CN103436562B - Preparation method of oxalic acid epoxy vegetable oil acid glyceride - Google Patents
Preparation method of oxalic acid epoxy vegetable oil acid glyceride Download PDFInfo
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Abstract
The invention discloses a preparation method of oxalic acid epoxy vegetable oil acid glyceride, which comprises the following steps that (1), lipase is taken as a catalyst, epoxy soybean oil and glyceryl triacetate perform acyl exchange reaction, and a reaction product is recovered, and (2), the reaction product in Step (1) is subjected to twice molecular distillation, wherein unreacted glyceryl triacetate is recovered by primary separation, and a low-temperature fraction mainly containing oxalic acid epoxy vegetable oil acid glyceride and a high-temperature fraction mainly containing acetic acid di-epoxy vegetable oil acid glyceride are obtained by secondary separation. According to the preparation method, epoxy soybean oil and glyceryl triacetate perform ester exchange reaction, a process is simple, a reaction condition is mild, side reactions are fewer and the product is easy to separate. The immobilized lipase is used in a solvent-free system for catalyzing epoxy fatty acid and acetic acid to perform the acyl exchange reaction, so that the method is better in economical efficiency and environmental protection property.
Description
Technical field
The present invention relates to a kind of preparation method of oxalic acid epoxidized vegetable oil acid glyceride.
Background technology
Add the material that can make polymkeric substance plasticity strengthen in polymer materials to and can be called softening agent, be also called fluidizer or plasticizer; A kind of conventional plastics additive, the macromolecular material auxiliary agent of widespread use in industrial production.Softening agent conventionally structurally has polarity or part has polarity, is liquid or low melting point solid that high boiling point, difficult volatilization and polymkeric substance have good compatibility, can make the pliability increase of material or make material liquefaction.The plasticising principle of fluidizer is to be generally distributed between the macromolecular chain of plastics, can reduce intermolecular reactive force, and polymer viscosity is reduced, and snappiness strengthens.Use suitable softening agent can improve the performance of macromolecular material, reduce production costs, improve productivity effect.
China is the big country of plastics production and consumption in the world, is also the country of fluidizer consumption maximum in the world.In recent years, the rate of increase of China's additives for plastics remains on 10% left and right, and considerably beyond the average growth rate per annum of world's additives for plastics 4%, market potential is huge, and development prospect is wide.But fluidizer all be take DOP(dioctyl phthalate (DOP) for a long time) etc. the product of adjacent benzene class as main, DOP is universal fluidizer, be mainly used in the processing of polyvinyl chloride fat, also can be used for the processing of the superpolymer such as acetate resin, ABS resin and rubber, also can be used for making paint, dyestuff, dispersion agent etc.The PVC that the DOP of take is softening agent can be used for manufacturer's fabricate-leather, agricultural film, wrapping material, cable etc.Along with fluidizer is being widely used of food and medicine articles for use field, the research of its toxicity is also just more and more come into one's own.The research discovery of U.S. environment protection department, DOP can cause tissue canceration, upsets internal secretion.Although DOP still has arguement to human carcinogen's conclusion at present, due to consider fluidizer particularly DOP there is potential carcinogenic danger, all taked in the world corresponding measure to limit its use, the U.S. has stopped the production of six kinds of new phthalate products, and European Union has forbidden using in some articles for children the PVC material that contains DOP.
At present, China is nontoxic, the fluidizer kind of environmental protection is quite deficient, 15% of the underproduce industrial fluidizer ultimate production of fluidizer of non-adjacent benzene class, wherein biodegradable and take biomass as raw-material environment-friendly type plastic agent rare especially.Country adopts vigorous measures, and greatly develops non-adjacent benzene class fluidizer industry, from source, stops fluidizer to the pollution in food, pharmaceutical industries production process.The development of Future in China fluidizer industry, will follow the principle of saving, green, low-carbon (LC), environmental protection, safety, constantly industry restructuring, carries forward vigorously technological innovation, development high-performance, low consumption, nontoxic, environmental protection, biodegradable product.
Epoxy soybean oil has good thermotolerance, photostabilization, oozing property, low temperature flexibility mutually, and volatility is low, be current plasticization effect better and belong to softening agent prepared by nontoxic, environmental protection, renewable resources, apply extensive especially.Can be for the auxiliary agent of food, medicine Plastic Packaging Materials, toy for children and home decoration material.But the molecular weight of epoxy soybean oil is large, viscosity is large, mobility is poor, epoxy soybean oil modification is prepared into the epoxidized vegetable oil acid glyceride that contains ethanoyl, can significantly improve these shortcomings.Oxalic acid epoxidized vegetable oil acid glyceride is the plastics non-toxic plasticizer that a kind of novel character is good, than epoxy soybean oil good stability, good fluidity is good with the consistency of plastic pvc.But; existing oxalic acid epoxidized vegetable oil acid glyceride synthetic method is that vegetables oil is changed into after unsaturated fatty acids direactive glyceride; the synthetic oxalic acid Unsaturatcd fatty acid glycerides of acetylize then obtains oxalic acid epoxidized vegetable oil acid glyceride after epoxidation again.This technological process route is longer, the direactive glyceride of unsaturated fatty acids itself is exactly to be worth nonionic emulsifier higher and that be difficult to obtain by chemical method, also do not realize at present large-scale industrial production, therefore this processing route cost is higher, and product separation purifying is also more complicated.
Summary of the invention
For existing synthetic oxalic acid epoxidized vegetable oil acid glyceride complex technical process, the shortcoming that separation and purification difficulty is large, the invention provides a kind of preparation method of oxalic acid epoxidized vegetable oil acid glyceride.In the present invention; take epoxy soybean oil and vanay as raw material; by fixed lipase catalyzed acyl group permutoid reaction; reaction product reclaims by molecular distillation separated, can obtain take oxalic acid epoxidized vegetable oil acid glyceride and single acetic acid diepoxy vegetable oil acid glyceryl ester as main product.This reaction process process does not simply have side reaction to occur, and the transformation efficiency of epoxy soybean oil is more than 90%; Product is easy to separation, removes epoxy soybean oil-contg in unreacted vanay after product below 10%.
The present invention for achieving the above object, is achieved through the following technical solutions:
A preparation method for oxalic acid epoxidized vegetable oil acid glyceride, is characterized in that, comprises the steps:
(1) take lipase as catalyzer, epoxy soybean oil and vanay carry out acyl group permutoid reaction (transformation efficiency of epoxy soybean oil is more than 90%), reclaim reaction product;
(2) step (1) reaction product is through two-stage molecular distillation, the unreacted vanay of first step Separation and Recovery, second stage separation obtains take oxalic acid epoxidized vegetable oil acid glyceride as main low temperature fraction, and take single acetic acid diepoxy vegetable oil acid glyceryl ester as main high temperature cut.
Mol ratio >=the 2:1 of the described vanay of step (1) and epoxy soybean oil.
The mol ratio of described vanay and epoxy soybean oil is 4:1～8:1.
Moisture content in the described acyl group permutoid reaction of step (1) system is below 0.1%wt.
Described lipase is immobilized lipase.
Described lipase is lipase Novozym435, Lipozyme RM IM or Lipozyme TL IM.
The condition of described first step molecular distillation purifying is that pressure is below 50Pa, and vaporization temperature is 100 ℃～130 ℃, and the condition of second stage molecular distillation purifying is that pressure is below 20Pa, and vaporization temperature is 150 ℃～180 ℃.
The temperature of described acyl group permutoid reaction is 40-60 ℃, and agitation condition 50-300rpm left and right, more than reaction times 6h.
Lipase is the general name of the class of enzymes of catalyzing oil hydrolysis by using, the reaction such as hydrolysis that can the natural lipid of catalysis, esterification, transesterify.The present invention studies and finds that lipase is except the animal-plant oil of catalysis natural origin or lipid acid and fatty acid ester react, can also catalysis with the fatty acid ester generation acyl group permutoid reaction of epoxide group.Further research is found, when lipase-catalyzed epoxyfatty acid acyl group reacts, the epoxide group on fatty acid chain is unaffected.By this response characteristic of immobilized lipase, for the acyl group permutoid reaction of epoxidized vegetable oil and vanay, result shows to obtain the epoxidized vegetable oil acid glyceride that contains one or two ethanoyl, and then has formed the present invention.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention adopts epoxy soybean oil and vanay to carry out transesterification reaction, and process is simple, and reaction conditions is gentle, and side reaction is few, and product is easy to separation.
(2) present method, owing to having used immobilized lipase catalysis epoxyfatty acid and acetic acid in solvent-free system to carry out acyl group permutoid reaction, has better economy and the feature of environmental protection.
(3) the present invention has synthesized a kind of molecular weight (relatively epoxy soybean oil), and stability and mobility are better, the non-toxic plastic softening agent good with the good character of plastic pvc consistency.
Embodiment
Introduce in more detail by the following examples enforcement of the present invention.In described embodiment, all per-cent all in mass.
Embodiment 1
In reaction vessel, add epoxy soybean oil 100g; the mol ratio of vanay 65.4g(vanay and epoxy soybean oil is about 3:1); 8.2g lipase Novozym435(is provided by Novozymes Company), in the constant temperature blender with magnetic force of 50 ℃, with the stirring velocity of 200rpm, carry out acyl group permutoid reaction 6h.After question response finishes, the centrifugal or filtering separation Novozym435 by reaction mixture, reclaims acyl group permutoid reaction product.Reaction product is through two-stage molecular distillation purifying: the condition of first step molecular distillation purifying is that pressure is 30Pa, and vaporization temperature is 120 ℃, and the condition of second stage molecular distillation purifying is that pressure is 10Pa, and vaporization temperature is 170 ℃.Collect the light phase of second stage molecular distillation, obtain take oxalic acid epoxidized vegetable oil acid glyceride as main product 78.4g.Its acid number is 0.2 after testing, oxirane value 2.4, iodine number 2.6.In LC-MS analysis product, epoxyfatty acid triglyceride level does not detect, and single acetic acid diepoxy vegetable oil acid glyceride content is 3.6%, oxalic acid epoxidized vegetable oil acid glyceride 95.9%, and other fatty acid glycerine ester contents are 1.5%.
Embodiment 2
In reaction vessel, add epoxy soybean oil 100g; the mol ratio of vanay 130.8g(vanay and epoxy soybean oil is about 6:1); 12g lipase Novozym435 carries out acyl group permutoid reaction 6h with the stirring velocity of 200rpm in the constant temperature blender with magnetic force of 50 ℃.After question response finishes, the centrifugal or filtering separation Novozym435 by reaction mixture, reclaims acyl group permutoid reaction product.Reaction product is through two-stage molecular distillation purifying: the condition of first step molecular distillation purifying is that pressure is 30Pa, and vaporization temperature is 120 ℃, and the condition of second stage molecular distillation purifying is that pressure is 10Pa, and vaporization temperature is 170 ℃.Collect second stage molecular distillation and gently obtain mutually take oxalic acid epoxidized vegetable oil acid glyceride as main product 94.2g.Obtaining its oxirane value of acetic acid epoxidized vegetable oil acid glyceride mixture is 2.3, and acid number is 0.3, iodine number 2.5.In LC-MS analysis product, epoxy soybean oil does not detect, and single acetic acid diepoxy vegetable oil acid glyceride content is 2.2%, oxalic acid epoxidized vegetable oil acid glyceride 96.2%, and other fatty acid glycerine ester contents are 1.7%.
Embodiment 3
In reaction vessel, add epoxy soybean oil 100g; the mol ratio of vanay 130.8g(vanay and epoxy soybean oil is about 6:1); 23g Lipozyme RM IM carries out acyl group permutoid reaction 6h with the stirring velocity of 200rpm in the constant temperature blender with magnetic force of 50 ℃.After question response finishes, the centrifugal or filtering separation Lipozyme RM IM by reaction mixture, reclaims acyl group permutoid reaction product.Reaction product is through two-stage molecular distillation purifying: the condition of first step molecular distillation purifying is that pressure is 30Pa, and vaporization temperature is 120 ℃, and the condition of second stage molecular distillation purifying is that pressure is 10Pa, and vaporization temperature is 170 ℃.Collect second stage molecular distillation and gently obtain mutually take oxalic acid epoxidized vegetable oil acid glyceride as main product 92.3g.Obtaining its oxirane value of acetic acid epoxidized vegetable oil acid glyceride mixture is 2.3, and acid number is 0.25, iodine number 2.5.In LC-MS analysis product, epoxy soybean oil does not detect, and single acetic acid diepoxy vegetable oil acid glyceride content is 2.6%, oxalic acid epoxidized vegetable oil acid glyceride 96%, and other fatty acid glycerine ester contents are 1.4%.
Comparative example 1
Unsaturated mono-glycerides preparation: by 500g soybean oil, 150g glycerine, 15g immobilized lipase Novozym435 adds in reaction vessel, adding the 1250g trimethyl carbinol is solvent, stirring is carried out glycerolysis reaction and is prepared direactive glyceride, temperature of reaction is 50 ℃, and the reaction times is 8h, glycerine solution to fat products in the content of mono-glycerides be 70.5%.Utilize molecular distillation separation and purification direactive glyceride, molecular distillation condition is: vacuum tightness 0～5Pa, and vaporization temperature is 180 ℃, charging flow velocity 1.5mL/min, knifing motor speed 200r/min, 40 ℃ of condensing temperatures, 80 ℃ of preheating temperatures, 100 ℃ of opening for feed temperature; Obtaining content of monoglyceride in lighting end is 97%.
Acetylize: whipping appts, thermometer are being housed, are hanging in the there-necked flask of water device and reflux condensing tube; direactive glyceride 300g, the Glacial acetic acid 136g, benzene 110g and catalyst sulfuric acid (98%) 1.5g that once add above-mentioned sample soybean oil glycerine solution to obtain; water back flow reaction is hung in intensification; stopped reaction when aquifer yield reaches theoretical amount, decompression is extracted unreacted acetic acid out and is hung aqua benzene.Be recycled oily matter oxalic acid soybean oil acid glyceride.
Epoxidation: by above-mentioned quantitative oxalic acid soybean oil acid glyceride 500g, formic acid 22g, add in the four-hole bottle with whipping appts, thermometer, dropping funnel, reflux condensing tube, under stirring, be warming up to 55 ℃, under stirring, slowly splash into 50% hydrogen peroxide 200g(98% concentrated sulfuric acid catalyst 0.7g), after adding, at 75～80 ℃, react 4 hours, separate lower floor's sour water, upper strata oleoyl first with buck, be washed to neutrality, acid number can underpressure distillation below 0.6 except anhydrating, and filter and obtain light yellow oil oxalic acid epoxy soybean olein.Its oxirane value is 2.43, acid number 1.68, iodine number 2.46.
Claims (5)
1. a preparation method for oxalic acid epoxidized vegetable oil acid glyceride, is characterized in that, comprises the steps:
(1) take lipase as catalyzer, epoxy soybean oil and vanay carry out acyl group permutoid reaction, reclaim reaction product; The mol ratio of described vanay and epoxy soybean oil is 4:1～8:1, and the temperature of acyl group permutoid reaction is 40-60 ℃, and agitation condition 50-300rpm, more than reaction times 6h;
(2) step (1) reaction product is through two-stage molecular distillation, the unreacted vanay of first step Separation and Recovery, second stage separation obtains take oxalic acid epoxidized vegetable oil acid glyceride as main low temperature fraction, and take single acetic acid diepoxy vegetable oil acid glyceryl ester as main high temperature cut.
2. preparation method according to claim 1, is characterized in that, the moisture content in the described acyl group permutoid reaction of step (1) system is below 0.1%wt.
3. preparation method according to claim 1 and 2, is characterized in that, described lipase is immobilized lipase.
4. preparation method according to claim 3, is characterized in that, described lipase is lipase Novozym435, Lipozyme RM IM or Lipozyme TL IM.
5. preparation method according to claim 1 and 2, it is characterized in that, the condition of described first step molecular distillation purifying is that pressure is below 50Pa, and vaporization temperature is 100 ℃～130 ℃, the condition of second stage molecular distillation purifying is that pressure is below 20Pa, and vaporization temperature is 150 ℃～180 ℃.
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| CN110887906A (en) * | 2019-11-25 | 2020-03-17 | 贵州省产品质量监督检验院 | Method for rapidly determining epoxidized soybean oil in food |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285946A (en) * | 2011-06-28 | 2011-12-21 | 广州市海珥玛植物油脂有限公司 | Diacetyl epoxy glyceryl oleates and synthesis method thereof |
| CN102337306A (en) * | 2010-12-03 | 2012-02-01 | 江南大学 | Method for producing acylated monoglyceride plasticizer by holoenzyme method and produced acylated monoglyceride plasticizer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337306A (en) * | 2010-12-03 | 2012-02-01 | 江南大学 | Method for producing acylated monoglyceride plasticizer by holoenzyme method and produced acylated monoglyceride plasticizer |
| CN102285946A (en) * | 2011-06-28 | 2011-12-21 | 广州市海珥玛植物油脂有限公司 | Diacetyl epoxy glyceryl oleates and synthesis method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Lipase from Rhizomucor miehei as a biocatalyst in fats and oils modification;Rafael C. Rodrigues et al.;《Journal of Molecular Catalysis B: Enzymatic》;20101231;15-32 * |
| Rafael C. Rodrigues et al..Lipase from Rhizomucor miehei as a biocatalyst in fats and oils modification.《Journal of Molecular Catalysis B: Enzymatic》.2010,15-32. * |
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