CN101928216A - Preparation method of ester applied to lubricating oil and ester applied to lubricating oil - Google Patents
Preparation method of ester applied to lubricating oil and ester applied to lubricating oil Download PDFInfo
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- CN101928216A CN101928216A CN2009100877188A CN200910087718A CN101928216A CN 101928216 A CN101928216 A CN 101928216A CN 2009100877188 A CN2009100877188 A CN 2009100877188A CN 200910087718 A CN200910087718 A CN 200910087718A CN 101928216 A CN101928216 A CN 101928216A
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Abstract
The invention provides a preparation method of ester applied to lubricating oil and the ester applied to lubricating oil prepared by the method. The method comprises the following steps: carrying out esterification action on aliphatic series polyalcohol and sufficient or excessive aliphatic series carboxylic acid; carrying out contact reaction on the product of the esterification action and acid capturing agent; removing unreacted acid capturing agent. The preparation method of the invention can effectively improve yield of ester, fully reduce acid value of ester, thus reducing the acid value of base oil, especially the acid value of refrigerating machine oil to a large extent, achieving environment-friendliness, lowering consumption of raw materials, eliminating emulsification in the process of alkalicleaning and improving storage stability of ester. In the invention, the acid value of the ester applied to the lubricating oil is extremely low which is lower than 0.02mgKOH/g, the ester is colorless and transparent and is the high quality base oil of lubricating oil.
Description
Technical field
The present invention relates to a kind of preparation method of lubricant ester and the lubricant ester for preparing by this method.
Background technology
Lubricating oil in esters is the excellent performance of polyol ester class lubricating oil especially, technology and using environment-friendly are strong, and biodegradable at short notice, meet the industry policy of Sustainable development, use environment friendly refrigerating fluid as forcing in 2013 at home, thereby replace freonll-11 comprehensively; Along with energy conservation and environment protection, existing traditional refrigeration air-conditioner will progressively be replaced by convertible frequency air-conditioner, also will use the polyol ester refrigerator oil simultaneously.Along with the adjustment of China's new round industrial structure, synthetic ester lubricant is no matter from himself performance advantage, or on the performance requriements of relevant industries, will obtain faster development.
Polyhydric alcohol fatty acid ester (POE) polyhydric alcohol fatty acid ester that preferably is obstructed, as neopentyl glycol fatty acid ester, trimethylolpropane fatty acid ester, pentaerythritol fatty ester, bis pentaervthritol ester and polyol blend fatty acid ester etc., with its excellent lubrication, thermotolerance, thermo-oxidative stability, low-temperature fluidity, biodegradability etc., increase day by day as the application of lubricant base.Simultaneously, for adapting to environmental protection and energy-conservation demand, polyol ester is as the substitute of traditional mineral oil, its use range also progressively enlarges, for example along with the progressively use of not chloride refrigeration agent hydrogen fluorohydrocarbon, need provide compatible with it lubricating oil, and polyol ester is the main component in this hydrofluorocarbon refrigeration agent usefulness lubricating oil.
Polyhydric alcohol fatty acid ester mainly prepares by the esterification of pure and mild acid, need under the condition of very high temperature of reaction and excess carboxylic acid, carry out, therefore employed carboxylic acid of this reaction and an acidic catalyst have residual in esterification reaction product, and the color and luster of use technical grade lipid acid and the resulting ester of polyol reaction is variation with the raising of degree of esterification, therefore need carry out depickling, decolouring processing to esterification reaction product.
A kind of method of manufacturing of lubricant ester is disclosed among the CN1347867A, this method is included in the carboxylic acid carboxyl with respect to 1 mole, it is under the existence of reductive agent that the lewis acid catalyst of 0.0001-0.005 mole and the phosphorus of 0.0003-0.005 mole are arranged, and carries out the step of alcohol and carboxylic acid reaction; And with the ester class separation steps that obtains.Carry out the method that the purified method preferably adopts the alkali cleaning depickling and carries out adsorption treatment with sorbent material with the separation of ester class and to ester.In this patent application ester is carried out the purified method directly with the washing of the aqueous solution liquid of alkali, the yield of ester is low, the consumption height of alkali, and the consumption height of raw material carboxylic acid, and emulsion takes place easily with the solution washing of alkali, and can not fully reduce acid number.
Disclose a kind of method of manufacturing of lubricant ester among the CN1449374A, this method comprises, obtains the operation of esterification crude product by the alcohol and carboxylic acid reaction; And, add varsol, and the alcoholic solvent of the 1-3 carbon atom of the preferred 3-50 of interpolation weight part of 5-100 weight part with respect to this esterification crude product of 100 weight parts, use alkali aqueous solution to carry out the operation of depickling then; Varsol is selected from least a in toluene, dimethylbenzene, hexanaphthene and the normal heptane.This method can solve full-bodied ester the emulsive problem takes place in alkaline cleaning procedure, but produces environmental problem owing to introducing volatile varsol, and the consumption of the consumption of alkali and raw material carboxylic acid is all very big, and the yield of ester is low.
CN1636960A discloses a kind of manufacture method of lubricant ester, and this method comprises, (1) makes aliphatic polyol and the reaction of representative examples of saturated aliphatic monocarboxylic acid and obtains containing the resultant of reaction of ester; (2) resultant of reaction that operation (1) is obtained carries out reduced pressure treatment, removes the representative examples of saturated aliphatic monocarboxylic acid from this resultant of reaction; (3) resultant of reaction after operation (2) depickling is decoloured; (4) by being contacted, the resultant of reaction that can adsorb after the decolouring of the monocarboxylic sour sorbent material of representative examples of saturated aliphatic and operation (3) removes the representative examples of saturated aliphatic monocarboxylic acid.The acid sorbent material can adopt activated alumina, atlapulgite, aluminium hydroxide, the synthetic zeolite that the anionresin adsorptive power is arranged or ion exchange resin or hydrotalcite etc.This method has been omitted alkali cleaning and washing process, but deacidification effect is relatively poor, expends a large amount of sorbent materials, and the yield of ester is low.
Summary of the invention
The objective of the invention is to overcome the lower defective of yield of ester in the manufacture method of above-mentioned prior art lubricant ester, the preparation method of the higher lubricant ester of a kind of yield of ester is provided, a kind of lubricant ester also is provided.
The invention provides a kind of preparation method of lubricant ester, this method is included in and makes aliphatic polyol and capacity or excess fats family carboxylic acid carry out esterification under the esterification condition, product and acid-capture agent contact reacts with described esterification, remove unreacted acid-capture agent, acid-capture agent is the compound shown in formula 1 and/or the formula 2;
Wherein, R
1For having the alkyl with straight or branched structure, the aryl or aralkyl of 5-22 carbon atom, R
2For having the alkyl with straight or branched structure, the aryl or aralkyl of 3-22 carbon atom.
The present invention also provides a kind of lubricant ester, and this lubricant ester obtains by preparation method of the present invention.
The preparation method of lubricant ester provided by the invention can effectively improve the yield of ester, and the yield of ester can reach more than the 95 weight %; Can fully reduce the acid number of ester, the acid number of ester is reduced to below the 0.007mgKOH/g, thereby reduce the especially acid number of refrigerator oil of base oil largely; Realize environmental friendliness, reduce consumption of raw materials, eliminated the emulsion in the alkali washing process process, improved the stability in storage of ester.
The acid number of lubricant ester provided by the invention is very low, and below 0.007mgKOH/g, and color is water white transparency, is the very high lubricant base of quality.
Embodiment
Hydroxyl in term as herein described " hydroxyl value " the expression 1g sample the milligram number of suitable potassium hydroxide, represent (adopting GB GBT 7383 to measure) with mgKOH/g.
In term as herein described " acid number " expression and the milligram number of the required consumption potassium hydroxide of free acid in the 1g sample, represent that what of free acid content in the sample are the size of acid number reflected with mgKOH/g.
The preparation method of lubricant ester provided by the invention comprises, under the esterification condition, make aliphatic polyol and capacity or excess fats family carboxylic acid carry out esterification, product and acid-capture agent contact reacts with described esterification, remove unreacted acid-capture agent, acid-capture agent is the compound shown in formula 1 and/or the formula 2:
Wherein, R
1For having the alkyl with straight or branched structure, the aryl or aralkyl of 5-22 carbon atom, R
2For having the alkyl with straight or branched structure, the aryl or aralkyl of 3-22 carbon atom.
Wherein, R
1For having the alkyl with straight or branched structure, the aryl or aralkyl of 5-22 carbon atom, more preferably R
1For having the alkyl with branched structure of 5-22 carbon atom, most preferably be alkyl, being the alkyl that the carbonyl alpha-carbon atom is replaced fully with " newly " structure;
R
2For having the alkyl with straight or branched structure, the aryl or aralkyl of 3-22 carbon atom, preferred R
2For having the alkyl with branched structure of 5-22 carbon atom, most preferably be alkyl, being the alkyl that the ether alpha-carbon atom is replaced fully with " newly " structure.
As the compound shown in the formula 1, more preferably R
1For having the alkyl of branched structure, most preferably have " newly " structure, be the alkyl that the carbonyl alpha-carbon atom is replaced fully.The example of compound shown in the formula 1 comprise n-nonanoic acid glycidyl ester, enanthic acid glycidyl ester, valeric acid glycidyl ester, stearic acid glycidyl ester, Unimac 5680 glycidyl ester, oleic acid glycidyl ester, phenylformic acid glycidyl ester, p t butylbenzoic acid glycidyl ester, glycidyl acrylate, glycidyl methacrylate and 2,2 '-in the dimethyl-octa acid glycidyl ester one or more.Wherein preferred n-nonanoic acid glycidyl ester, enanthic acid glycidyl ester, stearic acid glycidyl ester and 2,2 '-in the dimethyl-octa acid glycidyl ester one or more.
As the compound shown in the formula 2, more preferably R
2For having the alkyl of branched structure, most preferably have " newly " structure, be the alkyl that the ether alpha-carbon atom is replaced fully.The example of compound comprises isopropyl glycidyl ether shown in the formula 2, glycidyl allyl ether, butylglycidyl ether, tertiary butyl glycidyl ether, the amyl group glycidyl ether, the heptyl glycidyl ether, octyl glycidyl ether, the nonyl glycidyl ether, decyl glycidyl ether, the undecyl glycidyl ether, lauryl diglycidyl ether, the tridecyl glycidyl ether, the tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentylglycol diglycidyl ether, the trishydroxymethyl triglycidyl ether, tetramethylolmethane four glycidyl ethers, 1, the 4-butanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, the sorbyl alcohol polyglycidyl ether, the polyalkylene glycol monoglycidyl ether, the polyalkylene glycol diglycidylether; Arylolycidyl ethers is as phenyl glycidyl ether, resorcinol diglycidyl ether; The alkaryl glycidyl ether is as n-butylphenyl glycidyl ether, isobutyl phenenyl glycidyl ether, secondary butyl phenenyl glycidyl ether, tert-butyl-phenyl glycidyl ether, amyl group phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl phenyl glycidyl ether, decyl phenyl glycidyl ether, to the nonyl phenyl glycidyl ether; And epoxidized vegetable oil, as in the epoxide of soybean oil, oleum lini, cottonseed wet goods vegetables oil one or more.One or more in preferred tertiary butylglycidyl ether, 2-ethylhexyl glycidyl ether, neopentylglycol diglycidyl ether, trishydroxymethyl triglycidyl ether, tetramethylolmethane four glycidyl ethers wherein.
According to preparation method provided by the invention, because the compound shown in the formula 2 has the performance of the excellence of thermostability, stability to hydrolysis, consistency and low-temperature stability, therefore described acid-capture agent is preferably the compound shown in the formula 2.
According to preparation method provided by the invention, adopt the free acid reaction in acid-capture agent and the described esterification reaction product, can remove free acid residual in the esterification reaction product, thereby further reduce the acid number of this product.
According to preparation method provided by the invention, in the preferred case, with the product of described esterification and the catalytic condition of acid-capture agent make with the acid-capture agent contact reacts after the acid number of product be below the 1mgKOH/g, be preferably below the 0.5mgKOH/g, can judge whether this contact reacts finishes with this.
According to preparation method provided by the invention, in the preferred case, the consumption of described acid-capture agent is that doubly, more preferably 1-2 is doubly for the 1-5 of the equivalents of contained carboxylic acid in the product of described esterification.
According to preparation method provided by the invention, in the preferred case, the product and the catalytic condition of acid-capture agent of described esterification are comprised described catalytic temperature is 130-250 ℃, is preferably 180-230 ℃ that the described catalytic time is 1-5 hour, is preferably 2-4 hour.
According to preparation method provided by the invention, in the preferred case, the method for removing unreacted acid-capture agent comprises, will distill under the temperature of the pressure of 1-10kPa, 180-230 ℃ with the catalytic product of acid-capture agent.
The reaction product that the reaction of above-mentioned acid-capture agent and free acid is generated can be used as a small amount of component of base oil and is present in the base oil as lubricant ester, compatible fully with lubricating oil, and do not influence the quality and the performance of lubricating oil, and can improve the yield of lubricant ester, make full use of free acid.
According to preparation method provided by the invention, polyhydric alcohol fatty acid ester in the described esterification reaction products resulting can be the esterified ester of part of hydroxyl, it also can be the esterified ester of whole hydroxyls, the hydroxyl value of preferred this polyhydric alcohol fatty acid ester be 20mgKOH/g following, more preferably below the 10mgKOH/g, preferably with this hydroxyl value as the standard of judging whether esterification finishes.
According to preparation method provided by the invention, the esterification of aliphatic polyol and aliphatic carboxylic acid, consider that from the angle that improves esterification reaction rate the equivalence ratio of preferred aliphat carboxylic acid and aliphatic polyol is 1-1.5, more preferably 1.01-1.2,1.01-1.1 most preferably.This equivalence ratio is the ratio of the hydroxyl number of each polyhydroxy reactant (polyvalent alcohol that uses two or more is all polyhydroxy reactants) with respect to the carboxyl number of fatty acid component (fatty acid component that uses two or more is all fatty acid components).Use fatty acid component by this equivalence ratio, help weeding of grease aliphatic carboxylic acid in follow-up operation.
According to preparation method provided by the invention, in the preferred case, described esterification condition comprises, the temperature of esterification is that 180-260 ℃, time of esterification are 5-15 hour, and the equivalence ratio of described aliphatic carboxylic acid and described aliphatic polyol is 1-1.5, be preferably 1-1.2,1.01-1.1 more preferably.
According to preparation method provided by the invention, in this esterification, consider that from the angle of the viscosity that generates ester described aliphatic polyol is preferably the aliphatic polyol with 2-15 carbon atom, more preferably 5-10; In addition, the hydroxyl in the molecule also can be adjusted the viscosity of ester, therefore, contains 2-8 hydroxyl in the preferred polyol molecule; Consider that from stable on heating angle polyvalent alcohol preferably is obstructed.
As aliphatic polyol, can be selected from the following compound one or more: 1, ammediol, the 2-methyl isophthalic acid, ammediol, 2-ethyl-2-methyl isophthalic acid, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-methyl-2-sec.-propyl-1, ammediol, 2,2-diethyl-1, ammediol, 2-normal-butyl-2-ethyl-1, ammediol, two (3-hydroxyls-2, the 2-dimethyl propyl) ether, TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, two trimethylolethanes, ditrimethylolpropane, three TriMethylolPropane(TMP)s, tetramethylolmethane, Dipentaerythritol, tripentaerythritol, ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, five ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, the 2-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 7-heptanediol, 1, the new glycol of 8-, 1, the 9-nonanediol, 1, the 10-decanediol, 1,11-undecane glycol, 1, the 12-dodecanediol, glycerine, Glycerol dimer, triglycerin, the Polyglycerine polyvalent alcohol, 1,3,5-penta triol, sorbyl alcohol, sorbitan, the sorbyl alcohol glycerol condensate, ribitol, arabitol, Xylitol, N.F,USP MANNITOL, and carbohydrate such as wood sugar, pectinose, ribose, rhamnosyl, glucose, fructose, semi-lactosi, seminose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, the etherate of melizitose and these carbohydrates.
Described aliphatic carboxylic acid can be considered the carbonatoms 4-12 of preferred aliphat carboxylic acid, further preferred 5-10 for having the aliphatics monocarboxylic acid of 1-24 carbon atom from the low-temperature fluidity of generation ester with to the angle of corrosion of metal.From considering that with the consistency angle of refrigeration agent the monocarboxylic carbonatoms of preferred aliphat is less than 12; Consider that from the angle of the oilness that generates ester preferred carbonatoms is greater than 4.
This aliphatic carboxylic acid can be the aliphatic carboxylic acid of straight chain, also can be the aliphatic carboxylic acid of side chain, can be representative examples of saturated aliphatic carboxylic, also can be the unsaturated aliphatic carboxylic acid.Consider preferred straight chain fatty acid from the oilness aspect; Consider that from the hydrolytic resistance aspect preferred branched chain fatty acid more preferably has the carboxylic acid of side chain on the α position of carbonyl.
As the aliphatics monocarboxylic acid, can be selected from the following compound one or more: straight chain representative examples of saturated aliphatic monocarboxylic acid such as valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, margaric acid, octadecanoic acid, nondecylic acid, arachic acid; Side chain aliphatics saturated monocarboxylic acid such as isopropylformic acid, isovaleric acid, trimethylacetic acid, 2-ethyl valeric acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, 3-thylhexoic acid, 2-methyl enanthic acid, cyclohexyl acetic acid, 3,5,5-tri-methyl hexanoic acid, 2-methyloctanoic acid, Unimac 5680; Unsaturated aliphatic monocarboxylic acid such as decylenic acid, undecylenic acid, dodecenoic acid, tridecylenic acid, tetradecenoic acid, pentadecylenic acid, hexadecylenic acid, heptadecenoic acid, oleic acid; Alpha-carbon atom is the aliphatics monocarboxylic acid (eo-acid) of quaternary carbon atom.
The array mode that forms the used polynary alcohols and fatty carboxylic acids of feedstock fat family of polyhydric alcohol fatty acid ester has no particular limits, and can select array mode according to the oilness of polyhydric alcohol fatty acid ester, stability to hydrolysis with the desired characteristics such as consistency of hydrogen fluorohydrocarbon.
According to preparation method provided by the invention, in the preferred case, described method also comprises, before the product and acid-capture agent contact reacts with esterification, product with esterification carries out underpressure distillation earlier, the condition of underpressure distillation make after the described underpressure distillation acid number of resulting product be 10mgKOH/g following, more preferably below the 5mgKOH/g, the preferred standard that whether finishes as underpressure distillation with this acid number.
According to preparation method provided by the invention, in the preferred case, the condition of described underpressure distillation comprises, the pressure of underpressure distillation is that the temperature of 1-103kPa, underpressure distillation is that 180-230 ℃, time of underpressure distillation are 0.5-2 hour, removing unreacted aliphatic carboxylic acid, and the aliphatic carboxylic acid that this is removed is recycled as reaction raw materials.
According to preparation method provided by the invention, in the preferred case, described method also comprises, removes product behind the unreacted acid-capture agent with the solution washing of alkali with described, and the condition of described washing makes that the acid number of the product after the described washing is below the 0.05mgKOH/g.
According to preparation method provided by the invention, catch after the sour step free acid of trace in the resulting product by the described product of removing behind the unreacted acid-capture agent can further be removed with the solution washing of alkali, can remove colloid and foreign pigment simultaneously.The condition of described washing comprises, under 70-90 ℃, with the basic solution washing that is 0.1-10 weight % of described product concentration of removing behind the unreacted acid-capture agent, described basic solution with catch that the weight ratio of resulting product is 1 after the sour step: 10-100, washing time is 0.5-2.5 hour, leaves standstill then 0.5-2.5 hour, then uses deionized water wash oil phase 3 times successively under the same conditions, the water oil quality is than 1: 2-10, thereby further depickling and flush away impurity.The concentration of basic solution is preferably 0.1-5 weight %, more preferably 0.1-2 weight %.Can be alkaline carbonates such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, ammonium salts such as volatile salt as the employed alkali of basic solution.Wherein, preferred sodium hydroxide, potassium hydroxide and yellow soda ash.
According to preparation method provided by the invention, in the preferred case, described method also comprises, remove product behind the unreacted acid-capture agent with the solution washing of alkali with described, the resulting product in described washing back is carried out adsorption bleaching with sorbent material, and it is below the 0.02mgKOH/g that the condition of adsorption bleaching makes the acid number of the product behind the described adsorption bleaching.
According to preparation method provided by the invention, described adsorption bleaching comprises, use sorbent material to above-mentioned washing after resulting product carried out adsorption bleaching 0.5-2.5 hour, filter out this decolorizing adsorbent then.Based on the weight of the resulting product in described washing back, the consumption of described sorbent material is 0.1-2 weight %, be preferably 0.1-2 weight %, 0.1-1 weight % more preferably.Described sorbent material comprises one or more in gac, atlapulgite, silica gel or the aluminum oxide.In the preferred case, carry out above-mentioned adsorption treatment before, will wash the resulting product in back earlier and under the pressure of 70-150 ℃ temperature and 1-10kPa, carry out reduced pressure treatment, to deviate from moisture wherein.
According to preparation method provided by the invention, the preparation method of lubricant ester of the present invention is preferably undertaken by aforesaid each step, and the acid number of final resulting this ester can reach 0.007mgKOH/g following (mensuration of acid number is carried out according to GB/T 7304); Colourity can reach 0.1 (mensuration of colourity is carried out according to GB/T 6540).
According to preparation method provided by the invention, can reduce the concentration of washing soda amount and alkaline solution significantly, the consumption and the sorbent material consumption of raw material acid have been reduced, and reduced the acid number of lubricant ester significantly, thoroughly stopped the emulsion of washing process, improved the yield of ester, will bring very big influence to increasing economic efficiency industrial.
According to the resulting ester of preparation method provided by the invention, its acid number and colourity are all very low, be very suitable for base oil, for example can be used as the base oil of refrigerator oil, lubricating oil, hydraulic efficiency oil, engine wet goods lubricating oil, be especially suitable for use as refrigerator oil as lubricating oil.In this ester, can also suitably add additives such as oxidation inhibitor, anti-wear agent, rust-preventive agent and make lubricating oil, particularly refrigerator oil as base oil.
Lubricant ester provided by the invention obtains by preparation method of the present invention.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
1, reaction process
Be blown into pipe, thermometer and have in the 2L four-hole boiling flask of water trap of condenser being provided with stirring rod, nitrogen, add tetramethylolmethane 272g (2.0mol), 2 ethyl hexanoic acid 1267.2g (8.8mol) (with respect to 1 normal hydroxyl of tetramethylolmethane, the carboxyl of 2 ethyl hexanoic acid is 1.10 equivalents).Under nitrogen gas stream,, remove the water that distills out in 250 ℃ of mixture reactions 10 hours that make in the flask.When the hydroxyl value of reaction product≤5.0mgKOH/g, reduce temperature of reaction to 200 ℃.
2, deacidification process
(1) underpressure distillation
Under 200 ℃, be decompressed to 1kPa, with reaction mixture distillation 1 hour, heat up in a steamer free 2 ethyl hexanoic acid 108g.The acid number of resulting product is 5.0mgKOH/g.
(2) catch sour step
After above-mentioned underpressure distillation, add 2 in the resulting product, 2 '-dimethyl-octa acid glycidyl ester 52g is (with respect to 1 normal carboxylic acid, 2,2 '-epoxy group(ing) of dimethyl-octa acid glycidyl ester is 2.0 equivalents), under this temperature of 200 ℃, reaction is 2 hours under nitrogen gas stream, carries out underpressure distillation 1 hour then under the pressure of 5kPa, heat up in a steamer unreacted 2,2 '-dimethyl-octa acid glycidyl ester 26g.The acid number of resulting product is 0.3mgKOH/g.
(3) alkali cleaning step
Under 90 ℃, to use with above-mentioned weight ratio of catching the resulting product of sour step be that 1: 10 0.5% potassium hydroxide aqueous solution washing is above-mentioned caught the resulting product of sour step 0.5 hour, left standstill again 0.5 hour, use deionized water (water weight of oil ratio is 1: 5) washing oil phase three times then successively, the pH that makes this oil phase is to neutral.Obtain the product after the alkali cleaning, acid number is 0.04mgKOH/g.
(4) adsorption step
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning step adds atlapulgite 6g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.Obtain lubricant ester 1282g as the base oil of lubricating oil.
Embodiment 2
Prepare lubricant ester according to the method described in the embodiment 1, the sour step of catching that different is in the deacidification process:
In the resulting product of reaction process, add 2-ethylhexyl glycidyl ether 43g (with respect to 1 normal carboxylic acid, the epoxy group(ing) of 2-ethylhexyl glycidyl ether is 2.0 equivalents), under 200 ℃ temperature, reaction is 2 hours under nitrogen gas stream, under the pressure of 1kPa, carry out underpressure distillation 1 hour then, heat up in a steamer unreacted 2-ethylhexyl glycidyl ether 21g.The acid number of resulting product is 0.3mgKOH/g.
Finally obtain lubricant ester 1286g as the base oil of lubricating oil.
Embodiment 3
1, reaction process
Be blown into pipe, thermometer and have in the 2L four-hole boiling flask of water trap of condenser being provided with stirring rod, nitrogen, add tetramethylolmethane 272g (2.0mol), 2 ethyl hexanoic acid 633.6g (4.4mol), 3,5,5-tri-methyl hexanoic acid 695.2g (4.4mol) is (with respect to 1 normal hydroxyl of tetramethylolmethane, the carboxyl of aforementioned 2 ethyl hexanoic acid and 3,5,5 Trimethylhexanoic acid adds up to 1.10 equivalents).Under nitrogen gas stream,, remove the water that distills out in 250 ℃ of mixture reaction 8-12 hours of making in the flask.When the hydroxyl value of reaction product≤5.0mgKOH/g, reduce temperature of reaction to 200 ℃.
2, deacidification process
(1) underpressure distillation
Under 200 ℃, be decompressed to 10kPa, with reaction mixture distillation 1 hour, heat up in a steamer free carboxylic acid 113g, the acid number of resulting product is 5.0mgKOH/g.
(2) catch sour step
In the resulting product of above-mentioned reaction process, add n-nonanoic acid glycidyl ester 23g (with respect to 1 normal carboxylic acid, the epoxy group(ing) of n-nonanoic acid glycidyl ester is 1.0 equivalents), under 180 ℃ temperature, reaction is 2 hours under nitrogen gas stream, under the pressure of 2kPa, carry out underpressure distillation 1 hour then, heat up in a steamer unreacted n-nonanoic acid glycidyl ester 5g.The acid number of resulting product is 0.8mgKOH/g.
(3) alkali cleaning step
Under 90 ℃, to use with above-mentioned weight ratio of catching the resulting product of sour step be that 1: 4 0.5% potassium hydroxide aqueous solution washing is above-mentioned caught the resulting product of sour step 0.5 hour, left standstill again 0.5 hour, use deionized water (water weight of oil ratio is 1: 4) washing oil phase three times then successively, the pH that makes this oil phase is to neutral.Obtain the product after the alkali cleaning, acid number is 0.04mgKOH/g.
(4) adsorption step
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning step adds atlapulgite 7g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.Obtain lubricant ester 1305g as the base oil of lubricating oil.
Embodiment 4
Prepare lubricant ester according to the method described in the embodiment 3, the sour step of catching that different is in the deacidification process:
In the resulting product of reaction process, add neopentylglycol diglycidyl ether 216g (with respect to 1 normal carboxylic acid, the epoxy group(ing) of neopentylglycol diglycidyl ether is 2.0 equivalents), under 200 ℃ temperature, reaction is 2 hours under nitrogen gas stream, under the pressure of 10kPa, carry out underpressure distillation 1 hour then, heat up in a steamer unreacted neopentylglycol diglycidyl ether 25g.The acid number of resulting product is 0.3mgKOH/g.
Finally obtain lubricant ester 1341g as the base oil of lubricating oil.
Embodiment 5
1, reaction process
Be blown into pipe, thermometer and have in the 2L four-hole boiling flask of water trap of condenser being provided with stirring rod, nitrogen, add dipentaerythritol 254g (1.0mol), 3,5,5-tri-methyl hexanoic acid 1042.8g (6.6mol) (1 normal hydroxyl of relative dipentaerythritol, 3,5, the carboxyl of 5-tri-methyl hexanoic acid is 1.10 equivalents).Under nitrogen gas stream,, remove the water that distills out in 250 ℃ of mixture reaction 8-12 hours of making in the flask.When the hydroxyl value of reaction product≤5.0mgKOH/g, reduce temperature of reaction to 230 ℃.
2, deacidification process
(1) underpressure distillation
Under 230 ℃, be decompressed to 100kPa, with reaction mixture distillation 1 hour, heat up in a steamer free 3,5,5 Trimethylhexanoic acid 88g, the acid number of resulting product is 5.0mgKOH/g.
(2) catch sour step
In the resulting product of above-mentioned reaction process, add stearic acid glycidyl ester 34g (with respect to 1 normal carboxylic acid, the epoxy group(ing) of stearic acid glycidyl ester is 1.0 equivalents), under this temperature of 230 ℃, reaction is 2 hours under nitrogen gas stream, under the pressure of 8kPa, carry out underpressure distillation 1 hour then, heat up in a steamer unreacted stearic acid glycidyl ester.The acid number of resulting product is 0.4mgKOH/g.
(3) alkali cleaning step
Under 90 ℃, to use with above-mentioned weight ratio of catching the resulting product of sour step be that 1: 5 0.5% potassium hydroxide aqueous solution washing is above-mentioned caught the resulting product of sour step 0.5 hour, left standstill again 0.5 hour, use deionized water (water weight of oil ratio is 1: 2) washing oil phase three times then successively, the pH that makes this oil phase is to neutral.Obtain the product after the alkali cleaning, acid number is 0.04mgKOH/g.
(4) adsorption step
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning step adds atlapulgite 5g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.Obtain lubricant ester 1097g as the base oil of lubricating oil.
Embodiment 6
Prepare lubricant ester according to the method described in the embodiment 5, the sour step of catching that different is in the deacidification process:
In the resulting product of reaction process, add tertiary butyl glycidyl ether 26g (with respect to 1 normal carboxylic acid, the epoxy group(ing) of tertiary butyl glycidyl ether is 2.0 equivalents), under 230 ℃ temperature, reaction is 2 hours under nitrogen gas stream, under the pressure of 130kPa, carry out underpressure distillation 1 hour then, heat up in a steamer unreacted tertiary butyl glycidyl ether 13g.The acid number of resulting product is 0.2mgKOH/g.
Finally obtain lubricant ester 1094g as the base oil of lubricating oil.
Comparative example 1
Carry out according to reaction process of describing among the embodiment 1 and the underpressure distillation step in the deacidification process, obtain product 1280g, acid number is 5.0mgKOH/g.Later deacidification process is as follows:
Under 90 ℃, by the resulting product of the above-mentioned reaction process of KOH solution washing of 2 times of equivalents (128g) 10% 0.5 hour, left standstill 0.5 hour, water weight of oil ratio is 20: 80 a deionized water wash oil phase 4 times successively then again, and the pH that makes this oil phase is to neutral.Obtain the product of alkali cleaning.
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning adds atlapulgite 12g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.
Obtain lubricant ester 1202g as the base oil of lubricating oil.
Comparative example 2
Carry out according to reaction process of describing among the embodiment 5 and the underpressure distillation step in the deacidification process, the acid number of resulting product is 5.0mgKOH/g.Later deacidification process is as follows:
Under 90 ℃, the KOH aqueous solution (containing KOH 11g) by 2 times of equivalents (110g) 10% washed the resulting product of above-mentioned reaction process 0.5 hour, left standstill 1.0 hours, water weight of oil ratio is 20: 80 a deionized water wash oil phase 4 times successively then again, and the pH that makes this oil phase is to neutral.Obtain the product of alkali cleaning.
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning adds atlapulgite 10g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.
Obtain lubricant ester 985g as the base oil of lubricating oil.
Comparative example 3
Carry out according to reaction process of describing among the embodiment 2 and the underpressure distillation step in the deacidification process, the acid number of resulting product is 5.0mgKOH/g.Later deacidification process is as follows:
Under 90 ℃, by the resulting product of the above-mentioned reaction process of KOH solution washing of 2 times of equivalents (128g) 10% 0.5 hour, left standstill 0.5 hour, water weight of oil ratio is 20: 80 a deionized water wash oil phase 4 times successively then again, and the pH that makes this oil phase is to neutral.Obtain the product of alkali cleaning.
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning adds atlapulgite 12g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.
Obtain lubricant ester 1202g as the base oil of lubricating oil.
Comparative example 4
Carry out according to reaction process of describing among the embodiment 6 and the underpressure distillation step in the deacidification process, the acid number of resulting product is 5.0mgKOH/g.Later deacidification process is as follows:
Under 90 ℃, by the resulting product of the above-mentioned reaction process of KOH solution washing of 2 times of equivalents (110g) 10% 0.5 hour, left standstill 1.0 hours, water weight of oil ratio is 20: 80 a deionized water wash oil phase 4 times successively then again, and the pH that makes this oil phase is to neutral.Obtain the product of alkali cleaning.
Product vacuum removal moisture under 100 ℃ temperature with above-mentioned alkali cleaning adds atlapulgite 10g then, is to stir 1 hour under 1.3kPa, temperature are 100 ℃ at pressure, filters.
Obtain lubricant ester 985g as the base oil of lubricating oil.
Embodiment 1-6 and the resulting ester of comparative example 1-4 are tested, and the mensuration of acid number is carried out according to GB/T7304, and the mensuration of colourity is carried out according to GB/T 6540, and the mensuration of kinematic viscosity is carried out according to GB/T265.The results are shown in Table 1 for gained.
Table 1
From embodiment 1-6 and comparative example 1-4 as can be seen, adopt the preparation method of lubricant ester provided by the invention can fully reduce the acid number of lubricant ester, make acid number can reach below the 0.007mgKOH/g; Carboxylic acid excessive when reacting can be reclaimed, thereby the consumption of raw material carboxylic acid can be reduced; Can reduce consumption and the concentration of alkaline solution and the consumption of sorbent material of alkali, thereby reduce discharging and reduced pollution environment.And the result from table 1 adopts the preparation method of lubricant ester provided by the invention as can be seen, can improve the yield of ester.
In addition, by with embodiment 1 and 2, embodiment 3 and 4, embodiment 5 and 6 test result compare, as can be seen, the lubricant ester of synthetic identical viscosities (identical synthesizing formula), use glycidyl ether as the effect of acid-capture agent significantly better than using glycidyl ester as acid-capture agent, the yield of resulting lubricant ester is higher, and the acid-capture agent among the present invention can effectively reduce the acid number of lubricant ester, adopt the identical prepared lubricant ester of raw alcohol, use product that glycidyl ether obtains as acid-capture agent than having lower acid number as acid-capture agent with glycidyl ester.
Claims (15)
1. the preparation method of a lubricant ester, this method is included in and makes aliphatic polyol and capacity or excess fats family carboxylic acid carry out esterification under the esterification condition, product and acid-capture agent contact reacts with described esterification, remove unreacted acid-capture agent, acid-capture agent is the compound shown in formula 1 and/or the formula 2;
Wherein, R
1For having the alkyl with straight or branched structure, the aryl or aralkyl of 5-22 carbon atom, R
2For having the alkyl with straight or branched structure, the aryl or aralkyl of 3-22 carbon atom.
2. preparation method according to claim 1, wherein, acid-capture agent is the compound shown in the formula 2, and R
2For having the alkyl with branched structure of 5-22 carbon atom.
3. preparation method according to claim 1 and 2, wherein, with the product of described esterification and the catalytic condition of acid-capture agent comprise make with the acid-capture agent contact reacts after the acid number of product be below the 1mgKOH/g.
4. preparation method according to claim 1 and 2, wherein, the consumption of described acid-capture agent be the equivalents of contained carboxylic acid in the product of described esterification 1-5 doubly.
5. preparation method according to claim 4, wherein, the consumption of described acid-capture agent be contained carboxylic acid equivalents in the product of described esterification 1-2 doubly.
6. preparation method according to claim 1 and 2 wherein, comprises that with the product and the catalytic condition of acid-capture agent of described esterification described catalytic temperature is 130-250 ℃, and the described catalytic time is 1-5 hour.
7. preparation method according to claim 6, wherein, described catalytic temperature is 180-230 ℃, the described catalytic time is 2-4 hour.
8. preparation method according to claim 1 and 2, wherein, the method for removing unreacted acid-capture agent comprises, will distill under the temperature of the pressure of 1-10kPa, 180-230 ℃ with the catalytic product of acid-capture agent.
9. preparation method according to claim 1, wherein, the condition of described esterification comprises that the hydroxyl value that makes described esterification reaction product is below the 20mgKOH/g.
10. according to claim 1 or 9 described preparation methods, described esterification condition comprises, esterification reaction temperature is that 180-260 ℃, reaction time of esterification are 5-15 hour, and the equivalence ratio of described aliphatic carboxylic acid and described aliphatic polyol is 1-1.5.
11. preparation method according to claim 1, wherein, described aliphatic polyol is the aliphatic polyol that has 2-15 carbon atom and have 2-8 hydroxyl, and described aliphatic carboxylic acid is the aliphatics monocarboxylic acid with 1-24 carbon atom.
12. preparation method according to claim 1, wherein, described method also comprises, before the product and acid-capture agent contact reacts with esterification, earlier the product with esterification carries out underpressure distillation, and the condition of underpressure distillation makes that the acid number of resulting product is below the 10mgKOH/g after the described underpressure distillation.
13. preparation method according to claim 1, wherein, described method also comprises, removes product behind the unreacted acid-capture agent with the solution washing of alkali with described, and the condition of described washing makes that the acid number of the product after the described washing is below the 0.05mgKOH/g.
14. preparation method according to claim 13, wherein, described method also comprises, remove product behind the unreacted acid-capture agent with behind the solution washing of alkali with described, product after the described washing is carried out adsorption bleaching with sorbent material, and the condition of adsorption bleaching comprises that making the acid number of the product behind the described adsorption bleaching is below the 0.02mgKOH/g.
15. a lubricant ester, this lubricant ester obtains by any described preparation method among the claim 1-14.
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