CN101974369A - Synthesis method of epoxidized soybean oil - Google Patents
Synthesis method of epoxidized soybean oil Download PDFInfo
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- CN101974369A CN101974369A CN2010102738534A CN201010273853A CN101974369A CN 101974369 A CN101974369 A CN 101974369A CN 2010102738534 A CN2010102738534 A CN 2010102738534A CN 201010273853 A CN201010273853 A CN 201010273853A CN 101974369 A CN101974369 A CN 101974369A
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- 239000003549 soybean oil Substances 0.000 title claims abstract description 86
- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 86
- 238000001308 synthesis method Methods 0.000 title abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 19
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims description 55
- 239000003153 chemical reaction reagent Substances 0.000 claims description 21
- 238000010189 synthetic method Methods 0.000 claims description 20
- 239000006174 pH buffer Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 239000012451 post-reaction mixture Substances 0.000 claims 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 abstract 1
- 239000006179 pH buffering agent Substances 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 20
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 14
- 229910052740 iodine Inorganic materials 0.000 description 14
- 239000011630 iodine Substances 0.000 description 14
- 230000007613 environmental effect Effects 0.000 description 8
- 239000004902 Softening Agent Substances 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000000872 buffer Substances 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 cyclic carbonate esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- QLFFCLRSMTUBEZ-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].[Na].OP(O)(O)=O QLFFCLRSMTUBEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- NWJXSVNLQJZDLV-UHFFFAOYSA-N formic acid;hydrogen peroxide Chemical compound OO.OC=O NWJXSVNLQJZDLV-UHFFFAOYSA-N 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a synthesis method of epoxidized soybean oil. In the method, soybean oil, oxydol and tungsten trioxide are respectively used as a raw material, an oxygen source and an active oxygen vector and are heated without adding organic solvent in the presence of a phase transfer catalyst to be subject to an epoxidation reaction so as to synthesize the epoxidized soybean oil. In the reaction system, a pH buffering agent is preferably added, and epoxidized soybean oil of higher quality can be obtained. By not using carboxylic acid as the active oxygen vector, not using strong acid as the catalyst and not using organic solvent in the scheme, the invention has the advantages of small catalyst dose, high reaction activity, less reaction byproduct, simple post treatment of products and no requirement for deacidification by water washing, thereby being an environment friendly and efficient synthesis method of epoxidized soybean oil.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of synthetic method of not having the epoxy soybean oil under carboxylic acid oxygen carrier, no strong acid catalyst, the condition of no solvent.
Technical background
Epoxy soybean oil is a kind of based on natural reproducible resource---the environmental friendly product of soybean oil, have important in the plastic plasticizer field and use widely, have nontoxic, fully biodegradable, photo and thermal stability is good, consistency good, volatility is low, mobility is little characteristics.When particularly being applied to polyvinyl chloride plasticising, not only have good plasticization effect, and contained epoxy group(ing) has heat stabilization to polyvinyl chloride.Enhancing along with people's environmental consciousness, and the raising that Product Safety is required, epoxy soybean oil will obtain application more and more widely in the softening agent field, particularly particularly important in the application in fields such as medical treatment, food product pack, daily necessities, family adornment, toy for children.It is worth noting, the application of epoxy soybean oil not only is confined to softening agent, also constantly be developed based on new variety such as the soybean oil polyvalent alcohol of epoxy soybean oil, epoxy soybean oil acrylate, epoxy soybean oil cyclic carbonate esters in recent years, particularly obtain important application in aspects such as non-isocyanate polyurethane, photocuring environmental protection coating material and printing ink at novel degradable polyurethane.Therefore, epoxy soybean oil has very extensively and important practical value, and synthetic method is significant efficiently to research and develop it.
Through the epoxidation reaction preparation, present widely used epoxy soybean oil synthetic method is to be that oxygen source, formic acid are the active oxygen carrier with the hydrogen peroxide to epoxy soybean oil, adds or does not add strong acid catalyst and carry out epoxidation reaction by soybean oil.The serious problems that this method exists are to contain a large amount of formic acid in the system, formic acid itself has the strong stimulation smell, and be corrosive, not only easily human body is damaged, and strong to the corrodibility of equipment, particularly adding under the strong acid catalyst situation, corrosion to equipment is more serious, and after epoxidation reaction, need to cause a large amount of acidic industrial effluents with the massive laundering deacidification.Therefore this method is not a kind of eco-friendly cleaner production.And the common reaction efficiency of this method is not high, under sour environment the open loop side reaction of epoxy group(ing) more serious, be difficult to obtain the epoxy soybean oil of high epoxy value (＞6.5).Therefore how to develop a kind of environmental protection, the epoxy soybean oil synthetic method gets more and more people's extensive concerning efficiently.
Patent CN101445495A discloses the soybean oil epoxidizing method of a kind of less energy-consumption, few waste water, epoxidation systems is hydrogen peroxide-formic acid, its focus is the aftertreatment of crude product, reach the effect of falling acid and drying products with once washing again by steam distillation, reduce the generation of trade effluent; Patent CN101235021A then discloses the method that a kind of heteropoly acid catalysis prepares epoxy soybean oil, with solid-state heteropolyacid salt Q
mYM
pO
q(H
2O)
nBe catalyzer, do not add carboxylic acid, no protonic acid, solvent-free, the no acidic waste water of epoxidation process produces, but the oxirane value of product not high (oxirane value＜6.0); Patent CN101591588A discloses the method for a kind of organic rhenium oxide-urea peroxide catalytic preparation epoxy soybean oil, this method is that oxygen source, organic rhenium oxide are the active oxygen carrier with the urea peroxide, avoided the use of carboxylic acid and strong acid equally, and obtained high epoxy value epoxy soybean oil (oxirane value＞7), but used catalyst system cost is higher, the urea peroxide large usage quantity is 50%～100% of soybean oil quality, and urea peroxide reaction back produces a large amount of by product urea.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of environmental protection, efficiently, soybean oil epoxidizing method cheaply.
More preferably, the present invention is by providing optimized technical scheme, in environmental protection, can also guarantee to obtain the epoxy soybean oil of oxirane value＞6.5 on the beneficial effect basis efficiently, cheaply.
Purpose of the present invention is achieved by the following technical programs:
Provide a kind of environmental protection, efficiently, the synthetic method of epoxy soybean oil cheaply, be to be that raw material, hydrogen peroxide are oxygen source, tungstic oxide (WO with the soybean oil
3) be the active oxygen carrier, do not add organic solvent, in the presence of phase-transfer catalyst, the synthetic epoxy soybean oil that obtains of epoxidation reaction is carried out in heating.
Described soybean oil epoxidizing method specifically may further comprise the steps:
(1) in reaction vessel, add tungstic oxide, part hydrogen peroxide, phase-transfer catalyst and soybean oil respectively by proportioning, after stirring, temperature reaction;
(2) hydrogen peroxide of dropping remainder in 1.5～2h, control hydrogen peroxide rate of addition, the temperature of control reaction system, hydrogen peroxide drips off the back and continues to react for some time, total reaction time 4～8h (the dropping time that comprises hydrogen peroxide);
(3) after reaction finished, reaction mixture washed with warm water, and standing demix is removed water, and organic phase gets the epoxy soybean oil production after underpressure distillation dewaters, filters.Usually washing gets final product for 1 time.
Preferably, the synthetic method of epoxy soybean oil of the present invention is to be that raw material, hydrogen peroxide are oxygen source, tungstic oxide (WO with the soybean oil
3) be the active oxygen carrier, do not add organic solvent, in the presence of phase-transfer catalyst and pH buffer reagent were common, epoxidation reaction was carried out in heating, the epoxy soybean oil of acquisition oxirane value＞6.5.
Different with the previous reaction step is step (1), and step (1) is to add tungstic oxide, part hydrogen peroxide, phase-transfer catalyst, pH buffer reagent and soybean oil respectively by proportioning in reaction vessel, after stirring, and temperature reaction.
The consumption of described tungstic oxide is preferably 0.2%～0.7% of soybean oil quality;
The consumption of described hydrogen peroxide (in clean hydrogen peroxide) is 18.5%～22.5% of a soybean oil quality; It is 50% hydrogen peroxide that the present invention preferably adopts mass percent concentration.
Described hydrogen peroxide is divided into two portions to be added, can be according to 5～15: 95～85 ratio is divided into two portions with described hydrogen peroxide and adds; Optimized technical scheme is the ratio according to 10: 90, i.e. during reaction beginning, add 10% hydrogen peroxide earlier, and remaining 90% hydrogen peroxide drips in reaction process.
Preferred three n-octyl methyl quaternary ammonium the dihydrogen phosphate ([CH of described phase-transfer catalyst
3(n-C
8H
17)
3N]
+H
2PO
4 -), the effect of phase-transfer catalyst is that the intermediate product that contains active oxygen that the reaction of hydrogen peroxide and tungstic oxide generates is transferred to the oil phase from water, promotes the carrying out of epoxidation reaction; Tungstic oxide and phase-transfer catalyst consumption increase, and epoxidation reaction is had promoter action, can obtain the product of high epoxy value and low iodine number in shorter time, but the corresponding increase of production cost.The consumption of the preferred phase-transfer catalyst of the present invention is 0.3%～1% of a soybean oil quality.If use other phase-transfer catalysts, its consumption can be consulted and used.
Described pH buffer reagent can be selected sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic etc., preferably phosphoric acid disodium hydrogen of the present invention for use.The purpose that the present invention adds the pH buffer reagent is the epoxidation reaction that makes soybean oil near carrying out under the neutrallty condition, thereby suppress the open loop side reaction that epoxy group(ing) causes because of acid, experimental results show that, add suitable pH buffer reagent and help improving the product oxirane value, the quality of gained epoxy soybean oil is better improved.The present invention is by long-term a large amount of creativeness experiment and analysis, when the pH buffer reagent is not added in summary, under the lower situation of other catalyst levelss and temperature of reaction, same reaction is in the time, the remaining iodine number of product is lower, be that double bond conversion rate is higher, but the oxirane value of product is low all the better, illustrates that the open loop side reaction of epoxy group(ing) in the reaction process is more serious.If but when pH buffer reagent consumption increased, epoxidation reaction speed can descend, when being increased to certain numerical value, even the consumption of tungstic oxide and phase-transfer catalyst is relative higher, obtain epoxy soybean oil though can successfully synthesize, the remaining iodine number of product is higher, and oxirane value has also reduced.PH buffer reagent preferably phosphoric acid disodium hydrogen of the present invention is with Na
2HPO
412H
2The O meter, its consumption is 0～1% of a soybean oil quality, preferably its consumption is 0.2%～1% of a soybean oil quality.The consumption of other pH buffer reagent can be consulted and used.
Preferred 55～70 ℃ of the temperature range of the described reaction of step (1), more preferred 60～65 ℃.
Can obtain oxirane value＞6.5 according to the preferred technical solution of the present invention, the epoxy soybean oil of residual iodine number＜5.0.The residual iodine number of described epoxy soybean oil is by the mensuration GB/T1676-2008 of National Standard softening agent iodine number " measure; The epoxy soybean oil oxirane value is by the mensuration GB/T1677-2008 of National Standard softening agent oxirane value " measure.
Beneficial effect of the present invention:
The present invention prepares epoxy soybean oil with hydrogen peroxide as oxygen source, and cost is low, and the reacted by product of hydrogen peroxide is water, is a kind of cleaning oxygen source; Do not use carboxylic acid as the active oxygen carrier, do not use strong acid in the reaction system of the present invention design as catalyzer, not not with an organic solvent yet, the catalyst system therefor consumption is little, the reactive behavior height, byproduct of reaction is few, product postprocessing is simple, does not need with massive laundering deacidification, is a kind of environmental protection, epoxy soybean oil synthetic method efficiently.
The present invention provides more optimized technical scheme simultaneously, in synthetic system, adopt suitable pH buffer reagent, and sum up suitable amount ranges, on the basis of the above-mentioned beneficial effect of the present invention, more can guarantee to obtain oxirane value＞6.5, the epoxy soybean oil of residual iodine number＜5.0.
Embodiment
In order to understand the present invention better, further set forth the present invention below in conjunction with specific embodiment, the synthetic thought according to the present invention, simple the substituting of allied substances should belong to scope of the present invention.Employed test method is the existing ordinary method in present technique field if no special instructions among the following embodiment; Employed material, reagent etc. if no special instructions, are the reagent and the material that can obtain from commercial channels.
Embodiment 1
(1) adding tungstic oxide 0.7g, mass concentration in the reaction vessel respectively is 50% hydrogen peroxide 4.5g, phase-transfer catalyst 1g, pH buffer reagent Na
2HPO
412H
2O 1g and soybean oil (the soybean oil iodine number is about 127) 100g after stirring, is warming up to 65～70 ℃;
(2) drip remaining hydrogen peroxide 40.5g in 1.5～2h, control hydrogen peroxide rate of addition makes temperature of reaction system maintain 65～70 ℃, and hydrogen peroxide drips off the back and continues reaction for some time, total reaction time 4h (comprising that hydrogen peroxide drips the time);
(3) after reaction finished, reaction mixture washed once with warm water, and standing demix is removed water, and organic phase gets the epoxy soybean oil production after underpressure distillation dewaters, filters.
Mensuration GB/T1676-2008 according to National Standard softening agent iodine number " to measure the residual iodine number of present embodiment epoxy soybean oil be 4.0, much smaller than 5.0; Mensuration GB/T1677-2008 by National Standard softening agent oxirane value " to measure present embodiment epoxy soybean oil oxirane value be 6.52, greater than 6.5.
Adopt the soybean oil raw material (iodine number be about 127) identical with embodiment 1, according to preparation method and the measuring method of embodiment 1, experiment condition and the experimental result of embodiment 1～12 are shown in Table 1:
Reactant ratio, reaction conditions and the reaction result * of table 1 epoxy soybean oil building-up reactions embodiment
* used soybean oil iodine number is about 127, and each embodiment soybean oil consumption is 100 grams
The mass concentration of the used hydrogen peroxide of * is 30%
By the detection of oxirane value shown in the table 1 as can be known, synthetic method of the present invention is successfully synthesized and is obtained epoxy soybean oil.
By embodiment 6 and 7 more as can be known, when not adding the pH buffer reagent, under the lower situation of other catalyst levelss and temperature of reaction, same reaction is in the time, the remaining iodine number of product is lower, be that double bond conversion rate is higher, but the oxirane value of product is low all the better, illustrates that the open loop side reaction of epoxy group(ing) in the reaction process is more serious.If but when the buffer reagent consumption increased, epoxidation reaction speed can descend, as embodiment 4 and 6 relatively, when the buffer reagent consumption is increased to 0.6% by 0.2%, even the consumption of tungstic oxide and phase-transfer catalyst is relative higher, but the remaining iodine number of product wants high, and oxirane value is also low; Particularly when the consumption of buffer reagent was increased to 2%, even correspondingly increase tungstic oxide and phase-transfer catalyst consumption (seeing embodiment 9), the oxirane value of products therefrom also obviously reduced, and only 2.90.
In the synthetic method of the present invention, the principal element that influences the epoxy soybean oil quality is not a temperature of reaction, is catalyzer and buffer reagent; Improve temperature when promoting epoxidation reaction, also the open loop side reaction to epoxy group(ing) has promoter action.Temperature is too low, and epoxidation reaction is slow, and as embodiment 11, when temperature of reaction was 50～55 ℃, the products therefrom oxirane value only was 5.49, compares with other embodiment under the simulated condition, and oxirane value reduces; The temperature of reaction height, though epoxidation reaction speed is fast, the epoxy ring-opening side reaction is serious, can not get the high epoxy value product, as embodiment 10.So the invention provides preferred range of reaction temperature is 55～70 ℃, more preferred 60～65 ℃.
Claims (10)
1. epoxy soybean oil synthetic method is characterized in that with the hydrogen peroxide being that oxygen source, tungstic oxide are the active oxygen carrier, heating is carried out epoxidation reaction to soybean oil and prepared described epoxy soybean oil in the presence of phase-transfer catalyst.
2. epoxy soybean oil synthetic method according to claim 1 is characterized in that may further comprise the steps:
(1) tungstic oxide, part hydrogen peroxide, phase-transfer catalyst and soybean oil are stirred after, carry out temperature reaction;
(2) hydrogen peroxide of dropping remainder in step (1) reaction system, hydrogen peroxide drips off the back and continues reaction;
(3) after reaction finishes, will wash with warm water through step (2) post reaction mixture, standing demix is removed water, and organic phase gets epoxy soybean oil after underpressure distillation dewaters, filters.
3. an epoxy soybean oil synthetic method is characterized in that with the hydrogen peroxide being that oxygen source, tungstic oxide are the active oxygen carrier, reacting by heating prepares described epoxy soybean oil in the presence of phase-transfer catalyst and pH buffer reagent.
4. epoxy soybean oil synthetic method according to claim 3 is characterized in that may further comprise the steps:
(1) tungstic oxide, part hydrogen peroxide, phase-transfer catalyst, pH buffer reagent and soybean oil are stirred after, carry out temperature reaction;
(2) hydrogen peroxide of dropping remainder in step (1) reaction system, hydrogen peroxide drips off the back and continues reaction;
(3) after reaction finishes, will wash with warm water through step (2) post reaction mixture, standing demix is removed water, and organic phase gets epoxy soybean oil after underpressure distillation dewaters, filters.
5. according to claim 1 or 3 described epoxy soybean oil synthetic methods, the consumption that it is characterized in that described tungstic oxide is 0.2%～0.7% of a soybean oil quality.
6. according to claim 1 or 3 described epoxy soybean oil synthetic methods, the consumption that it is characterized in that described hydrogen peroxide is 18.5%～22.5% of soybean oil quality in clean hydrogen peroxide.
7. according to claim 1 or 3 described epoxy soybean oil synthetic methods, the mass concentration that it is characterized in that described hydrogen peroxide is 50%.
8. according to claim 1 or 3 described epoxy soybean oil synthetic methods, it is characterized in that described phase-transfer catalyst is three n-octyl methyl quaternary ammonium dihydrogen phosphates, its molecular formula is [CH
3(n-C
8H
17)
3N]
+H
2PO
4 -, consumption is 0.3%～1% of a soybean oil quality.
9. epoxy soybean oil synthetic method according to claim 3 is characterized in that described pH buffer reagent is a Sodium phosphate dibasic, with Na
2HPO
412H
2The O meter, consumption is 0～1% of a soybean oil quality; Preferable amount is 0.2%～1% of a soybean oil quality.
10. according to claim 1 or 3 described epoxy soybean oil synthetic methods, it is characterized in that step (1) and the described temperature of reaction of step (2) are 55～70 ℃, be preferably 60～65 ℃.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703225A (en) * | 2012-06-11 | 2012-10-03 | 刘忠 | Epoxidized soybean oil plasticizer and production method thereof |
| CN103224837A (en) * | 2013-04-24 | 2013-07-31 | 华南理工大学 | Rapid and green preparation method of epoxidation soybean oil |
| CN103911036A (en) * | 2014-04-30 | 2014-07-09 | 苏州安洁科技股份有限公司 | Gloss black printing ink for silk screen printing |
| CN106221244A (en) * | 2016-08-23 | 2016-12-14 | 成都米特瑞新材料科技有限公司 | Epoxy linseed oil and citric acid composite plasticizer |
| CN106398236A (en) * | 2016-08-23 | 2017-02-15 | 成都米特瑞新材料科技有限公司 | Process for compounding plasticizer by using epoxy linseed oil and citric acid |
| CN113214190A (en) * | 2021-05-10 | 2021-08-06 | 邵阳学院 | Method for synthesizing epoxidized soybean oil by catalyzing bean dreg-based solid acid |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703225A (en) * | 2012-06-11 | 2012-10-03 | 刘忠 | Epoxidized soybean oil plasticizer and production method thereof |
| CN103224837A (en) * | 2013-04-24 | 2013-07-31 | 华南理工大学 | Rapid and green preparation method of epoxidation soybean oil |
| CN103224837B (en) * | 2013-04-24 | 2014-07-16 | 华南理工大学 | Rapid and green preparation method of epoxidation soybean oil |
| CN103911036A (en) * | 2014-04-30 | 2014-07-09 | 苏州安洁科技股份有限公司 | Gloss black printing ink for silk screen printing |
| CN103911036B (en) * | 2014-04-30 | 2016-01-20 | 苏州安洁科技股份有限公司 | Silk screen printing bright black ink |
| CN106221244A (en) * | 2016-08-23 | 2016-12-14 | 成都米特瑞新材料科技有限公司 | Epoxy linseed oil and citric acid composite plasticizer |
| CN106398236A (en) * | 2016-08-23 | 2017-02-15 | 成都米特瑞新材料科技有限公司 | Process for compounding plasticizer by using epoxy linseed oil and citric acid |
| CN106398236B (en) * | 2016-08-23 | 2018-07-06 | 成都米特瑞新材料科技有限公司 | Process for compounding plasticizer by using epoxy linseed oil and citric acid |
| CN113214190A (en) * | 2021-05-10 | 2021-08-06 | 邵阳学院 | Method for synthesizing epoxidized soybean oil by catalyzing bean dreg-based solid acid |
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