CN101774985B - Method for preparing epoxidized methyl acetorieinoleate - Google Patents
Method for preparing epoxidized methyl acetorieinoleate Download PDFInfo
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- CN101774985B CN101774985B CN2010101067994A CN201010106799A CN101774985B CN 101774985 B CN101774985 B CN 101774985B CN 2010101067994 A CN2010101067994 A CN 2010101067994A CN 201010106799 A CN201010106799 A CN 201010106799A CN 101774985 B CN101774985 B CN 101774985B
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Abstract
The invention relates to a method for preparing epoxidized methyl acetorieinoleate, which is processed by the following steps: (1) under the condition that the reaction pressure is the normal pressure and the reaction temperature is between the room temperature and 140 DEG C, adding a solid acid NaHSO4 catalyst into a mixed liquor of methyl ricinoleate and acetic anhydride, stirring the mixture, wherein the usage amount of the solid acid NaHSO4 catalyst occupies more than or equal to 0.1 percent of methyl ricinoleate by mass, the mole ratio of the methyl ricinoleate to the acetic anhydride is 1:1.5-2.5 and the reaction time is between 0.1 and 10 hours; (2) directly making the reaction liquid in the step (1) carry out epoxidation with aqueous solution of H2O2, wherein the mole ratio of methyl acetylricinolate to H2O2 is 1:1-2, the reaction temperature is between the room temperature and 100 DEG C, the reaction time is between 1 and 10 hours and the reaction pressure is the normal pressure; and (3) after washing the crude epoxidized methyl acetorieinoleate until the epoxidized methyl acetorieinoleate is neutral, dehydrating to obtain the refined epoxidized methyl acetorieinoleate. The method reduces the acetylation reaction temperature from 140 DEG C to between 60 and 80 DEG C and catalyzes the epoxidation of the acetylated product so as to improve the epoxide number of the epoxidation product.
Description
Technical field
The present invention relates to a kind of method for preparing epoxidized methyl acetorieinoleate, it adopts the ricinolic acid methyl esters is raw material, solid acid NaHSO
4Make catalyzer and prepare epoxidized methyl acetorieinoleate through acetylize, epoxidation.
Background technology
Epoxidized methyl acetorieinoleate is to plant to have efficient, nontoxic, degradable plant epoxy plasticizer, epoxide group can capture the PVC isolated free radical Cl-that degrades, can significantly improve fast light, the thermotolerance of PVC goods, have advantages such as heat-resisting, cold-resistant, nontoxic, can be applicable to process the various wrapping material that contact with food, toy and medicine equipment.It still is a PVC auxiliary heat stabilizer commonly used, uses the consumption that can reduce organic metal salt simultaneously with the organo-metallic salt stabilizing agent, can directly substitute traditional phthalic ester plasticizer, is the direction of softening agent industry product adjustment from now on.So the development space of epoxidized methyl acetorieinoleate is wide.
At present, the preparation epoxidized methyl acetorieinoleate needs to go on foot through acidylate and epoxy reaction two, and acylation reaction is under than higher temperature, does not add catalyzer and reacts [National University of the Inner Mongol's journal, 2006,21 (1): 39-40].Zheng Shunji etc. have reported acetylation [Shaanxi Tech Univ's journal of lanolin (main component is a fatty acid triglycercide); 2003; 21 (1): 31-34]; adopt no catalysis high temperature (140 ℃) lanolin and aceticanhydride to carry out acetylization reaction; transformation efficiency 84.7%; distill unnecessary aceticanhydride, washed several times with water promptly gets product again.But, cause the purity of product to descend because hydroxyl bond at high temperature alkoxide and dehydration reaction can take place in the ricinolic acid methyl esters; Contain in the ricinolic acid methyl esters molecule one unsaturated two strong, polymerization reaction take place easily at high temperature influences the yield and the color and luster of reactor product, the product processing of need decolouring; And react under higher temperature, the energy consumption demand is bigger; In addition, this production process need increase distillation workshop section, distills unnecessary aceticanhydride, and washes, and produces trade effluent.
Epoxy reaction adopts the vitriol oil, organic acid, resin, tosic acid etc. to make catalyzer to add the carrying out of fast response usually.Also have the acidity of utilizing formic acid or acetate self under the catalyst-free situation realize epoxidised report [Shi Saiquan etc. no sulphuric acid environment epoxidised soybean oil synthesis condition is optimized. chemical industry progress .2008,27 (5): 753-756], but the reaction times is long.
Therefore above-mentioned deficiency still has is worth improved place.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art; the method for preparing epoxidized methyl acetorieinoleate that a kind of acetylization reaction temperature is low, Epoxidation activity is high is provided; aceticanhydride and catalyzer that acetylization reaction is excessive are not removed; and be used for next step epoxidation process; reduce the separating measure of aceticanhydride and catalyzer, adopted solid acid NaHSO simultaneously
4Have advantages such as low price, non-volatile and high flexibility, thereby overcome the severe corrosive of other catalyzer and the shortcoming of contaminate environment, realize the object of the invention.
The object of the invention realizes that main the improvement on a large amount of experiment sieving bases selected common low-cost solid acid NaHSO
4Make catalyzer, can directly apply to the acidylate and the epoxy reaction of ricinolic acid methyl esters, catalyzer need not separate in the reaction process, can directly use.Acetate after the acylation reaction and catalyzer can directly carry out epoxidation reaction, need not handle, and reduce reactions steps, shorten the reaction times, have reduced loss, the reduction product cost of the energy and goods and materials in the production process.
Ricinolic acid methyl esters acetylization reaction formula of the present invention is as follows:
Methyl acetylricinolate epoxidation reaction formula of the present invention is as follows:
A kind of method for preparing epoxidized methyl acetorieinoleate that the present invention proposes, described method is carried out successively as follows:
(1) reaction pressure is a condition of normal pressure, and temperature of reaction is room temperature～140 ℃, is preferably 60-80 ℃, with solid acid NaHSO
4Catalyzer joins in the mixed solution of ricinolic acid methyl esters and aceticanhydride, stirs, and carries out the acetyl reaction; The solid acid NaHSO of wherein said catalyzer
4Consumption be the ricinolic acid methyl esters in mass 〉=0.1%, catalyst levels preferably is 0.5-1.5% in mass, the mol ratio 1 of wherein said ricinolic acid methyl esters and acid anhydrides: 1.5-2.5; Reaction times 0.1-10h;
(2) the direct and H with the reaction solution of step (1)
2O
2The aqueous solution carries out epoxidation reaction, and the acetate that aceticanhydride that catalyzer and acetylize are unnecessary and reaction produce can directly be participated in epoxy reaction, does not influence reaction, cuts down the consumption of energy; H wherein
2O
2The concentration of the aqueous solution is 30%-55%, described methyl acetylricinolate and H
2O
2Mol ratio be 1: 1-2; Wherein said temperature of reaction room temperature～100 ℃ is preferably 50-70 ℃, reaction times 1-10h, and reaction pressure is a normal pressure.
(3) the thick epoxidized methyl acetorieinoleate of step (2) is washed to neutrality after, must make with extra care epoxidized methyl acetorieinoleate after the dehydration.
Reaction raw materials is same as the prior art, can be the ricinolic acid methyl esters that adopts usually.
Advantage of the present invention is:
1, the present invention adopts solid acid NaHSO
4As catalyzer, catalyzer is cheap and easy to get, and catalyzer can fully contact with reactant in the reaction process, has reduced the acetylize temperature.Because do not need too high-temperature, avoided hydroxyl bond in the ricinolic acid methyl esters that the generation of alkoxide and dehydration reaction at high temperature takes place, can also improve the purity of product.
2, the methyl acetylricinolate that makes directly carries out epoxy reaction, the solid acid NaHSO in the acidylate product
4Can be used as the catalyzer of epoxy process, acetate can be directly used in epoxidation process, simplifies technological process.
3, the inventive method is simple, easy handling, and the reaction times is short, and the yield height is little to equipment corrosion, both can reduce the energy, can reduce cost again.Reduced the acetylization reaction temperature, dropped to 60-80 ℃ from 140 ℃; And owing to owing to contain NaHSO in the acetylize product
4, the epoxidation reaction of catalyzing acetylization product, thus the oxirane value of epoxidation product improved.
The interval value that the present invention provides not is the accurate end value of mathematical concept, and test and Selection has association when interval, and suitably departing from end value is not cannot.
Below in conjunction with several specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the technical scheme qualification total to the present invention, some do not depart from the unsubstantiality of utility model design and change In the view of the technician; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
The comparative example: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), do not add catalyzer, reacted 2 hours down at 140 ℃, transformation efficiency is 83.4%; Hydrogen peroxide add-on 30% (concentration is 30%, and is as follows) does not add other catalyzer, and 65 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 3 hours again, and the product oxirane value is 3.3.
Embodiment 1: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), catalyst solid acid NaHSO
4Add-on is 1.5%, reacts 1 hour down at 70 ℃, and transformation efficiency reaches 93.37%; Hydrogen peroxide add-on 30%, 60 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 2.5 hours again, and the product oxirane value is 4.8..
Embodiment 2: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), catalyst solid acid NaHSO
4Add-on is 0.5%, reacts 2 hours down at 80 ℃, and transformation efficiency reaches 96.21%; Hydrogen peroxide add-on 40%, 60 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 3 hours again, and the product oxirane value is 4.9.
Embodiment 3: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), catalyst solid acid NaHSO
4Add-on is 1%, reacts 3 hours down at 60 ℃, and transformation efficiency reaches 90.36%; Hydrogen peroxide add-on 40%, 70 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 2 hours again, and the product oxirane value is 5.0.
Embodiment 4: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2.5), catalyst solid acid NaHSO
4Add-on is 1%, reacts 1 hour down at 70 ℃, and transformation efficiency reaches 94.41%; Hydrogen peroxide add-on 30%, 65 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 2 hours again, and the product oxirane value is 5.2.
Embodiment 5: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2.5), catalyst solid acid NaHSO
4Add-on is 0.5%, reacts 2 hours down at 60 ℃.Transformation efficiency reaches 90.31%; Hydrogen peroxide add-on 40%, 60 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 2.5 hours again, and the product oxirane value is 5.1.
Embodiment 6: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2.5), catalyst solid acid NaHSO
4Add-on is 1.5%, reacts 3 hours down at 80 ℃.Transformation efficiency reaches 96.35%; Hydrogen peroxide add-on 30%, 60 ℃ of temperature of reaction dripped hydrogen peroxide 0.5 hour, reacted 2 hours again, and the product oxirane value is 5.5.
Claims (2)
1. method for preparing epoxidized methyl acetorieinoleate is characterized in that carrying out as follows:
(1) reaction pressure is a normal pressure, and temperature of reaction is room temperature～140 ℃, with solid acid NaHSO
4Catalyzer joins in the mixed solution of ricinolic acid methyl esters and aceticanhydride, stirs, and carries out the acetyl reaction; The mol ratio 1 of wherein said ricinolic acid methyl esters and acid anhydrides: 1.5-2.5; Reaction times 0.1-10h; Wherein said catalyst levels accounts for the ricinolic acid methyl esters and is 0.5-1.5% in mass;
(2) the direct and H with the reaction solution of step (1)
2O
2The aqueous solution carries out epoxidation reaction, wherein H
2O
2The concentration of the aqueous solution is 30%-55%, described methyl acetylricinolate and H
2O
2Mol ratio be 1: 1-2; Wherein said temperature of reaction room temperature～100 ℃, reaction times 1-10h, reaction pressure is a normal pressure;
(3) the thick epoxidized methyl acetorieinoleate of step (2) is washed to neutrality after, dehydration must be made with extra care epoxidized methyl acetorieinoleate.
2. a kind of method for preparing epoxidized methyl acetorieinoleate according to claim 1 is characterized in that step (1) temperature of reaction is 60-80 ℃; Step (2) temperature of reaction is 50-70 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102060812B (en) * | 2010-12-28 | 2012-07-25 | 江苏高科石化股份有限公司 | Method for preparing epoxy fatty acid methyl ester |
| CN103666770B (en) * | 2013-12-03 | 2015-02-04 | 中国林业科学研究院林产化学工业研究所 | Preparation method of epoxy modified castor oil |
| CN105085442B (en) * | 2015-07-23 | 2019-01-04 | 广州市海珥玛植物油脂有限公司 | The double acetyl epoxidized vegetable oil esters of binary acid and its synthetic method |
| CN105801520A (en) * | 2016-04-07 | 2016-07-27 | 南京工业大学 | Method for preparing epoxy fatty acid ester by using microreactor |
| CN107176910B (en) * | 2017-05-17 | 2019-10-22 | 中国林业科学研究院林产化学工业研究所 | A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application |
| CN108530681B (en) * | 2018-01-23 | 2020-05-05 | 四川大学 | Method for improving compatibility of epoxy methyl acetylricinoleate plasticizer and PVC resin |
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