CN107794122A - A kind of synthesis method of epoxidized soybean oil - Google Patents
A kind of synthesis method of epoxidized soybean oil Download PDFInfo
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- CN107794122A CN107794122A CN201711140231.2A CN201711140231A CN107794122A CN 107794122 A CN107794122 A CN 107794122A CN 201711140231 A CN201711140231 A CN 201711140231A CN 107794122 A CN107794122 A CN 107794122A
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- soybean oil
- epoxidized soybean
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
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- Life Sciences & Earth Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of synthesis method of epoxidized soybean oil, using TBHP as oxygen source, heats the epoxidized soybean oil is prepared to soybean oil progress epoxidation reaction in the presence of a phase transfer catalyst；The TBHP dosage is 0.5 3.5 for the mol ratio with carbon-carbon double bond in soybean oil；The phase transfer catalyst is TBAB, and its molecular formula is C16H36BrN, its dosage are the 10 50% of soybean oil quality.Simple to operate, catalyst is cheap, simplifies technological process, reduces process costs, while overcomes the drawbacks of conventional method is caused using carboxylic acid and solvent etc., is only catalyzed with TBAB, and epoxide number just up to 3.5%, has certain Research Prospects.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to the epoxy soybean under a kind of no strong acid, condition of no solvent
The synthetic method of oil.
Background technology
Plant soybean oil is a kind of undersaturated triglyceride, and its fatty acid component mainly includes stearic acid, oil
Acid, linoleic acid plus linolenic acid, it is cheap, it is the preferred raw materials for producing epoxidized soybean oil.The food that plasticiser triggers in recent years
Safety problem grows in intensity, up to thousand kinds of foods by plasticiser pollution threat, therefore find a kind of environment-friendlyplasticizer plasticizer into
For it is very urgent the problem of.Epoxidized soybean oil is a kind of environment-friendly, the plasticizer of function admirable, is suffered from extensively in many fields
General application prospect, and a kind of important non-toxic organic synthetic intermediate.
At present, the method for producing epoxidized soybean oil is broadly divided into solvent method and solventless method, and catalyst is key point.Its
In, solvent method production procedure is long, investment is big, environmental pollution is serious, poor product quality, and the technique has been eliminated.Non-solvent method is
Under catalyst action, formic acid or acetic acid and hydroperoxidation generation epoxidizing agent, then epoxidizing agent and soybean oil reaction
Obtain epoxy soybean oil product.Though the method has compared with high epoxy value, catalyst price, solvent is also using, make separation work
Skill becomes difficult.Therefore need badly a kind of simple to operate, catalyst is cheap, and technological process is simple, the cheap life of process costs
The method for producing epoxidized soybean oil.
The content of the invention
Based on above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of simple to operate, urges
Agent is cheap, and technological process is simple, the method for the cheap production epoxidized soybean oil of process costs.
In order to solve the above-mentioned technical problem, the present invention provides a kind of synthesis method of epoxidized soybean oil, with tert-butyl hydroperoxide
Hydrogen (TBHP) is oxygen source, heats the epoxy is prepared to soybean oil progress epoxidation reaction in the presence of a phase transfer catalyst
Soybean oil, the TBHP dosage are 0.5-3.5 for the mol ratio with carbon-carbon double bond in soybean oil；The phase transfer
Catalyst is TBAB, and its molecular formula is C16H36BrN, its dosage are the 10-50% of soybean oil quality；The tertiary fourth
Base hydrogen peroxide is added dropwise dropwise in 1h-2h with single channel syringe pump.
As the preferred of above-mentioned technical proposal, synthesis method of epoxidized soybean oil provided by the invention further comprises following skill
Art feature it is part or all of：
As the improvement of above-mentioned technical proposal, described a kind of synthesis method of epoxidized soybean oil, with TBHP
For oxygen source, heat in the presence of a phase transfer catalyst and the epoxidized soybean oil is prepared to soybean oil progress epoxidation reaction；
The TBHP dosage is 0.5-3.5 for the mol ratio with carbon-carbon double bond in soybean oil；
The phase transfer catalyst is TBAB, and its molecular formula is C16H36BrN, its dosage are soybean oil quality
10-50%.
As the improvement of above-mentioned technical proposal, a kind of described synthesis method of epoxidized soybean oil, comprise the following steps：
Step 1: after soybean oil, phase transfer catalyst are stirred, temperature reaction is carried out；
Step 2: TBHP is added dropwise in the reaction system formed to step 1, is dripped off in 1-2h, continue to be incubated
React 1-6h；
Step 3: take the reaction solution obtained by step 2 to be extracted 2-5 times with dichloromethane, the matter of the reaction solution and extractant
Measure ratio 1：1.5-3, aqueous phase then is removed with saturated aqueous common salt, the mass ratio of reaction solution and saturated aqueous common salt is 1：1.5-3 add nothing
Aqueous sodium persulfate-continue drying, the mass ratio of the reaction solution and anhydrous sodium sulfate is 10：0.5-2, revolving remove solvent and produced
The faint yellow thick liquid of thing is epoxidized soybean oil, and epoxide number is determined by GB 1677-81 hydrochloric acid-acetone method；
As the improvement of above-mentioned technical proposal, temperature reaction is carried out in the step 1, keeping temperature is 45-85 DEG C.
As the improvement of above-mentioned technical proposal, the phase transfer catalyst is TBAB, and its molecular formula is
C16H36BrN, structural formula areIts dosage is the 10-50% of soybean oil quality
As the improvement of above-mentioned technical proposal, the course of reaction keeping temperature of the step 2 is 45-85 DEG C.
As the improvement of above-mentioned technical proposal, the mass fraction of the TBHP aqueous solution is 65%.
Compared with prior art, technical scheme has the advantages that：The method is simple to operate, catalyst
It is cheap, technological process is simplified, reduces process costs, while overcomes conventional method and is caused using carboxylic acid and solvent etc.
The drawbacks of, only it is catalyzed with TBAB, epoxide number just up to 3.5%, has certain Research Prospects.Table 1 below -3 be it is each because
Influence of the element to epoxide number：
Influence of the mol ratio of the oxygen source of table 1 and carbon-carbon double bond to epoxide number
| Mol ratio | 0.5:1 | 0.75:1 | 1:1 | 1.25:1 | 1.5:1 | 2:1 |
| Epoxide number | 2.24 | 2.66 | 2.94 | 3.36 | 3.5 | 2.24 |
(mol ratio of oxygen source and carbon-carbon double bond is 1 for influence of the reaction time of table 2 to epoxide number：1)
| Reaction time | 1h | 2h | 3h | 4h | 5h | 6h |
| Epoxide number | 1.4 | 1.8 | 2.5 | 2.3 | 2.2 | 2.0 |
(mol ratio of oxygen source and carbon-carbon double bond is 1 for influence of the reaction temperature of table 3 to epoxide number：1)
| Reaction temperature | 25℃ | 45℃ | 55℃ | 65℃ | 75℃ | 85℃ |
| Epoxide number | 1.6 | 2.1 | 2.3 | 2.5 | 2.4 | 2.2 |
By upper table as can be seen that being individually catalyzed with TBAB, epoxide number can be made to reach 3.5% or so, had
Certain Research Prospects.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the present invention can
Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the accompanying drawing of embodiment will be simply situated between below
Continue.
Fig. 1 is the epoxidized soybean oil synthetic reaction schematic diagram of the embodiment of the present invention 1；
Fig. 2 is the infrared spectrogram of the synthetic product of the embodiment of the present invention 1.
Embodiment
The following detailed description of the present invention embodiment, its as part of this specification, by embodiment come
Illustrate the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Embodiment 1
A kind of synthesis method of epoxidized soybean oil, comprises the following steps：
(1) after 10.0g soybean oils, 3.0g phase transfer catalysts stirring, temperature reaction is carried out, is warming up to 65 DEG C；
(2) 9.0g t-butyl peroxies (65%) are added dropwise into (1) reaction system with single channel syringe and change hydrogen, dripped in 1h
It is complete, continue to react 3h；
(3) extracted 3 times with dichloromethane after stopping reaction, the mass ratio of reaction solution and extract is 1：2, saturated aqueous common salt
The mass ratio of removing aqueous phase, reaction solution and saturated aqueous common salt is 1：2, addition anhydrous sodium sulfate, which continues drying, (has prevented a small amount of water
Divide clean without removing), the mass ratio of reaction solution and anhydrous sodium sulfate is 10：1, it is faint yellow that revolving, which removes solvent and obtains product,
Thick liquid is epoxidized soybean oil, and epoxide number, epoxide number 3.5% are determined by GB 1677-81 hydrochloric acid-acetone method
Fig. 2 is the infrared spectrogram of the synthetic product of the embodiment of the present invention 1, and 1- is without TBAB in figure；2- is added
TBAB；Occur epoxy peak at 845cm-1 after adding TBAB, said epoxidized soybean oil generation.
Embodiment 2
A kind of synthesis method of epoxidized soybean oil, comprises the following steps：
(1) after 10.0g soybean oils, 3.0g phase transfer catalysts stirring, temperature reaction is carried out, is warming up to 65 DEG C；
(2) 6.0g (65%) TBHP is added dropwise into (1) reaction system with single channel syringe, is dripped in 1h
It is complete, continue to react 3h；
(3) extracted 3 times with dichloromethane after stopping reaction, the mass ratio of reaction solution and extract is 1：2, saturated aqueous common salt
The mass ratio of removing aqueous phase, reaction solution and saturated aqueous common salt is 1：2, addition anhydrous sodium sulfate, which continues drying, (has prevented a small amount of water
Divide clean without removing), the mass ratio of reaction solution and anhydrous sodium sulfate is 10：1, it is faint yellow that revolving, which removes solvent and obtains product,
Thick liquid is epoxidized soybean oil, determines epoxide number by GB 1677-81 hydrochloric acid-acetone method, epoxide number is up to 2.94%.
Embodiment 3
A kind of synthesis method of epoxidized soybean oil, comprises the following steps：
(1) after 10.0g soybean oils, 3.0g phase transfer catalysts stirring, temperature reaction is carried out, is warming up to 85 DEG C；
(2) 6.0g (65%) TBHP is added dropwise into (1) reaction system with single channel syringe, is dripped in 1h
It is complete, continue to react 3h；
(3) extracted 3 times with dichloromethane after stopping reaction, the mass ratio of reaction solution and extract is 1：2, saturated aqueous common salt
The mass ratio of removing aqueous phase, reaction solution and saturated aqueous common salt is 1：2, addition anhydrous sodium sulfate, which continues drying, (has prevented a small amount of water
Divide clean without removing), the mass ratio of reaction solution and anhydrous sodium sulfate is 10：1, it is faint yellow that revolving, which removes solvent and obtains product,
Thick liquid is epoxidized soybean oil, determines epoxide number by GB 1677-81 hydrochloric acid-acetone method, epoxide number is up to 2.2%.
Each raw material cited by the present invention, and bound, the section value of each raw material of the present invention, and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
Described above is the preferred embodiment of the present invention, can not limit the right model of the present invention with this certainly
Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, may be used also
To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.
Claims (7)
- A kind of 1. synthesis method of epoxidized soybean oil, it is characterised in that：Using TBHP as oxygen source, in phase transfer catalyst In the presence of heating to soybean oil carry out epoxidation reaction the epoxidized soybean oil is prepared；The TBHP dosage is 0.5-3.5 for the mol ratio with carbon-carbon double bond in soybean oil；The phase transfer catalyst is TBAB, and its molecular formula is C16H36BrN, its dosage are the 10- of soybean oil quality 50%.
- 2. synthesis method of epoxidized soybean oil as claimed in claim 1, it is characterised in that comprise the following steps：Step 1: after soybean oil, phase transfer catalyst are stirred, temperature reaction is carried out；Step 2: TBHP is added dropwise in the reaction system formed to step 1, dripped off in 1-2h, continue insulation reaction 1-6h；Step 3: take the reaction solution obtained by step 2 to be extracted 2-5 times with dichloromethane, the mass ratio of the reaction solution and extractant 1：1.5-3, aqueous phase then is removed with saturated aqueous common salt, the mass ratio of reaction solution and saturated aqueous common salt is 1：1.5-3, add anhydrous sulphur Sour sodium-continue drying, the mass ratio of the reaction solution and anhydrous sodium sulfate is 10：0.5-2, it is light that revolving removing solvent obtains product Yellow thick liquid is epoxidized soybean oil.
- 3. synthesis method of epoxidized soybean oil as claimed in claim 2, it is characterised in that：Carry out heating up instead in the step 1 Should, keeping temperature is 45-85 DEG C.
- 4. synthesis method of epoxidized soybean oil as claimed in claim 2, it is characterised in that：The phase transfer catalyst is the tetrabutyl Ammonium bromide, its molecular formula are C16H36BrN, structural formula are
- 5. synthesis method of epoxidized soybean oil as claimed in claim 2, it is characterised in that：The dosage of the phase transfer catalyst is The 10-50% of soybean oil quality.
- 6. synthesis method of epoxidized soybean oil as claimed in claim 2, it is characterised in that：The course of reaction of the step 2 is kept Temperature is 45-85 DEG C.
- 7. synthesis method of epoxidized soybean oil as claimed in claim 2, it is characterised in that：The TBHP aqueous solution Mass fraction be 65%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948305A (en) * | 2018-08-31 | 2018-12-07 | 五洲丰农业科技有限公司 | A kind of preparation method and applications of slow controlled release coated fertilizer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015002746A2 (en) * | 2013-07-01 | 2015-01-08 | Ferro Corporation | Biobased epoxidized fatty acid ester plasticizers |
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2017
- 2017-11-16 CN CN201711140231.2A patent/CN107794122A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015002746A2 (en) * | 2013-07-01 | 2015-01-08 | Ferro Corporation | Biobased epoxidized fatty acid ester plasticizers |
Non-Patent Citations (4)
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| 叶金星: "相转移催化α,β-不饱和酮环氧化反应研究", 《中国优秀博硕士学位论文全文数据库 (博士) 工程科技Ⅰ辑》 * |
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| CN108948305A (en) * | 2018-08-31 | 2018-12-07 | 五洲丰农业科技有限公司 | A kind of preparation method and applications of slow controlled release coated fertilizer |
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Application publication date: 20180313 |