CN101914014A - Method for synthesizing and purifying synthetic ester oil for cosmetics and synthetic ester oil for cosmetics obtained by same - Google Patents
Method for synthesizing and purifying synthetic ester oil for cosmetics and synthetic ester oil for cosmetics obtained by same Download PDFInfo
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Abstract
The invention relates to a method for synthesizing and purifying synthetic ester oil for cosmetics and the synthetic ester oil for the cosmetics obtained by the same, in particular to the method for synthesizing and purifying the synthetic ester oil for the cosmetics. High-purity odorless and smelless synthetic ester oil for the cosmetics is obtained by the following steps of: adopting a novel pseudo-homogeneous catalyst in a synthesis process; adding a reaction cocatalyst; performing alkali washing; and controlling technological parameters. The method of the invention does not need an independent purification step, so that a process for purifying the synthetic ester oil for the cosmetics is simplified.
Description
Technical field
The invention belongs to cosmetic field.More specifically, the present invention relates to the used for cosmetic Synthetic Oil.
Background technology
Cosmetic industry is the higher-end businesses of fine chemicals, and annual cosmetic industry is very huge to greasy requirement, and only Synthetic Oil is one, and requirement reaches more than ten ten thousand tons.At present, domestic used for cosmetic Synthetic Oil is mainly by import.Homemade grease, at smell, color all has very large gap with imported product on the quality stability.
Present technology is to use tosic acid, and thionamic acid, strong acid such as the vitriol oil be as catalyzer, and these catalyzer can cause the reaction system color yellow that shoals, and the product that obtains is not suitable for cosmetic industry.
Simultaneously, domestic employing highly basic depickling decoloration process produces a large amount of soap bases, these soap bases can the weight 2-10 of absorption own doubly oil and fat product, had a strong impact on last yield, the single step yield is lower.
The present invention adopts promotor, has prevented the reaction system colour-change, takes off flavor technology with depickling and combines, and can obtain complete water white oil and fat product.
Take off a large amount of soap base problems of generation in the flavor process for depickling, the present invention also passes through the adding of soap base solubility promoter, and cooperates stirring velocity, and temperature has been avoided the generation of soap base, has significantly improved yield, and once through yield is at least more than 90%.
Summary of the invention
The particular requirement that is based on cosmetic industry of the present invention is developed a kind of new and easy synthetic and purification process that is used for the used for cosmetic Synthetic Oil, and is made the Synthetic Oil that can access colorless and odorless in this way.
An object of the present invention is to provide a kind of method of synthetic and purifying used for cosmetic Synthetic Oil, can obtain the used for cosmetic Synthetic Oil of high purity and colorless and odorless by this method.
Another purpose of the present invention provides the used for cosmetic Synthetic Oil of a kind of high purity and colorless and odorless.
In one aspect, the invention provides a kind of method of synthetic and purifying used for cosmetic Synthetic Oil, may further comprise the steps:
(a) in the presence of catalyzer and promotor, will react to refluxing as the pure and mild acid of reactant heat temperature raising in reactor, until no globule generation and record the reaction mixture acid number and no longer descend, and finish esterification;
(b) reaction mixture is cooled to 50-65 ℃, adds alkali lye and be warming up to 70-90 ℃ then, thereby finish the alkali cleaning step, and obtain supernatant liquid by removing sub-cloud alkali lye; And
(c) extremely neutral with the supernatant liquid that washed with de-ionized water obtained, moisture, solvent and unreacted alcohol and the acid of underpressure distillation to remove remnants then, thus obtain required product.
In a preferred implementation, in step (b), add the soap base solvent so that reaction mixture is further carried out deodorization.
In a further preferred embodiment, the soap base solvent is the mixture of oil-dissolving solvent and water-soluble solvent, and wherein this oil-dissolving solvent is selected from least a in the group of being made up of arene, alkanes, halogenated hydrocarbon, cycloalkane, ethers, ketone and their derivative; This water-soluble solvent is selected from least a in the group of being made up of alcohols, aldehydes, ester class.
In a preferred implementation, add sorbent material afterwards with flavor that products therefrom is further decoloured in step (c).
In a preferred implementation, catalyzer is to be selected from by sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, thionamic acid, phenylbenzimidazole sulfonic acid, alkylsulphonic acid, strongly-acid ion exchange resin, solid acid, metal oxide M
xO
y, metal chloride MCl
xIn the group of forming one or more, wherein M is Zn, Ti, Sn or Fe.
In a preferred implementation, promotor be selected from by S-WAT, sulfurous acid, sodium bisulfite, Sulfothiorine, phosphorous acid, sodium phosphite, inferior sodium phosphate, nitrous acid, Sodium Nitrite, gallic acid ester, tertiary butyl methoxyphenol, ditertbutylparacresol, tertiary butylated hydroquinone, ethoxyquinoline, methyl polysiloxane, tocopherol, carotene, xitix, sesamol, Rosmarinus officinalis, in the group formed of forulic acid, gossypol, flavonoid, sterol, EDTA, citric acid, polyphosphoric acid one or more.
In a preferred implementation, in described reactant, mole proportioning that feeds intake of alkyd is that wherein hydroxyl and carboxyl scale dimension are held between the 0.5-1.5
In a preferred implementation, in step (a), add the band aqua, this band aqua is benzene,toluene,xylene, trimethylbenzene, hexane, hexanaphthene, normal heptane, sherwood oil, dithiocarbonic anhydride, chloroform, C
12-20In the group that isoparaffin is formed one or more, perhaps described band aqua is to be selected from N
2, He or Ar rare gas element.
In a preferred implementation, in step (b), use one or more to be selected from by NaOH, KOH, NaCO
3, NaHCO
3, K
2CO
3, the alkali lye in the group formed of thanomin, trolamine carries out described alkali cleaning.
In yet another aspect, the invention provides a kind of used for cosmetic Synthetic Oil that obtains by aforesaid method.
By method of the present invention, obtained the used for cosmetic Synthetic Oil of the required high purity colorless and odorless of cosmetic industry, by method of the present invention, the yield of the used for cosmetic Synthetic Oil of acquisition is at least more than 90%.In addition, method of the present invention has been simplified the purifying technique of used for cosmetic Synthetic Oil.
Embodiment
Below will describe the specific embodiment of the present invention in illustrational mode, by such description, these or other feature of the present invention, advantage are with more than you know.Should be appreciated that such embodiment is not used in the purpose that limits the scope of the invention.
According to an embodiment of the invention, the present invention carries out chemical deodorization decoloring to the used for cosmetic Synthetic Oil, is included in to use the promotor of control reaction color in this used for cosmetic Synthetic Oil process of preparation and use strong alkali solution to carry out alkali cleaning.
In another embodiment of the present invention, the invention provides a kind of method of synthetic and purifying used for cosmetic Synthetic Oil, may further comprise the steps:
(a) in the presence of catalyzer and promotor, will react to refluxing as the pure and mild acid of reactant heat temperature raising in reactor, until no globule generation and record the reaction mixture acid number and no longer descend, and finish esterification;
(b) reaction mixture is cooled to 50-65 ℃, adds alkali lye and be warming up to 70-90 ℃ then, thereby finish the alkali cleaning step, and obtain supernatant liquid by removing sub-cloud alkali lye; And
(c) extremely neutral with the supernatant liquid that washed with de-ionized water obtained, moisture, solvent and unreacted alcohol and the acid of underpressure distillation to remove remnants then, thus obtain required product.
As mentioning herein, the used for cosmetic grease comprises and is not limited to: natural animal-plant grease, for example Oleum Cocois, palm-kernel oil, plam oil, peanut oil, soybean oil, Oleum Gossypii semen, sesame oil, Semen Maydis oil, Thistle oil, wheatgerm oil, Viscotrol C, sweet almond oil, Rice pollard oil, tea tree oil, sunflower seed oil, sweet oil, shea butter, Lipoval A, algal oil, Jojoba oil, Oleum Hippophae or the like; Synthetic Oil, Wickenol 111 for example, Isopropyl myristate, sad caprin, stearin, butyl stearate, octyl stearate, the different stearyl ester of Unimac 5680, Wickenol 155, Octyl adipate, hexanodioic acid two oleyl alcohol esters, Tetradecyl tetradecanoate, Laurate methyl, isononyl isononanoate, the different monooctyl ester of different n-nonanoic acid, tetramethylolmethane four oleins, tetramethylolmethane four mountain Yu's acid esters, pentaerythritol tetraoctyl stearate, dioctyl phthalate (DOP), Dinonylphthalate or the like, the present invention relates generally to Synthetic Oil, for example isononyl isononanoate (ININ).
As used in this article, be preferably carboxylic acid as the acid of reactant, it can be that monobasic or poly-basic organic acid are (with chemical formula R
1COOH represents), such as but not limited to: acetate, butyric acid, n-nonanoic acid, sad, capric acid, PIVALIC ACID CRUDE (25), hexanodioic acid, toxilic acid, oxysuccinic acid, citric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Unimac 5680, mountain Yu's acid, oleic acid, linolic acid, phenylformic acid, Whitfield's ointment, phthalic acid, benzene tricarboxylic acid etc., and derivative, can use in them one or more, and these acid all can be commercially available.
As used herein, can be that monobasic or polynary organic alcohol are (with chemical formula R as the alcohol of reactant
2OH), such as but not limited to: ethanol, propyl alcohol, Virahol, butanols, octanol, nonyl alcohol, hexanol, hexylene glycol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, i-octadecanol, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), propylene glycol, butyleneglycol, phenol, p-cresol etc., and derivative, can use in them one or more, and these alcohol all can be commercially available.
Described acid and alcohol form the reaction of ester and can represent by following formula:
R
1COOH+R
2OH→R
1COOR
2+H
2O
As long as because the stink of product derives from use therein carboxylic acid in the esterification, therefore preferably, in the method according to the invention, mole proportioning that feeds intake of the alkyd in the reactant maintains hydroxyl and carboxyl ratio between 0.5-1.5.More preferably, in described reactant, if described alcohol is monohydroxy-alcohol, and described acid is monocarboxylic acid, and the mole proportioning of so described pure and mild acid is greater than 1, and preferred acid-alcohol ratio is between the 1-13, and especially to recommend acid-alcohol ratio be 1.2-1.5; If described alcohol is polyvalent alcohol, and described acid is monoprotic acid, the mole proportioning of so described alcohol and described acid is less than 1, preferable range, preferred suggestion is 0.5-0.9 for hydroxyl and carboxyl ratio, so that it is lower to control the amount of carboxylic acid wherein, thereby reach the smell of controlling product by the amount that reduces carboxylic acid.
In the esterification process of the inventive method, esterification preferably heats to reactant in having the reactor that water trap refluxes carries out under the reflux conditions (being generally about 80-260 ℃), do not have the obvious globule to produce in water trap, the reaction times is generally about 3-48h.
As used herein,, be preferably homogeneous catalyst, can include but not limited to: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, thionamic acid, phenylbenzimidazole sulfonic acid, alkylsulphonic acid, strongly-acid ion exchange resin, solid acid, metal oxide M as catalyzer
xO
y, metal chloride MCl
xIn the group of forming one or more, wherein M is Zn, Ti, Sn or Fe.Can use in them one or more, and these catalyzer all can be commercially available.Based on the gross weight of reactant acid and alcohol, the amount of the catalyzer that uses is 0.1-20wt%, is preferably 0.2-5wt%, is more preferably 0.2-0.6wt%.And the example of solid acid used herein includes but not limited to following several types solid acid, as the solid super-strong acid of load halogen, and the solid super-strong acid of carried heteropoly acid, load vitriolic solid super-strong acid M
xO
y/ SO
4 2-, metal oxide-loaded solid super-strong acid, the solid super-strong acid of composite oxides/rare earth/molecular sieve preferentially selects existing market to use more wide load vitriolic solid super-strong acid M
xO
y/ SO
4 2-, especially recommend commercial at present ZrO
2/ SO
4 2-, TiO
2/ SO
4 2-, Fe
2O
3/ SO
4 2-, or ZrO
2/ S
2O
8 2-
In the present invention, promotor is including but not limited to S-WAT, sulfurous acid, sodium bisulfite, Sulfothiorine, phosphorous acid, sodium phosphite, inferior sodium phosphate, nitrous acid, Sodium Nitrite, gallic acid ester, tertiary butyl methoxyphenol (BHA), ditertbutylparacresol (BHT), tertiary butylated hydroquinone, ethoxyquinoline, methyl polysiloxane, tocopherol and derivative thereof, carotene and derivative thereof, xitix and derivative thereof, sesamol, Rosmarinus officinalis class material, forulic acid and ester class thereof, gossypol, flavonoid and derivative thereof, sterol, EDTA, citric acid and ester class thereof, polyphosphoric acid and salt thereof, and the mixture of above two or more materials.Its effect is the color of control product.This promotor can stop the side reaction in the sour and pure esterification reaction process to take place, thereby reduces the color of reaction solution, makes the color of product reach the requirement of expectation, and preferred product is a water white transparency.Based on the gross weight of reactant acid and alcohol, the amount of the promotor that uses is 50-200wt%, is preferably 50-100wt%.
Preferably, add the band aqua in the esterif iotacation step (a) of the inventive method, purpose is to take away the water that produces in the reaction process by the band aqua, thereby adds the speed of fast response, improves reaction efficiency.In the present invention, reaction time of esterification can be shortened to below 12h by adding the band aqua.
In the method for this paper, the band aqua can be a benzene, toluene, dimethylbenzene, trimethylbenzene, hexane, hexanaphthene, normal heptane, sherwood oil, dithiocarbonic anhydride, chloroform, C
12-20Alkane can use wherein one or more.Based on the gross weight of reactant acid and alcohol, the amount of the band aqua that uses is 10-50wt%.The band aqua also can be N
2, rare gas elementes such as He or Ar.In addition, also can take the mode of vacuumizing from reaction system, to take moisture out of.
Because the amount for remaining carboxylic acid in the used for cosmetic Synthetic Oil product has strict demand.Based on the amount of initial carboxylic acid, remaining carboxylic acid preferably is lower than 1wt%, more preferably less than 0.1wt%, most preferably is 0, does not promptly have remaining carboxylic acid in the product.Therefore, method of the present invention comprises the alkali cleaning step.More specifically, the temperature of the reaction solution after esterification is finished reduces, and carries out alkaline step to for example adding alkali lye after about 50-65 ℃.
In the alkali cleaning step of the inventive method, excessive acid and the reaction of the highly basic of adding, this reaction can be represented with following formula:
xRCOOH+M(OH)x→x(RCOO)M+xH2O
In alkaline cleaning procedure, preferably adopt in the highly basic and unreacted carboxylic acid, as mentioned above, owing to further remove carboxylic acid fully, thus the smell of product can be further improved, essentially no special odor preferably reaches tasteless degree.
As used herein, alkali can be but be not limited to mineral alkali for example NaOH, KOH, Ca (OH)
2, CaO, Na
2CO
3, NaHCO
3, NH
3, perhaps organic bases is such as but not limited to trolamine, methyldiethanolamine etc.Based on the unreacted sour molar weight of product, the alkaline amount of using is 80-150mol%, is preferably 80-120mol%.And the temperature of the preferred alkali lye that adds is close with cooled temperature of charge, promptly also for about 50-65 ℃.
After adding alkali lye, by quick stirring (stirring velocity is about 15-500rpm) and for example be warmed up to 70-120 ℃ to finish the alkali cleaning step in the 20-50min.After alkali cleaning, the reaction solution layering is removed lower floor's alkali lye and is obtained supernatant liquid.This supernatant liquor of the preferred washed with de-ionized water of water is to neutral.
Usually in alkaline cleaning procedure, unreacted carboxylic acid can with the alkali lye neutralization reaction, produce a large amount of soap bases, and the industrial employing whizzer of conventional grease takes off soap.Yet, thisly be not easy to subsequent process by centrifugal method of taking off soap and separate, and loss 5-10% yield.Therefore, in the method for the invention, adopted adding soap base solubility promoter, and can be convenient to later separation, and made and can not produce the solid soap base in the alkaline cleaning procedure, improved the yield 3-8% of the inventive method by control stirring velocity, feed temperature.
Preferably, in the step (b) of the inventive method, add the soap base solvent so that reaction mixture is further carried out deodorization.As used herein, as the soap base solubility promoter, can be the mixture of two kinds of solvents.Wherein a kind of solvent polarity is low, is called oil-dissolving solvent, includes but not limited to: arene and derivative thereof, alkanes, halogenated hydrocarbon and derivative thereof, cycloalkane and derivative thereof, ethers and derivative thereof, ketone and derivative thereof, for example, benzene, toluene, dimethylbenzene, trimethylbenzene, normal heptane, sherwood oil, C
12-20Isoparaffin, hexanaphthene, normal hexane, dithiocarbonic anhydride, chloroform.The preferential boiling point of selecting is at 60-150 ℃ low polar solvent.Another solvent polarity height is called water-soluble solvent, includes but not limited to alcohols, aldehydes, and the ester class, for example, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and isomer thereof.The preferential boiling point of selecting is at 60-150 ℃ of inertia alcohols.
Preferably, utilize underpressure distillation to obtain more highly purified product at last with the dehydration dealcoholysis.
In the methods of the invention, if necessary, after the decompression dehydration dealcoholysis, the flavor that can decolour is handled.In the art, be generally used for the method for grease deodorization depickling mainly by vapor distillation deodorization, deodour by adsorber or alkali-refining deacidification deodorization etc.
In the method for the invention, as required, preferably after dehydration dealcoholysis step, also comprise adding sorbent material with flavor that products therefrom is further decoloured.
As used herein, as sorbent material, can mention but be not limited to: atlapulgite, gac, neutral alumina, diatomite, molecular sieve etc.Can use wherein one or more, and based on the gross weight of reaction solution, the amount of the sorbent material that uses is 0.1-10wt%, is preferably 0.2-1wt%.The time that sorbent material takes off flavor is generally about 30min-4h.Afterwards, by removing by filter sorbent material, and obtain product.
By aforesaid method, a kind of used for cosmetic Synthetic Oil that the present invention obtains, for example main component is the used for cosmetic Synthetic Oil of isononyl isononanoate (ININ).In the present invention, the yield of the used for cosmetic Synthetic Oil of acquisition is more than 90%, even more than 95%, for example is 98%.
In the present invention, the used for cosmetic Synthetic Oil that is obtained is a colorless and odorless, and wherein hydroxyl value is lower than 50mgKOH/g, preferably is lower than 5mgKOH; Moisture is lower than 0.5wt%, preferably is lower than 0.1wt%; Saponification value is about 187-202mgKOH/g, is preferably 190-195mgKOH/g; Acid number is lower than 2mgKOH/g, preferably is lower than 0.5mgKOH/g.
Various details embodiment can further understand and realize the present invention by these embodiment.
Embodiment
Embodiment 1: synthetic used for cosmetic isononyl isononanoate
Add with different n-nonanoic acid 350g, isononyl alcohol 400g, vitriol oil 5g, as the S-WAT 1g of promotor, as the hexanaphthene 100g of band aqua and to have in the reactor of water trap reflux, reflux to 140 ℃ under agitation, reacted 4 hours, and showed that up to no longer including the globule generation esterification finished.Reaction material liquid is cooled to 65 ℃, under agitation adds 8%Na
2CO
3Alkali lye 100g, the temperature of this alkali lye is identical with the reaction material liquid temp, stirs (300-500rpm) fast and be warmed up to 80 ℃ in 30min, stirs and slows down to 50-150rpm, continues to be warming up to 90 ℃, finishes the alkali cleaning step.After the alkali cleaning, standing demix is also discharged lower floor's alkali lye.The upper strata stillness of night to obtaining, be washed till neutrality with deionized water.Afterwards to supernatant liquor reduced vacuum gauge pressure 0.099MPa, distillation dehydration dealcoholysis.Afterwards, press product weight and add the 6%wt atlapulgite, under 80 ℃ of temperature, fully stir 60min, atlapulgite is removed in centrifuging, thereby obtains the product isononyl isononanoate, and yield is about 95%, and is colourless, odorlessness.Hydroxyl value is lower than 5mgOH/g (detection method ST-N 0801.20-1999), moisture is lower than 0.1% (detection method GB-T 9696-2008), saponification value 190mgKOH/g (detection method GB-T 5534-1995), acid number are lower than 0.5mgKOH/g (detection method GB-T 5530-2005).
Embodiment 2: the synthetic sad caprin of used for cosmetic
With sad capric acid (45: mixing acid 450g 55wt), glycerine 70g, tosic acid 1.4g, 2,6-ditertbutylparacresol (BHT) 0.5g has in the reactor of water trap reflux, be heated with stirring to 160 ℃, be evacuated to below the gauge pressure 0.9kg, reacted 16 hours, and showed that to loseing the globule generation esterification finished.Reaction material liquid is cooled to 55 ℃, under agitation adds synthermal 17%NaOH solution 500g, soap base solubility promoter Virahol 500g and hexanaphthene 500g, stir and be warming up to 75 ℃, kept 30 minutes, finish the alkali cleaning step.After the alkali cleaning, lower floor's alkali lye is discharged in layering.Get the upper strata stillness of night, use deionized water: the mixed solution of hexanaphthene 1: 1 (wt/wt) is washed till neutrality.The supernatant liquor that obtains under reduced pressure distills with dehydration and decylization hexane.Add the 0.5%wt activated carbon, under 80 ℃, fully stir 60min, activated carbon is removed in centrifuging.Obtain the sad caprin of product, yield is 92%, and this product is colourless and odorlessness.Its hydroxyl value is lower than 5mgOH/g, and moisture is lower than 0.15%, saponification value 337mgKOH/g, and acid number is lower than 0.5mgKOH/g.
Embodiment 3: synthetic used for cosmetic pentaerythritol tetraoctyl stearate
Add Unimac 5680 750g, tetramethylolmethane 80g, tetrabutyl titanate 8g, sodium phosphite 1g in the flask that has backflow and feed nitrogen 50L/h.Under agitation be heated to 240 ℃, reacted 20 hours, do not finish esterification to there being globule generation.Reaction material liquid is cooled to 50 ℃, under agitation adds synthermal 18%NaOH solution 800g, Virahol 800g and hexanaphthene 800g, stir and be warming up to 75 ℃, 30min finishes the alkali cleaning step.After the alkali cleaning, lower floor's alkali lye is discharged in layering.Get the upper strata stillness of night, use deionized water: the mixed solution of hexanaphthene 1: 1 (wt/wt) is washed till neutrality.The supernatant liquor decompression is distilled with dehydration and decylization hexane down.Add 0.5wt% activated carbon and 0.5 super-cell, under 80 ℃, fully stir 60min, atlapulgite is removed in centrifuging.Obtain the product pentaerythritol tetraoctyl stearate, yield is 98%, and product is light yellow transparent and do not have the liquid of special odor.Its hydroxyl value is lower than 5mgOH/g, and moisture is lower than 0.15%, saponification value 187KOH/g, and acid number is lower than 0.5mgKOH/g.
Comparative example: synthetic iso-octyl palmitate
With palmitinic acid 400g, isooctyl alcohol 280g, tosic acid 1.2g, add and have in the reactor of water trap reflux, vacuumize 0.099Mpa reflux to 140 ℃ under agitation, reacted about 4 hours, no longer include the globule and produce and show that esterification finishes.This moment, the feed liquid jaundice was cooled to 60 ℃ with reaction material liquid, under agitation added 8%KOH alkali lye 50g, and the temperature of this alkali lye is identical with the reaction material liquid temp, stirs (400rpm) fast and be warmed up to 90 ℃ in 30min, finished the alkali cleaning step.After the alkali cleaning, produce a large amount of soap bases, can't realize standing demix, filter soap base, filtrate layering and discharge lower floor's alkali lye again with filter cloth.The upper strata stillness of night to obtaining, be washed till neutrality with deionized water.Afterwards to supernatant liquor reduced vacuum gauge pressure 0.099MPa, distillation dehydration dealcoholysis.Afterwards, press product weight and add the 6%wt atlapulgite, under 80 ℃ of temperature, fully stir 60min, atlapulgite is removed in centrifuging, thereby obtains the product iso-octyl palmitate, and yield is about 45%, and is faint yellow, and special odor is arranged.
In the method for the invention,, stop side reaction to take place, make the product color reach the makeup requirement, even be colourless by in esterification reaction process, adding promotor.In addition, by the control saponification value, hydroxyl value, peroxide value, indexs such as acid number, purity and corresponding index have reached the cosmetics-stage requirement, made the used for cosmetic Synthetic Oil of high purity colorless and odorless, its yield can be up to about 98%, and its residual acid acid number can be lower than 0.5mgKOH/g, and residual pure hydroxyl value can be lower than 5mgKOH/g.
Claims (10)
1. the method for a synthetic and purifying used for cosmetic Synthetic Oil may further comprise the steps:
(a) in the presence of catalyzer and promotor, will react to refluxing as the pure and mild acid of reactant heat temperature raising in reactor, until no globule generation and record the reaction mixture acid number and no longer descend, and finish esterification;
(b) reaction mixture is cooled to 50-65 ℃, adds alkali lye and be warming up to 70-90 ℃ then, thereby finish the alkali cleaning step, and obtain supernatant liquid by removing sub-cloud alkali lye; And
(c) extremely neutral with the supernatant liquid that washed with de-ionized water obtained, moisture, solvent and unreacted alcohol and the acid of underpressure distillation to remove remnants then, thus obtain required product.
2. method according to claim 1 wherein, adds the soap base solvent so that reaction mixture is further carried out deodorization in described step (b).
3. method according to claim 2, wherein, described soap base solvent is the mixture of oil-dissolving solvent and water-soluble solvent, and wherein said oil-dissolving solvent is selected from least a in the group of being made up of arene, alkanes, halogenated hydrocarbon, cycloalkane, ethers, ketone and their derivative; Described water-soluble solvent is selected from least a in the group of being made up of alcohols, aldehydes, ester class.
4. method according to claim 1 wherein, adds sorbent material with flavor that products therefrom is further decoloured afterwards in described step (c).
5. according to each described method in the claim 1 to 4, wherein, described catalyzer is to be selected from by sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, thionamic acid, phenylbenzimidazole sulfonic acid, alkylsulphonic acid, strongly-acid ion exchange resin, solid acid, metal oxide M
xO
y, metal chloride MCl
xIn the group of forming one or more, wherein M is Zn, Ti, Sn or Fe.
6. according to each described method in the claim 1 to 4, wherein, described promotor is to be selected from by S-WAT, sulfurous acid, sodium bisulfite, Sulfothiorine, phosphorous acid, sodium phosphite, inferior sodium phosphate, nitrous acid, Sodium Nitrite, gallic acid ester, tertiary butyl methoxyphenol, ditertbutylparacresol, tertiary butylated hydroquinone, ethoxyquinoline, methyl polysiloxane, tocopherol, carotene, xitix, sesamol, Rosmarinus officinalis, forulic acid, gossypol, flavonoid, sterol, EDTA, citric acid, in the group that polyphosphoric acid is formed one or more.
7. according to each described method in the claim 1 to 4, wherein, in described reactant, mole proportioning that feeds intake of alkyd is that wherein hydroxyl and carboxyl scale dimension are held between the 0.5-1.5.
8. according to each described method in the claim 1 to 4, wherein, add the band aqua in described step (a), described band aqua is benzene,toluene,xylene, trimethylbenzene, hexane, hexanaphthene, normal heptane, sherwood oil, dithiocarbonic anhydride, chloroform, C
12-20In the group that isoparaffin is formed one or more, perhaps described band aqua is to be selected from N
2, He or Ar rare gas element.
9. according to each described method in the claim 1 to 4, wherein, in described step (b), use one or more to be selected from by NaOH, KOH, NaCO
3, NaHCO
3, K
2CO
3, the alkali lye in the group formed of thanomin, trolamine carries out described alkali cleaning.
10. one kind is passed through the used for cosmetic Synthetic Oil that each described method obtains among the claim 1-9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010271475 CN101914014B (en) | 2010-09-03 | 2010-09-03 | Method for synthesizing and purifying synthetic ester oil for cosmetics and synthetic ester oil for cosmetics obtained by same |
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| CN 201010271475 CN101914014B (en) | 2010-09-03 | 2010-09-03 | Method for synthesizing and purifying synthetic ester oil for cosmetics and synthetic ester oil for cosmetics obtained by same |
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| CN101914014A true CN101914014A (en) | 2010-12-15 |
| CN101914014B CN101914014B (en) | 2013-09-25 |
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Cited By (11)
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| CN104232323A (en) * | 2013-06-24 | 2014-12-24 | 益海(连云港)油化工业有限公司 | Preparation process of fatty acid isooctyl ester |
| CN107417522A (en) * | 2017-05-22 | 2017-12-01 | 武汉桀升生物科技有限公司 | A kind of method for catalyzing and synthesizing the Compritol 888 ATO for pharmaceutic adjuvant |
| CN108774133A (en) * | 2018-08-06 | 2018-11-09 | 佛山市银美联合科技有限公司 | A method of removing ethyl hexanol or thylhexoic acid and esters building-up process smell |
| CN108893204A (en) * | 2018-07-18 | 2018-11-27 | 浙江大学 | Method of the inert gas with modified starch refined wool fat |
| CN109608331A (en) * | 2018-12-13 | 2019-04-12 | 东营市海科新源化工有限责任公司 | The preparation method of solid super acid catalyst and preparation method thereof, isononyl isononanoate |
| CN110526822A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | A kind of synthetic method of isooctyl ester nitrate |
| CN110845330A (en) * | 2019-11-25 | 2020-02-28 | 广东凯闻生物科技有限公司 | Triglycerol monostearate and preparation method and application thereof |
| CN114644557A (en) * | 2022-03-24 | 2022-06-21 | 华南理工大学 | Preparation method of isostearyl alcohol isostearate |
| WO2022134287A1 (en) * | 2020-12-25 | 2022-06-30 | 苏州大学 | Method for preparing carboxylic acid ester compound |
| WO2022134297A1 (en) * | 2020-12-25 | 2022-06-30 | 苏州大学 | Preparation method for carboxylate ester compound |
| CN115581966A (en) * | 2022-10-13 | 2023-01-10 | 广东凯闻生物科技有限公司 | Production process and application of triglycerol monostearate |
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| CN104232323B (en) * | 2013-06-24 | 2018-05-29 | 丰益油脂科技（连云港）有限公司 | The preparation process of fatty acid isooctyl |
| CN104232323A (en) * | 2013-06-24 | 2014-12-24 | 益海(连云港)油化工业有限公司 | Preparation process of fatty acid isooctyl ester |
| CN107417522A (en) * | 2017-05-22 | 2017-12-01 | 武汉桀升生物科技有限公司 | A kind of method for catalyzing and synthesizing the Compritol 888 ATO for pharmaceutic adjuvant |
| CN110526822A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | A kind of synthetic method of isooctyl ester nitrate |
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| CN108893204B (en) * | 2018-07-18 | 2020-06-05 | 浙江大学 | Method for synthesizing refined lanolin by inert gas with water method |
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| CN109608331B (en) * | 2018-12-13 | 2022-12-20 | 东营市海科新源化工有限责任公司 | Solid super acidic catalyst, preparation method thereof and preparation method of isononyl isononanoate |
| CN110845330A (en) * | 2019-11-25 | 2020-02-28 | 广东凯闻生物科技有限公司 | Triglycerol monostearate and preparation method and application thereof |
| WO2022134287A1 (en) * | 2020-12-25 | 2022-06-30 | 苏州大学 | Method for preparing carboxylic acid ester compound |
| WO2022134297A1 (en) * | 2020-12-25 | 2022-06-30 | 苏州大学 | Preparation method for carboxylate ester compound |
| CN114644557A (en) * | 2022-03-24 | 2022-06-21 | 华南理工大学 | Preparation method of isostearyl alcohol isostearate |
| CN115581966A (en) * | 2022-10-13 | 2023-01-10 | 广东凯闻生物科技有限公司 | Production process and application of triglycerol monostearate |
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