CN102993129A - Method for preparing 1,2-epoxyoctane - Google Patents
Method for preparing 1,2-epoxyoctane Download PDFInfo
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- CN102993129A CN102993129A CN2012104795761A CN201210479576A CN102993129A CN 102993129 A CN102993129 A CN 102993129A CN 2012104795761 A CN2012104795761 A CN 2012104795761A CN 201210479576 A CN201210479576 A CN 201210479576A CN 102993129 A CN102993129 A CN 102993129A
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- octene
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Abstract
The invention discloses a method for preparing 1,2-epoxyoctane. According to the method, epoxidation reaction is carried out on raw material 1-octylene to obtain 1,2-epoxyoctane. The method is characterized in that epoxidation reaction adopts hydrogen peroxide as oxidant, a polar solvent as a reaction medium and phosphotungstic acid as a catalyst, the content of the prepared 1,2-epoxyoctane is more than or equal to 95%, and the yield of 1,2-epoxyoctane is more than or equal to 75%, the catalyst can be recovered for 3 times,, and the average yield is more than or equal to 75%. The method is high in yield, and the cost is lowered; the energy consumption is low, the energy resources can be saved, the temperature of the epoxidation reaction is 45-55 DEG C; and the product quality is high, and the content of 1,2-epoxyoctane is more than or equal to 95%; no three wastes are emitted.
Description
Technical field
The present invention relates to the preparation of phosphotungstic acid quaternary and the method that the catalyzed 1-octylene epoxidation generates 1,2-octylene oxide thereof.
Background technology
1,2-octylene oxide can be used as solvent-stable agent, softening agent, lubricant addition material etc., also is used for organic synthesis.
1,2-octylene oxide has R-(+) and S-(-) two kinds of isomer, it be a kind of colourless-weak yellow liquid; Toxicology data shows that taking in dosage is 103 mg/kg (mouse), can produce lymphadenomatous toxicity, and ecological data show that this material may have harm to environment, should pay special attention to water body.
So far, external synthetic 1, the method of 2-octylene oxide is more, basically be under the effect of catalyzer, to carry out epoxidation reaction with oxygenant and obtain with the 1-octene, usually use comparatively frequent and economical and practical oxygenant that hydrogen peroxide, t-butyl hydrogen peroxide, oxygen etc. are arranged, these oxygenants will could generate 1,2-octylene oxide with 1-octene epoxidation usually preferably under the effect of catalyzer, in view of this, catalyzer is the key that this reaction can be carried out smoothly.For the 1-octene, large mainly with cheap H
2O
2As oxygenant, because the by product of its generation is water, environment is not had to pollute and be referred to as " Green Oxidant ", and used catalyzer mostly is greatly the composition metal organic compound, is that some contain the metal composites such as molybdenum, titanium, manganese, cobalt, tin, vanadium, productive rate is at 30%-99%, productive rate accounted for below 70% near half, 90% above productive rate only accounts for 1/4th, and the preparation of these catalyzer is comparatively complicated, do not reuse, relative cost is higher.
In the document [Green Chem., 2009,11,1589-1594], take the 1-octene as raw material, 30% hydrogen peroxide is oxygenant, in ionic liquid (ILs), in 70 ℃, with n-dodecane yl pyridines Suanphosphotungstate ([Dopy]
3[PW
12O
40]) make catalyzer, reacted 2 hours, generate 1,2-octylene oxide, yield is 10%.The method temperature of reaction is higher, and by product is many, and yield is low; Also used expensive ionic liquid as solvent, cost is high.
Summary of the invention
The present invention be directed to the deficiencies in the prior art, propose a kind of method for preparing 1,2-octylene oxide.
The technical scheme that the present invention prepares 1,2-octylene oxide is as follows:
The method is take the 1-octene as raw material, pass through epoxidation reaction, it is characterized in that it is oxygenant that epoxidation reaction adopts hydrogen peroxide, reaction medium is polar solvent, and catalyzer is phosphotungstic acid quaternary, obtain 1 through above-mentioned reaction, the 2-octylene oxide, content 〉=95%, yield 〉=75%, catalyzer can be recycled 3 times, average yield 〉=75%;
Described epoxidation reaction temperature 45-55 ℃;
The mol ratio of described 1-octene, hydrogen peroxide, phosphotungstic acid quaternary is 1:1.5:0.004;
Described reaction medium is halohydrocarbon such as methylene dichloride, trichloromethane, 1,2-ethylene dichloride isopolarity solvent;
Described catalyzer is the product that phospho-wolframic acid and quaternary ammonium salt reaction generate;
Described quaternary ammonium salt is long chain alkane ammonium halide such as cetyl trimethylammonium bromide, hexadecyl triphenyl brometo de amonio, Cetyltrimethylammonium bromide etc.;
The preparation temperature of described phosphotungstic acid quaternary is room temperature;
The mol ratio of described phospho-wolframic acid, quaternary ammonium salt and hydrogen peroxide is 1:3:107.
Described catalyzer can reuse 3 times.
1,2-octylene oxide assay vapor-phase chromatography.
Concrete preparation technology is as follows:
1, phosphotungstic acid quaternary Q
3PW
4O
16The preparation of catalyzer
Mol ratio by phospho-wolframic acid, quaternary ammonium salt and hydrogen peroxide is 1:3:107, accurately takes by weighing phospho-wolframic acid and places reactor, adds distilled water to just dissolving, then drips the H of concentration 〉=40%≤50%
2O
2, after dropwising, stirring at room 30 min; Then quaternary ammonium salt is dissolved in the halohydrocarbon fully, slowly splashes in the reactor, stir 30 min under the room temperature, filter and obtain the light yellow solid powder, with the unreacted quaternary ammonium salt of deionized water flush away, use AgNO
3Solution check, until in the filtrate without Br
-Till the ion, with solid be at last catalyzer 60 ℃ of oven dry, productive rate is 90.11%;
Described quaternary ammonium salt is a kind of in long chain alkane ammonium halide cetyl trimethylammonium bromide, hexadecyl triphenyl brometo de amonio, the Cetyltrimethylammonium bromide;
2, phosphotungstic acid quaternary Q
3PW
4O
16Catalysis H
2O
2Epoxidation 1-octene
Mol ratio by 1-octene, hydrogen peroxide, phosphotungstic acid quaternary is 1:1.5:0.004, takes by weighing first the 1-octene, places reactor, adds halohydrocarbon, to melting fully, adds catalyzer Q again
3PW
4O
16, after stirring, add at last the H of concentration 〉=40%≤50%
2O
2, react 7h under the 45-55 ℃ of condition, monitor with gas-chromatography in the reaction process, after reaction finishes, the total overall reaction thing is centrifugal, and taking precipitate is that catalyzer is for subsequent use, standing demix, organic phase deionized water wash, drying obtains the 1.2-octylene oxide, its content 〉=95%, productive rate 75%;
Described halohydrocarbon is methylene dichloride, trichloromethane, 1,2-ethylene dichloride a kind of;
3, catalyzer Q
3PW
4O
16Recycling
Utilize above-mentioned throw out catalyzer Q
3PW
4O
16, continue reaction according to processing condition and the technological process of step 2, obtain the 1.2-octylene oxide, average yield 75%, this catalyzer reaction repeated three times.
Preparation 1 provided by the invention, the method for 2-octylene oxide has following advantage: yield is higher, reaches more than 75%, and catalyzer recycling 3 times has reduced cost; Energy consumption is low, save energy, epoxidation reaction temperature 45-55 ℃; Quality product is high, 1,2-octylene oxide content 〉=95%; Three-waste free discharge.
Embodiment
Embodiment
1, phosphotungstic acid quaternary (Q
3PW
4O
16) preparation (Q is the abbreviation of cetyltrimethyl ammonium) of catalyzer
Accurately take by weighing 3.49 g (1.21mmol) phospho-wolframic acid in the reactor of 150 ml, add distilled water to just dissolving, then drip the H of 10.00 g (0.13mol) 44.15%
2O
2After dropwising, at 25 ℃, stir 30 min.Then 1.31 g (3.59mmol) cetyl trimethylammonium bromide is dissolved in the CH of 30 ml
2Cl
2In, slowly splash in the reactor, stir 30 min under the room temperature, filter and obtain the light yellow solid powder, with the unreacted quaternary ammonium salt of deionized water flush away, until in the filtrate without Br
-(use AgNO till the ion
3Solution check), at last with solid 60 ℃ of oven dry.Obtain the 1.71g product, productive rate is 90.11%.Q
3PW
4O
16FT-IR:2923.63 cm
-1, 2852.42 cm
-1(C-H stretching vibration absorption peak), 1079.01 cm
-1(P-O
1Strong antisymmetric stretching vibration absorption peak), 980.15cm
-1(W-O
4The stretching vibration absorption peak), 897.04 cm
-1(W-O
2-W stretching vibration absorption peak), 813.36 cm
-1(W-O
3-W stretching vibration absorption peak), 520 cm
-1(vibration of W-O-O).Q
3PW
4O
16Ultimate analysis: C:39.52%; H:7.68%; N:2.23% (theoretical value C:40.48%; H:7.45%; N:2.40%).
2, phosphotungstic acid quaternary (Q
3PW
4O
16) catalysis H
2O
2Epoxidation 1-octene
In 50 ml reactors, add successively 15 ml trichloromethanes, then 3.69 g (33mmol) 1-octene adds respectively 0.21 g (0.13mmol) Q
3PW
4O
16, after stirring, add again 3.79 g (49 mmol), 44.15% H
2O
2, react 7h under 50 ℃ of conditions, monitor with gas-chromatography in the reaction process, after reaction finishes, the total overall reaction thing is centrifugal, and taking precipitate is for subsequent use, standing demix, organic phase deionized water wash, drying, the content that obtains the 1.2-octylene oxide is 95.8%, productive rate 80.02%
3, catalyzer Q
3PW
4O
16Recycling
Utilize above-mentioned throw out catalyzer Q
3PW
4O
16, continue reaction according to the processing condition of step 2 and technological process, obtain the 1.2-octylene oxide, its result shows, and this catalyzer can reaction repeated three times, and productive rate is respectively 79.35%, 76.23%, 74.32%, and average yield is 76.63%.
Preparation method's Comparative Examples of preparation method embodiment proposed by the invention and document is compared, just can find out innovation of the present invention and advantage.
The main physical and chemical index of 1,2-octylene oxide
Molecular weight 128.21
The appearance colorless transparent liquid
62 ° of C of boiling point
37 ° of C refractive index of flash-point 1.418-1.421 (20 ° of C, 589 nm)
Proportion 0.8340-0.8390 (20/20)
Store: to humidity sensitive, easily the moisture absorption seals and preserves
The toxicity test of 1,2-octylene oxide:
Toxicology data shows that taking in dosage is 103 mg/kg (mouse), can produce lymphadenomatous toxicity, and ecological data show that this material may have harm to environment, should pay special attention to water body.
Claims (1)
1. method for preparing 1,2-octylene oxide is characterized in that:
(1) phosphotungstic acid quaternary Q
3PW
4O
16The preparation of catalyzer
Mol ratio by phospho-wolframic acid, quaternary ammonium salt and hydrogen peroxide is 1:3:107, accurately takes by weighing phospho-wolframic acid and places reactor, adds distilled water to just dissolving, then drips the H of concentration 〉=40%≤50%
2O
2, after dropwising, stirring at room 30 min; Then quaternary ammonium salt is dissolved in the halohydrocarbon fully, slowly splashes in the reactor, stir 30 min under the room temperature, filter and obtain the light yellow solid powder, with the unreacted quaternary ammonium salt of deionized water flush away, use AgNO
3Solution check, until in the filtrate without Br
-Till the ion, with solid be at last catalyzer 60 ℃ of oven dry, productive rate is 90.11%;
Described quaternary ammonium salt is a kind of in long chain alkane ammonium halide cetyl trimethylammonium bromide, hexadecyl triphenyl brometo de amonio, the Cetyltrimethylammonium bromide;
(2) phosphotungstic acid quaternary Q
3PW
4O
16Catalysis H
2O
2Epoxidation 1-octene
Mol ratio by 1-octene, hydrogen peroxide, phosphotungstic acid quaternary is 1:1.5:0.004, takes by weighing first the 1-octene, places reactor, adds halohydrocarbon, to melting fully, adds catalyzer Q again
3PW
4O
16, after stirring, add at last the H of concentration 〉=40%≤50%
2O
2, react 7h under the 45-55 ℃ of condition, monitor with gas-chromatography in the reaction process, after reaction finishes, the total overall reaction thing is centrifugal, and taking precipitate is that catalyzer is for subsequent use, standing demix, organic phase deionized water wash, drying obtains the 1.2-octylene oxide, its content 〉=95%, productive rate 75%;
Described halohydrocarbon is methylene dichloride, trichloromethane, 1,2-ethylene dichloride a kind of;
(3) catalyzer Q
3PW
4O
16Recycling
Utilize above-mentioned throw out catalyzer Q
3PW
4O
16, continue reaction according to processing condition and the technological process of step (2), obtain the 1.2-octylene oxide, average yield 75%, this catalyzer reaction repeated three times.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712954A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method of preparing 1, 2-epoxyoctane through epoxidation of 1-octene |
| CN106866585A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of epoxides |
| CN108358872A (en) * | 2018-03-21 | 2018-08-03 | 天津市职业大学 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
| CN108530564A (en) * | 2018-04-17 | 2018-09-14 | 中科广化（重庆）新材料研究院有限公司 | It a kind of epoxidized SBS, block macromolecular reactive amines toughener and its prepares and application in the epoxy |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712954A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method of preparing 1, 2-epoxyoctane through epoxidation of 1-octene |
| CN106866585A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of epoxides |
| CN108358872A (en) * | 2018-03-21 | 2018-08-03 | 天津市职业大学 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
| CN108530564A (en) * | 2018-04-17 | 2018-09-14 | 中科广化（重庆）新材料研究院有限公司 | It a kind of epoxidized SBS, block macromolecular reactive amines toughener and its prepares and application in the epoxy |
| CN108530564B (en) * | 2018-04-17 | 2021-05-07 | 中科广化（重庆）新材料研究院有限公司 | Epoxidized SBS (styrene-butadiene-styrene), block polymer active amine flexibilizer, preparation thereof and application thereof in epoxy resin |
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Application publication date: 20130327 |