CN112898241B - Preparation method of styrene oxide - Google Patents
Preparation method of styrene oxide Download PDFInfo
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- CN112898241B CN112898241B CN202110106589.3A CN202110106589A CN112898241B CN 112898241 B CN112898241 B CN 112898241B CN 202110106589 A CN202110106589 A CN 202110106589A CN 112898241 B CN112898241 B CN 112898241B
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- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
The invention discloses a preparation method of styrene oxide. Styrene is taken as an initial raw material, and styrene oxide is obtained through bromination and saponification reaction. The invention takes hydrogen peroxide as a main oxidant, adopts a mixed oxidant of hydrogen peroxide and sodium chlorate, avoids the strong oxidizing property of sodium chlorate and generates a great amount of by-products of phenyl-1, 2-dibromoethane, acetophenone and benzaldehyde; the catalyst is added in the bromination process, so that the selectivity is improved, and the generation of phenyl glycol is reduced; the method has the advantages of simple operation, high selectivity, less side reaction, high yield and high product purity, and is suitable for domestic industrial production. The total yield reaches more than 89.0 percent, and the product purity reaches more than 99.0 percent.
Description
Technical Field
The invention belongs to the field of chemistry or pharmaceutical chemistry, and particularly relates to a preparation method of styrene oxide.
Background
Styrene oxide is an important intermediate in organic synthesis, pharmaceutical industry and perfume industry, and can also be used as a diluent for epoxy resins, UV-absorbers, and flavoring agents, such as styrene oxide, which is hydrogenated to produce beta-phenylethanol, which has a rose fragrance, an important perfume, and styrene oxide is also an intermediate in the synthesis of levamisole. In recent years, the demand of the foreign beta-phenethyl alcohol and the medicine levamisole is continuously increased, and the supply and the shortage of the styrene oxide are required in the markets at home and abroad, thereby bringing wide prospects for the research of the styrene oxide. The chemical structural formula of the styrene oxide is as follows:
at present, two common preparation methods of styrene oxide exist:
Styrene is used as a raw material, oxygen, hydrogen peroxide, tert-butyl hydroperoxide, m-chloroperoxybenzoic acid and urea peroxide are used as oxidizing agents, and a selective oxidation catalyst is adopted to prepare the styrene oxide through selective oxidation. The reported selective oxidizing agents include cobalt tetraoxide, nano aluminum oxide, cobalt phthalocyanine multi-walled carbon nanotube composite catalyst, ceO2/Mn, MSN-NH 2/gold catalyst, 3-aminopropyl triethoxysilane, ceO2/Ag, (Mn, co, ni) -Salen complex, titanium Silicalite (TS), phosphotungstic acid, mn-Ti-Al-MCM-41 mesoporous molecular sieve, pd/carboxyl functional ionic liquid and the like, but the selectivity oxidation reported at present can be by-produced with benzoic acid, benzaldehyde, phenylacetaldehyde, acetophenone and phenyl glycol, and the purity of the product styrene oxide is low. For example, yang, xaoqing et al (Industrial & Engineering ChemistryResearch,59 (45), 19938-19951; 2020) reported the preparation of styrene oxide by selective oxidation using styrene as the starting material, cobalt tetraoxide as the catalyst, oxygen as the oxidant, and 24 hours at 90 ℃. The synthetic route is as follows:
the content of styrene oxide in the product prepared by the synthetic route is only 71.7%, the content of byproduct benzoic acid is 13.4%, the purity of the product is too low, and the synthetic route needs to be further improved and optimized.
The current source of oxygen for epoxidizing styrene by the oxyhalide method is oxyhalide, and the oxyhalide used includes chlorate, perchloric acid, hypohalous acid, hypochlorite and iodophthalide (PhIO). The cost of using the iodophthalide is high, the environment is easy to be seriously polluted, and the energy consumption is high. The domestic manufacturers mainly adopt a bromohydrin method for production, and the method has high yield which can reach about 80 percent. Lv Shaojie (chemistry of synthesis, 2000,8 (1): 71-74) reported the synthetic route as follows:
NaClO 3 excess will cause further oxidation of HBrO to Br 2 Thereby increasing the by-product phenyl-1, 2-dibromoethane.
In view of the disadvantages of the above-mentioned styrene oxide synthesis process, development of a styrene oxide preparation method which is easy to operate, high in selectivity, less in side reaction, high in yield and high in product purity and suitable for industrialization is still in need of further research.
Disclosure of Invention
Aiming at various defects of the route, the invention aims to provide a styrene oxide preparation method which is simple to operate, high in selectivity, less in side reaction, high in yield and purity and suitable for industrialization, and the specific technical scheme is as follows:
a method for preparing styrene oxide, characterized by being prepared by the following chemical reaction equation:
the specific preparation steps of the reaction equation are as follows:
(1) Bromination: taking water as a solvent, adding sodium bromide, sulfuric acid, sodium chlorate, styrene and a catalyst, dropwise adding hydrogen peroxide at a controlled temperature, heating to reflux, and carrying out heat preservation reaction. Cooling to 40-60deg.C, standing for at least 30 min, layering, and obtaining 2-bromo-1-phenylethanol at the lower layer.
(2) Saponification: adding 20% -50% sodium hydroxide aqueous solution into water as solvent, dropwise adding 2-bromo-1-phenylethanol at controlled temperature, keeping the temperature for reaction after dropwise adding, cooling to 30-40 ℃, standing for at least 30 minutes, layering, wherein the lower layer is sodium bromide solution, and can be used for the next bromination reaction, and the upper layer is styrene oxide.
The water consumption is 0.5-6 times of the weight of the styrene; the dosage of sodium bromide is 0.9-1.1 times of the weight of the styrene; the sulfuric acid content is 15.0-98.3%; the dosage (the pure folding amount) of the sulfuric acid is 0.4 to 0.9 times of the weight of the styrene; the dosage of the sodium chlorate is 0.05 to 0.2 times of the weight of the styrene; the dosage of the hydrogen peroxide is 1.05-1.4 times of the weight of the styrene; the dropping temperature of the hydrogen peroxide is controlled to be 30-75 ℃, the dropping time is 1-4 hours, the reflux heat preservation reaction temperature is 95-105 ℃, and the heat preservation time is 2-6 hours.
The catalyst is ammonium metavanadate (NH) 4 VO 3 ) Molybdenum hexacarbonyl (Mo (CO) 6 ) At least one of 1-butyl-3-methylimidazole tetrafluoroborate, wherein the dosage of the catalyst is 0.01-0.2 times of the weight of the styrene;
the water dosage is 0.4-1.0 times of the weight of the 2-bromo-1-phenylethanol; the dosage (the pure quantity) of the 20% -50% sodium hydroxide aqueous solution is 0.15-0.5 times of the weight of the 2-bromo-1-phenylethanol; the dripping temperature of the 2-bromo-1-phenyl ethanol is controlled to be 40-50 ℃, the dripping time is 1-4 hours, the heat preservation reaction temperature is 45-60 ℃, and the heat preservation time is 0.5-3 hours.
The invention has the beneficial effects that:
1) The invention provides a preparation method of styrene oxide, which uses hydrogen peroxide as a main oxidant and adopts a hydrogen peroxide/sodium chlorate mixed oxidant, so that the situation that the sodium chlorate has strong oxidability and a large amount of phenyl-1, 2-dibromoethane, acetophenone and benzaldehyde byproducts are generated is avoided;
2) According to the preparation method of styrene oxide, provided by the invention, the catalyst is added in the bromination process, so that the selectivity is improved, and the generation of phenyl glycol is reduced.
3) The preparation method of the styrene oxide provided by the invention has the total yield reaching more than 89.0%, the product purity reaching more than 99.0%, wherein the impurity styrene is less than or equal to 0.2%, the impurity acetophenone is less than or equal to 0.2%, the impurity benzaldehyde is less than or equal to 0.2%, and the impurity phenyl glycol is less than or equal to 0.3%.
Drawings
FIG. 1 is a GC spectrum of 2-bromo-1-phenylethanol
FIG. 2 is a GC spectrum of styrene oxide
Detailed Description
The present invention is described in detail below by way of specific examples, which are provided to illustrate, but not to limit, the present invention.
Example 1
Preparation of 2-bromo-1-phenylethanol:
280g of water and 90g of sodium bromide are added into a 1L four-neck flask, stirring is started, cooling is carried out, 47.5g of 98% sulfuric acid is dripped, 9.0g of sodium chlorate is added, 90g of styrene and 1.0g of ammonium metavanadate are added, the temperature is controlled to be 40-50 ℃, 110g of hydrogen peroxide is dripped, the dripping time is 1 hour, after the dripping is finished, the temperature is raised to reflux (98 ℃), and the reaction is carried out for 2 hours under heat preservation. Cooling to 40 ℃, standing for at least 30 minutes, layering, and obtaining 168.9g of 2-bromo-1-phenylethanol at the lower layer, wherein the yield is 97.2%. The GC detection purity is 96.5%, the styrene content is 0.6%, the phenyl-1, 2-dibromoethane content is 0.5%, the phenyl glycol content is 0.9%, the acetophenone content is 0.5%, and the benzaldehyde content is 0.2%.
Example 2
Preparation of 2-bromo-1-phenylethanol:
45g of water and 77.0g of sodium bromide are added into a 1L four-neck flask, stirring is started, cooling is carried out, 315g of 20% sulfuric acid and 4.5g of sodium chlorate are added, 90g of styrene and 9.0g of molybdenum hexacarbonyl are added, the temperature is controlled to be 65-70 ℃, 136g of hydrogen peroxide is dropwise added, the dropwise adding time is 3 hours, the temperature is raised to reflux (100 ℃), and the temperature is kept for 6 hours. Cooling to 50deg.C, standing for at least 30 min, layering, and obtaining 173.7g of 2-bromo-1-phenylethanol with a yield of 97.8%. The GC detection purity is 97.1%, the styrene content is 0.9%, the phenyl-1, 2-dibromoethane content is 0.8%, the phenyl glycol content is 0.7%, the acetophenone content is 0.4%, and the benzaldehyde content is 0.2%.
Example 3
Preparation of styrene oxide:
70g of water is added into a 1L four-neck flask, stirring is started, cooling is carried out, 152g of 30% sodium hydroxide aqueous solution is added, the temperature is controlled at 40-45 ℃, 168.9g of 2-bromo-1-phenylethanol is dropwise added, the dropwise adding time is 2 hours, and the reaction is carried out at 50-55 ℃ for 4 hours after the dropwise adding is completed. Cooling to 30deg.C, standing for at least 30 min, layering, wherein the lower layer is sodium bromide solution layer, and the upper layer is styrene oxide 96.7g with yield of 95.8%. The GC detection purity is 99.2%, the styrene content is 0.1%, the acetophenone content is 0.1%, the benzaldehyde content is 0.2%, and the phenyl glycol content is 0.3%.
Example 4
Preparation of styrene oxide:
138g of water is added into a 1L four-neck flask, stirring is started, cooling is carried out, 101g of 50% sodium hydroxide aqueous solution is added, the temperature is controlled at 45-50 ℃, 168.9g of 2-bromo-1-phenylethanol is dropwise added for 4 hours, and after the dropwise addition is finished, the reaction is carried out at 55-60 ℃ for 2 hours. Cooling to 30deg.C, standing for at least 30 min, layering, wherein the lower layer is sodium bromide solution layer, and the upper layer is styrene oxide 97.1 with a yield of 96.2%. The GC detection purity is 99.3%, the styrene content is 0.1%, the acetophenone content is 0.2%, the benzaldehyde content is 0.1%, and the phenyl glycol content is 0.2%.
Example 5
The recovered sodium bromide jacket was used in the preparation of 2-bromo-1-phenylethanol:
adding all the sodium bromide aqueous solution recovered in the example 4 into a 1L four-neck flask, regulating the pH to 5 by sulfuric acid, adding 15g of sodium bromide, starting stirring, cooling, adding 315g of 20% sulfuric acid, 4.5g of sodium chlorate, adding 90g of styrene and 9.0g of molybdenum hexacarbonyl, controlling the temperature to 65-70 ℃, dropwise adding 136g of hydrogen peroxide for 3 hours, heating to reflux (101 ℃) after dropwise adding, and carrying out heat preservation reaction for 6 hours. Cooling to 50 ℃, standing for at least 30 minutes, layering, and obtaining 173.2g of 2-bromo-1-phenylethanol from the lower layer, wherein the yield is 97.5%. The GC detection purity is 97.5%, the styrene content is 0.8%, the phenyl-1, 2-dibromoethane content is 0.6%, the phenyl glycol content is 0.7%, the acetophenone content is 0.6%, and the benzaldehyde content is 0.2%.
The present invention is not limited to the above embodiments, and any simple, equivalent changes or modifications of the above embodiments according to the technical matters of the present invention fall within the technical scope of the present invention.
Claims (3)
1. A method for preparing styrene oxide, characterized by being prepared by the following chemical reaction equation:
the specific preparation steps of the reaction equation are as follows:
(1) Bromination: taking water as a solvent, adding sodium bromide, sulfuric acid, sodium chlorate, styrene and a catalyst, dropwise adding hydrogen peroxide at a controlled temperature, heating to reflux, and carrying out heat preservation reaction; cooling to 40-60deg.C, standing for at least 30 min, layering, and obtaining 2-bromo-1-phenylethanol at the lower layer;
(2) Saponification: adding 20% -50% sodium hydroxide aqueous solution into water as a solvent, dropwise adding 2-bromo-1-phenylethanol at a controlled temperature, carrying out heat preservation reaction after dropwise adding, cooling to 30-40 ℃, standing for at least 30 minutes, layering, wherein the lower layer is sodium bromide solution, applying to the next bromination reaction, and obtaining styrene oxide on the upper layer;
in the reaction step (1), the catalyst is at least one of ammonium metavanadate and molybdenum hexacarbonyl, and the dosage of the catalyst is 0.01-0.2 times of the weight of the styrene.
2. The method for producing styrene oxide according to claim 1, wherein: in the reaction step (1), the water dosage is 0.5-6 times of the weight of the styrene; the dosage of sodium bromide is 0.9-1.1 times of the weight of the styrene; the sulfuric acid content is 15.0-98.3%; the pure amount of the sulfuric acid is 0.4 to 0.9 times of the weight of the styrene; the dosage of the sodium chlorate is 0.05 to 0.2 times of the weight of the styrene; the dosage of the hydrogen peroxide is 1.05-1.4 times of the weight of the styrene; the dropping temperature of the hydrogen peroxide is 30-75 ℃, the dropping time is 1-4 hours, the reflux heat preservation reaction temperature is 95-105 ℃, and the heat preservation time is 2-6 hours.
3. The method for producing styrene oxide according to claim 1, wherein:
in the reaction step (2), the water dosage is 0.4-1.0 times of the weight of the 2-bromo-1-phenylethanol;
the dosage of the 20% -50% sodium hydroxide aqueous solution is 0.15-0.5 times of the weight of the 2-bromo-1-phenylethanol; the 2-bromo-1-phenylethanol is added dropwise at 40-50 ℃ for 1-4 hours, the reaction temperature is kept at 45-60 ℃ and the reaction time is kept at 0.5-3 hours.
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| JP5633672B2 (en) * | 2010-05-21 | 2014-12-03 | 独立行政法人産業技術総合研究所 | Method for producing styrene oxide compound |
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