried out oxidation stability test.By four esters 1～12 and each 49.50g of ester A, 4, electrolysis copper cash (diameter 1.6mm, long 3m) after 4'-methylene-bis (2,6-, bis--tert.-butyl phenol) (Tokyo changes into industrial's system) 0.25g, IRGANOX L57 (Ciba company system) 0.25g, water 5mL, use sand paper #400 friction drops in pressure vessel.Then, in this pressure vessel, be pressed into oxygen to 620kPa, this pressure vessel packed in the thermostatic bath of 150 ℃, with per minute 100, rotate.When mensuration reaches the highest from the pressure of this pressure vessel until be reduced to the needed time of the pressure of 175kPa (RBOT life-span).Show the result in table 1～3.
In table 1～3, the RBOT life-span is longer, represents that oxidation and the stability to hydrolysis of four esters is better.
" condition 2 "
In pressure vessel, do not pack 4 into, 4'-methylene-bis (2,6-bis--tert.-butyl phenol), IRGANOX L57 and water, in addition, carry out the operation same with condition 1, for four esters 3 and 8, measure while reaching the highest from the pressure of this pressure vessel until be reduced to the needed time of the pressure of 175kPa (RBOT life-span).At this, the RBOT life-span is longer, represents that the oxidative stability of four esters is better.
(test example 6) weight reduces the mensuration (evaluation of thermostability) of temperature
Use thermogravimetric/differential calorimeter Tg-DTA6200 (Seiko Instruments company system), 5% weight of measuring four esters 5,6 and 9～12 under following condition reduces temperature.Show the result in table 4.
Measure temperature; 40～420 ℃, heat-up rate; 10 ℃/min, atmosphere; Nitrogen ventilation (300mL/ minute), sample receiver; Aluminum 15 μ l (opening), sample size; 3mg
Table 1
Table 2
Table 3
Table 4
From table 1～3, the kinematic viscosity at 100 ℃ of four esters 1～12 is 4.6～8.2mm2/ second, and viscosity index is more than 89, there is good low-temperature fluidity, yield point is below-42.5 ℃, has good 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 ℃.Four esters of the present invention have good thermostability.
In test example 3, four esters 1～4 and 6～8 double layer separation temperature are below-32 ℃, and wherein, four esters 1～3 and 7 are below 50 ℃.Four esters of the present invention have the good consistency to methylene fluoride refrigeration agent.
In test example 4, four esters 2～12 do not solidify, and do not observe precipitate.Four esters 2～12 in low temperature range long-term preserve or service condition under, also can 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.Known four esters of the present invention have high oxidation stability.
Utilizability in industry
According to the present invention, can provide four esters of the tetramethylolmethane for refrigerator wet goods balancedly with good low-temperature fluidity and good stability etc.
Claims (5)
1. four esters of tetramethylolmethane, it is the mixed ester of tetramethylolmethane and carboxylic acid, the straight chain aliphatic monocarboxylic acid that described carboxylic acid contains isopropylformic acid, 3,5,5 Trimethylhexanoic acid and carbonatoms 4～7.
2. four esters of tetramethylolmethane as claimed in claim 1, wherein, described carboxylic acid consists 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 claimed in claim 1 or 2, wherein, the straight chain aliphatic monocarboxylic acid of described carbonatoms 4～7 is butyric acid.
4. four esters of tetramethylolmethane as claimed in claim 1 or 2, wherein, the straight chain aliphatic monocarboxylic acid of described carbonatoms 4～7 is valeric acid.
5. four esters of the tetramethylolmethane as described in any one in claim 1～4, wherein, the kinematic viscosity of 100 ℃ is at 4.6～8.2mm
2in the scope of/second.
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| CN115433619A (en) * | 2021-06-03 | 2022-12-06 | 瑞孚化工（上海）有限公司 | Refrigerating machine oil composition and application thereof |
| CN116004298B (en) * | 2021-10-21 | 2024-05-17 | 联泓(江苏)新材料研究院有限公司 | Carboxylic acid ester composition, preparation method and application thereof |
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| CN113728079B (en) * | 2019-04-25 | 2022-08-05 | 日油株式会社 | Ester for refrigerator oil and working fluid composition containing the same |
Also Published As
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| JP2016193938A (en) | 2016-11-17 |
| CN103649040B (en) | 2016-06-15 |
| JP5990168B2 (en) | 2016-09-07 |
| TW201303005A (en) | 2013-01-16 |
| CN106008215A (en) | 2016-10-12 |
| WO2013008487A1 (en) | 2013-01-17 |
| JPWO2013008487A1 (en) | 2015-02-23 |
| TWI583783B (en) | 2017-05-21 |
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