CN100549001C - The method for preparing mixed epoxidized fatty acid monoester with rapeseed oil - Google Patents
The method for preparing mixed epoxidized fatty acid monoester with rapeseed oil Download PDFInfo
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- CN100549001C CN100549001C CNB2006100852717A CN200610085271A CN100549001C CN 100549001 C CN100549001 C CN 100549001C CN B2006100852717 A CNB2006100852717 A CN B2006100852717A CN 200610085271 A CN200610085271 A CN 200610085271A CN 100549001 C CN100549001 C CN 100549001C
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Abstract
What the present invention relates to is under a kind of solvent-free situation, by to alcohol with rapeseed oil in the presence of catalyzer, the mixing unsaturated fatty acids acid monoester that alcoholysis reaction prepares taking place, and then carry out process for epoxidation with epoxidizing agent, thereby prepares mixed epoxidized fatty acid monoester.The present invention is solvent-free, technology is simple, and environmental protection, economy have overcome the more difficult isolating shortcoming of mixing unsaturated fatty acids acid monoester and water, have improved conversion of raw material.The product color that adopts the present invention to make is shallow, steady quality; By product in the reaction process significantly reduces, the production efficiency height.And, in the present invention, adopt different polyvalent alcohols or their mixture, can prepare the mixing unsaturated fatty acids acid monoester of different performance.Make raw material and mix the unsaturated fatty acids acid monoester, prepare the mixed epoxidized fatty acid monoester of different indexs easily with this.
Description
Technical field
What the present invention relates to is under a kind of solvent-free situation, by to alcohol with rapeseed oil in the presence of catalyzer, the mixing unsaturated fatty acids acid monoester that alcoholysis reaction prepares taking place, and then carry out process for epoxidation with epoxidizing agent, belongs to technical field of organic synthesis.
Background technology
It is that raw material directly carries out epoxidised processing method with rapeseed oil, soybean oil directly that report was once arranged, and Zhi Bei epoxy rapeseed oil or epoxy soybean oil are mainly used in fields such as softening agent and tensio-active agent like this.Do not seen that rapeseed oil or soybean oil were raw material, and earlier carried out alcoholysis reaction and prepare and mix the unsaturated fatty acids acid monoester, more above-mentioned product had been carried out epoxidised processing method with alcohol; Zhi Bei mixed epoxidized fatty acid monoester again by a series of deep processing, is prepared the biopolyol of different varieties, different indexs thus, and they are mainly used in the urethane foam field.
Directly the epoxy rapeseed oil with the rapeseed oil preparation belongs to triglyceride level, molecular weight is bigger, and be the monoesters structure with rapeseed oil epoxidised again mixed epoxidized fatty acid monoester after alcoholysis, according to the difference of alcoholysis with alcohol, the functionality difference of product, bigger variation has correspondingly taken place owing to the change of functional group in the molecule in its physicochemical property; In addition, it has had certain hydrophilicity, and the solvability in water increases, and has improved the difficulty with water sepn.On the other hand, the steric hindrance of mixed epoxidized fatty acid monoester epoxide group is little than the steric hindrance in the epoxy rapeseed oil, and various conditions are comparatively convenient during deep processing.
Summary of the invention
The technical problem to be solved in the present invention just provides a kind of method for preparing mixed epoxidized fatty acid monoester with rapeseed oil.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: under condition of no solvent, with the rapeseed oil is starting raw material, in the presence of catalyzer, pass through alcoholysis reaction, obtain mixing the unsaturated fatty acids acid monoester, again epoxidizing agent is carried out epoxidation reaction with the aforesaid unsaturated fatty acids acid monoester that mixes, thereby prepare mixed epoxidized fatty acid monoester.
The principles of chemistry general formula of foundation of the present invention is as follows:
The alcoholysis reaction principle:
R ' OH represents alcohol.
The epoxidation reaction principle
Here R comprise-H-CH
3-C
6H
5-CH
3(CH
2)
nC
6H
5Deng.
Here R ' OOCHR
1=CHR
2Refer to mix the unsaturated fatty acids acid monoester.
In the above-mentioned alcoholysis reaction, temperature is controlled at 120 ℃--and between 240 ℃, when polyvalent alcohol and rapeseed oil carried out alcoholysis reaction, the reaction in early stage was synthesis under normal pressure, and the vacuum tightness of late phase reaction is 100-750Kpa, and the reaction times is 3～5h.
The catalyzer of alcoholysis reaction is the oxyhydroxide of alkali metal hydroxide, alkali-metal alkoxide, alkaline-earth metal, the oxide compound of alkaline-earth metal.Wherein alkali metal hydroxide can be selected sodium hydroxide, potassium hydroxide, lithium hydroxide for use; Alkali-metal alkoxide can be selected potassium methylate, sodium methylate, sodium ethylate, glycerine potassium alcoholate etc. for use; The oxyhydroxide of alkaline-earth metal is magnesium hydroxide, calcium hydroxide; The oxide compound of alkaline-earth metal is calcium oxide, magnesium oxide.
Catalyst consumption is the 0.01-2% of rapeseed oil quality consumption in the alcoholysis reaction.
Polyvalent alcohol in the above-mentioned alcoholysis reaction can be selected from:
Dibasic alcohol: propylene glycol, ethylene glycol, glycol ether, triglycol, 1,4-butyleneglycol etc.;
Trivalent alcohol: glycerol, TriMethylolPropane(TMP);
Tetravalent alcohol: tetramethylolmethane, methylglucoside;
Pentavalent alcohol: Xylitol;
Hexavalent alcohol: sorbyl alcohol, N.F,USP MANNITOL;
Preferred propylene glycol, ethylene glycol, glycol ether, triglycol, 1,4-butyleneglycol glycerol, TriMethylolPropane(TMP).
In the alcoholysis reaction, the consumption of alcohol and the mole ratio of rapeseed oil consumption are 2.0-3.8: 1.
The temperature of alcoholysis reaction is controlled between 70～240 ℃, and pressure is at-0.1～0.1MPa, 3～15 hours reaction times.
In the above-mentioned epoxidation reaction, temperature is controlled between 30 ℃～70 ℃, and the reaction times is 2.5h～12h.
The present invention adopts the peroxide organic acid as epoxidizing agent, when implementing, two kinds of methods is arranged usually:
First kind: directly adopt the peroxide organic acid as epoxidizing agent, the peroxide organic acid with mix the unsaturated fatty acids acid monoester and react, generate mixed epoxidized fatty acid monoester;
Second kind: adopt hydrogen peroxide as oxygenant, organic acid is as the precursor of transition oxygenant, and under catalyzer, hydrogen peroxide and organic acid react, generate the peroxide organic acid. make the peroxide organic acid and mix the unsaturated fatty acids acid monoester and carry out epoxidation reaction, the generation mixed epoxidized fatty acid monoester.This method has dual mode:
1, the peroxide organic acid prepares in advance
Hydrogen peroxide in the presence of catalyzer with the organic acid effect, generate the peroxide organic acid.
2, the limit coronite generates in epoxidization reaction process
Hydrogen peroxide is added drop-wise to contain in the solution that mixes unsaturated fatty acids monoesters and organic acid, catalyzer carries out epoxidation reaction.
In the epoxidation reaction, the peroxide organic acid comprises: peroxide organic acids such as peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, mistake oxyalkyl para Toluic Acid.When adopting second method, the organic acid that is adopted comprises organic acids such as formic acid, acetate, phenylformic acid, alkyl para Toluic Acid, adopts hydrogen peroxide as oxygenant, and catalyzer is phosphoric acid, sulfuric acid, acidic white earth, strong acidic ion resin etc.
The consumption of hydrogen peroxide is to calculate according to the unsaturated value that mixes the unsaturated fatty acids acid monoester, and actual add-on is 1.0～1.2 times of theoretical add-on.
The two concentration of employing dioxygen among the present invention is 30～40%.
When adopting phosphoric acid and sulfuric acid to make catalyzer, catalyst levels is to be mixed with 0.5%～5% of saturated fatty acid monoester weight, make catalyzer when adopting acidic white earth, its consumption is for mixing 1%～7% of unsaturated fatty acids acid monoester weight, when adopting strong acidic ion resin, its consumption is for mixing 1%～10% of unsaturated fatty acids acid monoester weight.
The consumption of formic acid also is to calculate according to the unsaturated value of unsaturated fatty acids acid monoester, and actual add-on is 0.2～0.8 times of theoretical add-on.
After epoxidation reaction finishes, be to the epoxidation product processed operation that deacidifies.
Deacidification technology has two kinds:
1) alkali cleaning → washing process: with excessive acid, use the salt water washing again in sodium carbonate solution with 1%～10% or 1%～10% the sodium hydroxide solution, wash with soft water the back.
2) salt water washing → washing process: after the saturated common salt water washing, with soft water washing 2～4 times.The saturated common salt amount of aqueous solution used is 20%～60% of a crude product, and soft water is 20%～60% of crude product.
In the deacidification technology, the temperature of alkali cleaning is 60 ℃～90 ℃, and the temperature of salt washing is 40 ℃～80 ℃.
The dehydration method of underpressure distillation.Vacuum tightness during underpressure distillation will be at 80kPa～750kPa, and temperature is 80 ℃-120 ℃, and the time is 30min-150min.
The mixed epoxidized fatty acid monoester that obtains with epoxidizing method of the present invention has the advantage of the following aspects:
1, adopts different polyvalent alcohols or their mixture, can prepare the mixing unsaturated fatty acids acid monoester of different performance.Make raw material and mix the unsaturated fatty acids acid monoester, prepare the mixed epoxidized fatty acid monoester of different indexs easily with this.
2, the lighter color of product, steady quality; By product in the reaction process significantly reduces, the production efficiency height.
3, this technology solventless method, technology is simple, environmental protection, economy.
4, the present invention has overcome mixing unsaturated fatty acids acid monoester and the more difficult isolating shortcoming of water, has improved conversion of raw material.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1
Add refining rapeseed oil 1000g, glycerol 221g in the glass still of 2L, potassium hydroxide 1.2g stirs and heats up, and control reaction temperature is at 160 ℃-240 ℃, and reaction 5h keeps 4h then under vacuum tightness is the situation of 150kPa.Be cooled to 75 ℃, add neutralizing agent 50% phosphatase 24 .2g and carry out neutralization reaction, keep 30min, add 250g water, standing demix behind the stirring 15min adds water 250g water again, layering removes the sub-cloud material after leaving standstill 30-60min behind the stirring 15min, to the upper strata material add again that a spot of soft water stirs, standing demix, separation, be to dewater under the 0.095MPa in vacuum tightness then, get final product to such an extent that mix the unsaturated fatty acids acid monoester.The unsaturated value of product is 3.46mol/kg.
Embodiment 2
Add refining rapeseed oil 1000g, glycol ether 254g in the glass still of 2L, potassium hydroxide 1.2g stirs and heats up, and control reaction temperature is at 160 ℃-240 ℃, and reaction 5.5h keeps 3h then under vacuum tightness is the situation of 150kPa.Be cooled to 75 ℃, add neutralizing agent 50% phosphatase 24 .2g and carry out neutralization reaction, keep 30min, add 250g water, standing demix behind the stirring 15min adds water 250g water again, layering removes the sub-cloud material after leaving standstill 30-60min behind the stirring 15min, to the upper strata material add again that a spot of soft water stirs, standing demix, separation, be to dewater under the 0.095MPa in vacuum tightness then, get final product to such an extent that mix the unsaturated fatty acids acid monoester.The unsaturated value of product is 3.38mol/kg.
Embodiment 3
Add refining rapeseed oil 1000g, propylene glycol 182g in the glass still of 2L, potassium hydroxide 1.1g stirs and heats up, and control reaction temperature is at 160 ℃-240 ℃, and reaction 5h keeps 4h then under vacuum tightness is the situation of 150kPa.Be cooled to 75 ℃, add neutralizing agent 50% phosphoric acid 3.9g and carry out neutralization reaction, keep 30min, add 250g water, standing demix behind the stirring 5min adds water 250g water again, layering removes the sub-cloud material after leaving standstill 30-60min behind the stirring 5min, to the upper strata material add again that a spot of soft water stirs, standing demix, separation, be to dewater under the 0.095MPa in vacuum tightness then, get final product to such an extent that mix the unsaturated fatty acids acid monoester.The unsaturated value of product is 3.54mol/kg.
Embodiment 4
In the glass still of 2L, add refining rapeseed oil 980g, propylene glycol 91.2g, TriMethylolPropane(TMP) 150g, 10% propylene glycol potassium 45g stirs and heats up, and control reaction temperature is at 160 ℃-240 ℃, and reaction 5h keeps 3h then under vacuum tightness is the situation of 150kPa.Be cooled to 75 ℃, add neutralizing agent 50% phosphatase 11 4.8g and carry out neutralization reaction, keep 30min, add 250g water, standing demix behind the stirring 15min adds water 250g water again, layering removes the sub-cloud material after leaving standstill 30-60min behind the stirring 5min, to the upper strata material add again that a spot of soft water stirs, standing demix, separation, be to dewater under the 0.095MPa in vacuum tightness then, get final product to such an extent that mix the unsaturated fatty acids acid monoester.The unsaturated value of product is 3.38mol/kg.
Embodiment 5
18% peroxyformic acid of 140 grams is added drop-wise in mixing unsaturated fatty acids acid monoester 100 grams (unsaturated value is 3.46mol/kg), the dropping time is 2h～3h, dropping temperature is 30 ℃～70 ℃, reaction is 5 hours under 30 ℃～70 ℃ temperature, back standing separation goes out the upper strata, respectively washes 2 times with saturated aqueous common salt and soft water, then under 80Kpa～750Kpa pressure, temperature is to carry out underpressure distillation under 80 ℃～120 ℃ conditions, promptly gets product epoxy mixing-in fat acid monoester.The oxirane value of testing product is 4.86%.
Embodiment 6
To mix unsaturated fatty acids acid monoester meter 200 grams (unsaturated value is 3.38mol/kg), 20 gram formic acid (80%), 8 acidic white earths that restrain, join in the three-necked bottle of 500ml, stir, drip 37% hydrogen peroxide of 76 grams, under 30 ℃～70 ℃ condition, react 2.5h～12h, by standing separation,, use saturated aqueous common salt and soft water washed twice again with 5% sodium carbonate solution washed twice, water is removed in back underpressure distillation, gets mixed epoxidized fatty acid monoester.The oxirane value of testing product is 4.78%.
Embodiment 7
To mix unsaturated fatty acids acid monoester 200 grams (unsaturated value is 3.54mol/kg), 85% formic acid, 18 grams, 50% sulfuric acid 2ml is added in the glass still, stir, be heated to 30 ℃～70 ℃, controlled temperature is about 30 ℃～70 ℃ then, 30% hydrogen peroxide, 96 grams are added drop-wise in the glass still, reacted 5 hours, back standing separation goes out the upper strata, respectively washes 2 times with saturated aqueous common salt and soft water, then under 80Kpa～750Kpa pressure, temperature is to carry out underpressure distillation under 80 ℃～120 ℃ conditions, promptly gets product epoxy mixing-in fat acid monoester.The oxirane value of testing product is 4.94%.
Embodiment 8
With 85% formic acid, 18 grams, 50% phosphoric acid, 6 grams, 94 grams, 30% hydrogen peroxide is 30 ℃～70 ℃ reactions down, generate the excessive peroxide organic formic acid of hydrogen peroxide, then it is added drop-wise to and is equipped with in 200 gram mixing unsaturated fatty acids acid monoester (unsaturated value is 3.54mol/kg) the glass stills, stir, controlled temperature is about 30 ℃～70 ℃, reaction 5h～12h, back standing separation goes out the upper strata, respectively washes 2 times with saturated aqueous common salt and soft water, then under 80Kpa～750Kpa pressure, temperature is to carry out underpressure distillation under 80 ℃～120 ℃ conditions, promptly gets product epoxy mixing-in fat acid monoester.The oxirane value of testing product is 4.88%.
Embodiment 9
With 85% formic acid, 18 grams, 4 gram 732# strong acidic ion resins, 94 grams, 30% hydrogen peroxide is 30 ℃～70 ℃ reactions down, generate the excessive peroxide organic formic acid of hydrogen peroxide, then it is added drop-wise to and is equipped with in 200 gram mixing unsaturated fatty acids acid monoester (unsaturated value is 3.54mol/kg) the glass stills, stir, controlled temperature is about 30 ℃～70 ℃, reaction 5h～12h, back standing separation goes out the upper strata, respectively washes 2 times with saturated aqueous common salt and soft water, then under 80Kpa～750Kpa pressure, temperature is to carry out underpressure distillation under 80 ℃～120 ℃ conditions, promptly gets product epoxy mixing-in fat acid monoester.The oxirane value of testing product is 4.95%.
Claims (16)
1, a kind of method for preparing mixed epoxidized fatty acid monoester with rapeseed oil, it is characterized in that under condition of no solvent, with the rapeseed oil is starting raw material, in the presence of catalyzer, pass through alcoholysis reaction, obtain mixing the unsaturated fatty acids acid monoester, again epoxidizing agent is carried out epoxidation reaction with the aforesaid unsaturated fatty acids acid monoester that mixes, thereby prepare mixed epoxidized fatty acid monoester.
2, in accordance with the method for claim 1, it is characterized in that the alcohol that uses in the alcoholysis reaction is polyvalent alcohol, is selected from:
Dibasic alcohol: propylene glycol or ethylene glycol, glycol ether, triglycol, 1,4-butyleneglycol;
Trivalent alcohol: glycerol or TriMethylolPropane(TMP);
Tetravalent alcohol: tetramethylolmethane or methylglucoside;
Pentavalent alcohol: Xylitol;
Hexavalent alcohol: sorbyl alcohol or N.F,USP MANNITOL;
In the alcoholysis reaction, the consumption of alcohol and the mole ratio of rapeseed oil consumption are 2.0～3.8: 1.
3, in accordance with the method for claim 1, the catalyzer that it is characterized in that alcoholysis reaction is the oxyhydroxide of alkali metal hydroxide, alkali-metal alkoxide, alkaline-earth metal, the oxide compound of alkaline-earth metal; Wherein alkali metal hydroxide is selected sodium hydroxide, potassium hydroxide, lithium hydroxide for use; Alkali-metal alkoxide is selected potassium methylate, sodium methylate, sodium ethylate, glycerine potassium alcoholate for use; The oxyhydroxide of alkaline-earth metal is magnesium hydroxide, calcium hydroxide; The oxide compound of alkaline-earth metal is calcium oxide, magnesium oxide; Catalyst consumption is the 0.01-2% of rapeseed oil quality consumption in the alcoholysis reaction.
4, in accordance with the method for claim 1, it is characterized in that epoxidizing agent is the peroxide organic acid.
5, in accordance with the method for claim 4, add the peroxide organic acid when it is characterized in that epoxidation reaction two kinds of methods arranged:
1) directly add the peroxide organic acid as epoxidizing agent, the peroxide organic acid with mix the unsaturated fatty acids acid monoester and react, generate mixed epoxidized fatty acid monoester;
2) adopt hydrogen peroxide as oxygenant, organic acid is as the precursor of transition oxygenant, under catalyzer, hydrogen peroxide and organic acid react, generate the peroxide organic acid, make the peroxide organic acid and mix the unsaturated fatty acids acid monoester and carry out epoxidation reaction, the generation mixed epoxidized fatty acid monoester.
6, in accordance with the method for claim 5, it is characterized in that organic acid is selected from formic acid, acetate, phenylformic acid, alkylbenzoic acid, alkylbenzene acetate, toluylic acid.
7, in accordance with the method for claim 5, when adding peroxide organic acid employing second method when it is characterized in that epoxidation reaction, described catalyzer is selected from acidic white earth, sulfuric acid, phosphoric acid, strong acidic ion resin; When catalyzer was selected sulfuric acid or phosphoric acid for use, its consumption accounted for and mixes 0.5%～5% of unsaturated fatty acids acid monoester weight; When catalyzer was acidic white earth, its consumption accounted for and mixes 1%～7% of unsaturated fatty acids acid monoester weight; When catalyzer was strong acidic ion resin, its consumption accounted for and mixes 1%～10% of unsaturated fatty acids acid monoester weight.
8, in accordance with the method for claim 5, the concentration that it is characterized in that hydrogen peroxide between 30%～40%, the consumption of hydrogen peroxide with mix the unsaturated fatty acids acid monoester in the mol ratio of unsaturated double-bond be 1.0～1.2: 1.
9, in accordance with the method for claim 5, it is characterized in that, used organic acid molar weight with mix the unsaturated fatty acids acid monoester in the mol ratio 0.2～0.8: 1 of unsaturated double-bond.
10, according to any described method of claim 1-9, it is characterized in that the alcoholysis reaction temperature is controlled between 70～240 ℃, pressure is at-0.1～0.1MPa, 3～15 hours reaction times.
According to any described method of claim 1-9, it is characterized in that 11, epoxidation reaction temperature is 30 ℃～70 ℃.
12,, it is characterized in that the epoxidation reaction time is 2.5～12 hours according to any described method of claim 1-9.
13, according to any described method of claim 1-9, it is characterized in that epoxidation reaction finishes after, dehydration deacidify.
14, in accordance with the method for claim 13, it is characterized in that one of following two kinds of methods of deacidification employing:
1) alkali cleaning → washing process: with excessive acid, use the salt water washing again in sodium carbonate solution with 1%～10% or 1%～10% the sodium hydroxide solution, wash with soft water the back;
2) salt water washing → washing process: after the saturated common salt water washing, with soft water washing 2～4 times; The saturated common salt amount of aqueous solution used is 20%～60% of a crude product, and soft water is 20%～60% of crude product.
15, in accordance with the method for claim 14, the temperature that it is characterized in that its alkali cleaning is 60 ℃～90 ℃, and the temperature of salt washing is 40 ℃～80 ℃.
16, in accordance with the method for claim 14, it is characterized in that dehydration employing vacuum distillation method, vacuum tightness will be at 80kPa～750kPa, and temperature is 80 ℃～120 ℃, and the time is 30～50 fens kinds.
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| CN101139328B (en) * | 2007-10-15 | 2011-02-02 | 源华能源科技（福建）有限公司 | Novel process for synthesizing epoxy aliphatic acid methyl ester |
| CN101691524A (en) * | 2009-10-20 | 2010-04-07 | 华东理工大学 | Method for preparing epoxidized soybean oil with high epoxy value by fractional step method |
| CN102628005A (en) * | 2012-04-10 | 2012-08-08 | 北京化工大学常州先进材料研究院 | Epoxidized fatty acid (ester) and preparation method thereof |
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Non-Patent Citations (2)
| Title |
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| 环氧大豆油生产工艺的改进. 施肖峰，王景军.中国油脂，第20卷第2期. 1995 |
| 环氧大豆油生产工艺的改进. 施肖峰，王景军.中国油脂，第20卷第2期. 1995 * |
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