CN109096143B - Method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid - Google Patents
Method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid Download PDFInfo
- Publication number
- CN109096143B CN109096143B CN201811172982.7A CN201811172982A CN109096143B CN 109096143 B CN109096143 B CN 109096143B CN 201811172982 A CN201811172982 A CN 201811172982A CN 109096143 B CN109096143 B CN 109096143B
- Authority
- CN
- China
- Prior art keywords
- acid
- triethylamine
- hydrogen peroxide
- diethylhydroxylamine
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
Abstract
The invention discloses a method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid, which comprises the following steps: (1) reacting a mixed aqueous solution of a solid acid catalyst loaded with heteropoly acid, triethylamine, acetic acid and hydrogen peroxide at 35-70 ℃ for 3-16 h, removing hydrogen peroxide and peracetic acid which are not completely reacted, and distilling to obtain triethylamine oxide; (2) and (3) distilling the triethylamine oxide at 50-80 ℃ under reduced pressure under the protection of inert gas, and when the distillate is obviously reduced, heating to 80-150 ℃ for cracking to obtain the triethylamine oxide. Compared with the traditional hydrogen peroxide oxidant, the method takes the peroxyacetic acid as the oxidant, the selectivity of the diethylhydroxylamine product is high, and the adopted supported heteropolyacid catalyst has high activity and high selectivity and can be repeatedly used.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to a method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid.
Background
N, N-Diethylhydroxylamine (DEHA), formula (C)2H5)2NOH is colorless transparent liquid in a pure product, is light yellow transparent liquid in an industrial product, and has the relative density of 1.867 (0-20 ℃), the melting point of-25 ℃, the boiling point of 125-130 ℃, the flash point of 45 ℃ and the refractive index of 1.4195(20 ℃). DEHA is non-toxic, has no pollution to products, has high solubility in monomers, is easy to remove from the monomers, and is convenient to use. DEHA is an organic reducing agent with medium strength, belongs to a disubstituted hydroxylamine compound, has the characteristics of high efficiency, low toxicity, no corrosion, easy separation and the like, has high polymerization inhibition performance in gas-liquid two phases, has no influence on polymerization inhibition efficiency along with temperature change, has polymerization inhibition effect close to that of tert-butylphenol at room temperature, has polymerization inhibition efficiency 2 times that of the tert-butylphenol at 120 ℃, and is commonly used as a polymerization inhibitor and an end terminator in the free radical polymerization of olefin monomers. In the synthetic styrene-butadiene rubber, DEHA is used as a terminatorWith good performance, has been widely used in some SBR plants in the united states and japan for a long time. DEHA can be used as antioxidant to prevent aging and deterioration of olefin monomer, polyolefin, synthetic fiber, etc., and has stabilizing effect on olefin-containing oil such as gasoline, kerosene, and diesel oil, and can prolong retention time. While DEHA is also a good free radical scavenger, the formation of photochemical smog can be effectively controlled by spraying 0.05ppm DEHA in the atmosphere, and in the silicone rubber industry, DEHA is an intermediate of greenhouse polyether or polyester silicone rubber and an excellent dispersant of silicone rubber. Is an important intermediate in organic synthesis and is also a reducing agent for selective hydrogenation of quinones. In the photographic industry, DEHA can be used to reduce quinones to produce photographic developers. In addition, the water supply system of the steam boiler can be used as an oxygen scavenger for protecting the boiler and can also be used as a corrosion inhibitor for the water side surface of metal equipment. Therefore, DEHA is of great significance in production research.
The synthesis of diethylhydroxylamine was studied as early as 1982 in Nakamurashinjzo et al, Japan, using acetaldoxime as a raw material, which was reduced by a mixture of hydrogen and nitrogen or hydrogen to diethylhydroxylamine under the action of a noble metal catalyst, an alkali metal hydroxide catalyst or an alkaline earth metal hydroxide catalyst. In 1985, Wangke's test of organic synthesis plant of Jilin chemical industry company takes triethylamine as raw material, and utilizes the action of hydrogen peroxide and composite catalyst to make two kinds of industrial-grade diethylhydroxylamine through three procedures of oxidation, dehydration and pyrolysis. In 1997, the chemical research institute of atomic energy science, china, Zhang Anyu, takes triethylamine as a raw material, and quantitatively synthesizes the diethylhydroxylamine through three steps of oxidation, dehydration and pyrolysis by utilizing the action of hydrogen peroxide and oxygen. In 1999, Wangchunde et al, university of Yangzhou, which used triethylamine as a raw material, synthesized diethylhydroxylamine by oxidation with industrial hydrogen peroxide under mild conditions. The result shows that the purity and the yield of the product are high, the synthetic route is simple and feasible, and the method is suitable for industrial production. In 2000, Diethylhydroxylamine was synthesized from Diethylamine and Triethylamine by Harbin university of Industrial by oxidation, catalytic pyrolysis under reduced pressure and rectification under the action of titanium silicalite catalyst and hydrogen peroxide. The experimental comparison shows that the triethylamine oxidation pyrolysis method is more stable and effective than the diethylamine oxidation method. It is known that dialkylhydroxylamines can be prepared by reacting compounds containing N-O chains with organometallic compounds or by reacting alkyl-substituted or alkylhydroxylamines with haloalkanes, as well as by oxidation of diethylamine and oxidative cleavage of triethylamine, etc. From the industrial aspects of synthesis cost, raw material price, yield, product purity and the like, the two most common methods for synthesizing DEHA are a diethylamine oxidation method and a triethylamine oxidative cracking method. The preparation of the diethylhydroxylamine by the diethylamine oxide has the disadvantages of complex process, low product purity and high production cost. At present, most manufacturers at home and abroad mainly adopt a triethylamine oxidative cracking method to produce N, N-diethyl hydroxylamine, but the method for preparing the N, N-diethyl hydroxylamine by oxidizing, dehydrating and cracking triethylamine and hydrogen peroxide obviously has the defect of low product purity.
Disclosure of Invention
In view of the above problems, the present invention provides a method for synthesizing diethylhydroxylamine by oxidation of peroxyacetic acid. The method adopts peracetic acid as an oxidant, triethylamine can be subjected to high-selectivity reaction under the oxidation action of the peracetic acid to obtain an intermediate product, namely triethylamine oxide, and the diethyl hydroxylamine with the yield of more than 80% is obtained through further dehydration and cracking.
The purpose of the invention can be realized by the following technical scheme:
a method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid comprises the following steps:
(1) reacting a mixed aqueous solution of a solid acid catalyst loaded with heteropoly acid, triethylamine, acetic acid and hydrogen peroxide at 35-70 ℃ for 3-16 h, removing hydrogen peroxide and peracetic acid which are not completely reacted, and distilling to obtain triethylamine oxide;
(2) and (3) distilling the triethylamine oxide at 50-80 ℃ under reduced pressure under the protection of inert gas, and when the distillate is obviously reduced, heating to 80-150 ℃ for cracking to obtain the triethylamine oxide.
Further, the preferable temperature in the step (1) is 45-70 ℃.
Further, the heteropoly acid in the step (1) is phosphotungstic acid.
Further, the solid acid catalyst in the step (1) is Amberlyst-15.
Further, the solid acid catalyst loaded with heteropoly acid in the step (1) has a solid loading of 15-35 wt%; the addition amount of the solid acid catalyst loaded with the heteropoly acid is 0.02-0.1% of the total mass of reactants (without solvent). The solid loading amount is calculated according to the mass difference of the solid acid catalyst before and after solid loading.
Further, the preparation method of the solid acid catalyst loaded with heteropoly acid in step (1) comprises:
immersing the solid acid catalyst in an alcohol solvent for 3-4 h, drying to a constant weight, adding a heteropoly acid aqueous solution, stirring for 4-6 h, washing with water to neutrality, and drying to a constant weight to obtain the catalyst.
Preferably, the alcohol solvent is ethanol.
Preferably, the drying is performed at 30-40 ℃.
Preferably, the concentration of the aqueous solution of the heteropoly acid is 1-5 wt%.
Further, the concentration of the aqueous hydrogen peroxide solution in the step (1) is 30-50 wt%.
Furthermore, in the step (1), the mass ratio of the triethylamine to the hydrogen peroxide to the acetic acid is 1: 1-1.1: 1-2.
Further, the preferable cracking temperature of the step (2) is 105-110 ℃.
Further, the pressure of the reduced pressure distillation in the step (2) is-0.09 MPa.
Further, the step (1) also comprises the step of standing for 18-36 hours after the reaction is finished.
Further, the step (2) also comprises the steps of washing, extracting and drying the product.
Further, the inert gas is nitrogen or argon.
The invention has the beneficial effects that:
(1) the supported heteropoly acid catalyst has high activity and high selectivity and can be repeatedly used.
(2) The process has high product selectivity, and the yield of the product diethylhydroxylamine is 84.41 percent at most.
Detailed description of the preferred embodiments
Example 1
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
firstly, Amberlyst-15 is immersed in ethanol solution, stirred for 3 hours at room temperature and then dried to balance weight at 40 ℃ for standby. Phosphotungstic acid (H) with the mass concentration of 1.0 percent3PW12O40·XH2O) aqueous solution is added into 6.0g of treated Amberlyst-15, stirred for 4h at room temperature, washed to be neutral after stirring, evaporated out water under negative pressure, dried at 40 ℃ to be balanced to obtain 7.43g of Amberlyst-15 immobilized phosphotungstic acid catalyst (the immobilization amount is 19.25%).
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 30.03g (0.50mol) of glacial acetic acid (HOAc) and 0.1g of amberlyst-15 immobilized heteropoly acid catalyst after treatment are added, the water bath is kept at the constant temperature of 50 ℃, 56.68g (0.50mol) of 30% hydrogen peroxide is added dropwise within 90min, the temperature is raised to 60 ℃ for reaction for 3h after the addition of hydrogen peroxide is finished, the reaction is kept still at room temperature for 24h, then 0.5g of manganese dioxide is added to decompose the excess hydrogen peroxide and peroxyacetic acid, and the stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 110 ℃ again, and collecting 60.04g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating liquid, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 36.85g of a product, wherein the yield is 82.67%, and the purity is 93.5% by gas chromatography analysis.
Example 2
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
firstly, Amberlyst-15 is immersed in ethanol solution, stirred for 3 hours at room temperature and then dried to balance weight at 40 ℃ for standby. Phosphorus-tungsten with the mass concentration of 2.0 percentAcid (H)3PW12O40·XH2O) aqueous solution is added into 6.0g of treated Amberlyst-15, stirred for 4h at room temperature, washed to be neutral after stirring, evaporated out water under negative pressure, dried at 40 ℃ to be balanced to obtain 7.85g of Amberlyst-15 immobilized phosphotungstic acid catalyst (the immobilization amount is 23.57%).
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 33.03g (0.55mol) of glacial acetic acid (HOAc) and 0.51g of amberlyst-15 immobilized heteropoly acid catalyst after treatment are added, the water bath is kept at the constant temperature of 50 ℃, 62.35g (0.55mol) of 30% hydrogen peroxide is added dropwise within 90min, the temperature is raised to 60 ℃ for reaction for 3h after the addition of the hydrogen peroxide is finished, the reaction is kept still at room temperature for 18h, then 0.5g of manganese dioxide is added to decompose the excessive hydrogen peroxide and peroxyacetic acid, and the stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 105 ℃ again, and collecting 62.46g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 37.58g of a product, wherein the yield is 84.32%, and the purity is 94.2% by gas chromatography analysis.
Example 3
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
firstly, Amberlyst-15 is immersed in ethanol solution, stirred for 3 hours at room temperature and then dried to balance weight at 40 ℃ for standby. Phosphotungstic acid (H) with the mass concentration of 3.0 percent3PW12O40·XH2O) aqueous solution is added into 6.0g of treated Amberlyst-15, stirred for 4h at room temperature, washed to be neutral after stirring, evaporated out water under negative pressure, dried at 40 ℃ to be balanced weight, and 8.64g of Amberlyst-15 immobilized phosphotungstic acid catalyst (the immobilized amount is 30.56%) is obtained.
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 45.04g (0.75mol) of glacial acetic acid (HOAc) and 0.4g of amberlyst-15 immobilized heteropoly acid catalyst after treatment are added, the water bath is kept at the constant temperature of 50 ℃, 56.68g (0.50mol) of 30% hydrogen peroxide is added dropwise within 90min, the temperature is raised to 70 ℃ for reaction for 8h after the dropwise addition is finished, the mixture is kept still at room temperature for 30h, then 0.5g of manganese dioxide is added to decompose the excessive hydrogen peroxide and peroxyacetic acid, and the stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 80 ℃, when the distillate is obviously reduced, heating to the target temperature of 150 ℃ again, and collecting 60.48g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating liquid, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 39.19g of a product, wherein the yield is 87.93%, and the purity is 94.6% by gas chromatography analysis.
Example 4
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
amberlyst-15 is firstly immersed in ethanol solution, stirred for 4 hours at room temperature and then dried to balance weight at 40 ℃ for standby. Phosphotungstic acid (H) with the mass concentration of 3.5 percent3PW12O40·XH2O) aqueous solution is added into 6.0g of treated Amberlyst-15, stirred for 6h at room temperature, washed to be neutral after stirring, evaporated out water under negative pressure, dried at 40 ℃ to be balanced to obtain 9.23g of Amberlyst-15 immobilized phosphotungstic acid catalyst (the immobilization amount is 34.99%).
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 49.54g (0.825mol) of glacial acetic acid (HOAc) and 0.20g of amberlyst-15 immobilized heteropoly acid catalyst after treatment are added, the water bath is kept at the constant temperature of 35 ℃, 62.35g (0.55mol) of 30% hydrogen peroxide is added dropwise within 90min, reaction is carried out at 35 ℃ for 16h after dropwise addition, standing is carried out at room temperature for 36h, then 0.5g of manganese dioxide is added to decompose excessive hydrogen peroxide and peroxyacetic acid, and stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 50 ℃, when the distillate is obviously reduced, heating to the target temperature of 80 ℃ again, and collecting 59.66g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 39.35g of a product, wherein the yield is 88.28 percent, and the purity is 94.8 percent by gas chromatography analysis.
Example 5
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
firstly, Amberlyst-15 is immersed in ethanol solution, stirred for 3 hours at room temperature and then dried to balance weight at 40 ℃ for standby. Phosphotungstic acid (H) with the mass concentration of 4.0 percent3PW12O40·XH2O) aqueous solution is added into 6.0g of treated Amberlyst-15, stirred for 5h at room temperature, washed to be neutral after stirring, evaporated to be water under negative pressure and dried at 30 ℃ to be balanced weight, and 8.06g (25.56 percent of immobilized amount) of the Amberlyst-15 immobilized phosphotungstic acid catalyst is obtained.
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 60.05g (1.00mol) of glacial acetic acid (HOAc) and 0.35g of amberlyst-15 immobilized heteropoly acid catalyst after treatment are added, the water bath is kept at the constant temperature of 45 ℃, 56.68g (0.50mol) of 30% hydrogen peroxide is added dropwise within 90min, reaction is carried out at 45 ℃ for 12h after dropwise addition is finished, standing is carried out for 24h at room temperature, then 0.5g of manganese dioxide is added to decompose excessive hydrogen peroxide and peroxyacetic acid, and stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 105 ℃ again, and collecting 61.94g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating liquid, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 38.69g of a product, wherein the yield is 86.80%, and the purity is 94.1% by gas chromatography analysis.
Example 6
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
firstly, Amberlyst-15 is immersed in ethanol solution, stirred for 3 hours at room temperature and then dried to balance weight at 40 ℃ for standby. Phosphotungstic acid (H) with the mass concentration of 5.0 percent3PW12O40·XH2O) aqueous solution is added into 6.0g of treated Amberlyst-15, stirred for 4h at room temperature, washed to be neutral after stirring, evaporated out water under negative pressure, dried at 40 ℃ to be balanced to obtain 7.06g (the immobilized amount is 15.01%) of Amberlyst-15 immobilized phosphotungstic acid catalyst.
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 60.05g (1.00mol) of glacial acetic acid (HOAc) and 0.28g of amberlyst-15 immobilized heteropoly acid catalyst after treatment are added, the water bath is kept at the constant temperature of 50 ℃, 62.35g (0.55mol) of 30 percent hydrogen peroxide is added dropwise within 90min, the temperature is raised to 60 ℃ for reaction for 3h after the addition of the hydrogen peroxide is finished, the reaction is kept still at room temperature for 24h, then 0.5g of manganese dioxide is added to decompose the excess hydrogen peroxide and peroxyacetic acid, and the stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 120 ℃ again, and collecting 63.48g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 37.62g of a product, wherein the yield is 84.41%, and the purity is 94.5% by gas chromatography analysis.
Example 7 comparative example
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
the Amberlyst-15 immobilized phosphotungstic acid catalyst prepared in example 6(1) was used.
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 0.20g of amberlyst-15 immobilized heteropoly acid catalyst after treatment is added, the temperature of a water bath is kept constant to 50 ℃, 62.35g (0.55mol) of 30% hydrogen peroxide is added dropwise within 90min, after the addition of the hydrogen peroxide is finished, the temperature is raised to 60 ℃ for reaction for 3h, the mixture is kept still at room temperature for 24h, then 0.5g of manganese dioxide is added to decompose excessive hydrogen peroxide, and the mixture is stirred until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 110 ℃ again, and collecting 58.48g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 33.16g of a product, wherein the yield is 74.41 percent, and the purity is 94.2 percent by gas chromatography analysis.
Example 8 comparative example
Preparation of Amberlyst-15 immobilized phosphotungstic acid catalyst:
the Amberlyst-15 immobilized phosphotungstic acid catalyst prepared in example 6(1) was used. Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 0.20g of amberlyst-15 supported heteropoly acid catalyst after treatment is added, the temperature of a water bath is kept constant at 50 ℃, 60.28g (0.55mol) of peroxyacetic acid solution is dripped within 90min, after dripping, the temperature is raised to 60 ℃ for reaction for 3h, the mixture is kept still at room temperature for 28h, then 0.5g of manganese dioxide is added to decompose excessive hydrogen peroxide and peroxyacetic acid, and stirring is carried out until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 105-110 ℃ again, and collecting 58.48g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating liquid, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 39.86g of a product, wherein the yield is 89.41%, and the purity is 94.6% by gas chromatography analysis.
Example 9 comparative example
Preparation of triethylamine oxide:
50.6g (0.50mol) of triethylamine (DEA) and 100g of aqueous solution are stirred and mixed into a three-neck flask, 66.06g (1.10mol) of glacial acetic acid (HOAc) is added, the water bath is kept at the constant temperature of 50 ℃, 62.35g (0.55mol) of 30% hydrogen peroxide is added dropwise within 90min, after the addition of the hydrogen peroxide is finished, the temperature is raised to 60 ℃ for reaction for 3h, the mixture is kept still for 24h at room temperature, then 0.5g of manganese dioxide is added to decompose excessive hydrogen peroxide and peroxyacetic acid, and the mixture is stirred until no bubbles are generated. Distilling to obtain colorless viscous triethylamine oxide.
Preparation of diethylhydroxylamine: and (3) under the protection of nitrogen, decompressing the colorless sticky matter to-0.09 MPa, heating to 70 ℃, when the distillate is obviously reduced, heating to the target temperature of 105-110 ℃ again, and collecting 61.48g of distillate after the distillation is finished. Adding 20g of sodium chloride into the distillate, stirring, separating, extracting a brine layer by using 100ml of isopropyl ether, distilling off the isopropyl ether, combining organic phases, drying by using 5.0g of anhydrous magnesium sulfate to obtain 33.6g of a product, wherein the yield is 75.45%, and the purity is 94.5% by gas chromatography analysis.
Claims (10)
1. A method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid is characterized by comprising the following steps:
(1) reacting a mixed aqueous solution of a solid acid catalyst loaded with heteropoly acid, triethylamine, acetic acid and hydrogen peroxide at 35-70 ℃ for 3-16 h, removing hydrogen peroxide and peracetic acid which are not completely reacted, and distilling to obtain triethylamine oxide; the heteropoly acid is phosphotungstic acid;
(2) and (3) distilling the triethylamine oxide at 50-80 ℃ under reduced pressure under the protection of inert gas, and when the distillate is obviously reduced, heating to 80-150 ℃ for cracking to obtain the triethylamine oxide.
2. The method according to claim 1, wherein the reaction temperature in the step (1) is 45 to 70 ℃.
3. The method of claim 1, wherein the solid acid catalyst of step (1) is Amberlyst-15.
4. The method according to claim 1, wherein the solid acid catalyst loaded with heteropoly acid in the step (1) has a catalyst solid loading of 15-35 wt%; the addition amount of the solid acid catalyst loaded with the heteropoly acid is 0.02-0.1% of the mass of the total reactants without solvent.
5. The method according to claim 1, wherein the heteropolyacid-supported solid acid catalyst of step (1) is prepared by a method comprising:
immersing the solid acid catalyst in an alcohol solvent for 3-4 h, drying to a constant weight, adding a heteropoly acid aqueous solution, stirring for 4-6 h, washing with water to neutrality, and drying to a constant weight to obtain the catalyst.
6. The method according to claim 5, wherein the drying is drying at 30-40 ℃.
7. The method according to claim 5, wherein the aqueous solution of the heteropoly acid has a concentration of 1-5% wt.
8. The method according to claim 1, wherein in the step (1), the mass ratio of the triethylamine, the hydrogen peroxide and the acetic acid is 1: 1-1.1: 1-2.
9. The method of claim 1, wherein the cracking temperature in step (2) is 105-110 ℃.
10. The method according to claim 1, wherein the step (1) further comprises the step of standing for 18-36 hours after the reaction is finished.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811172982.7A CN109096143B (en) | 2018-10-09 | 2018-10-09 | Method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811172982.7A CN109096143B (en) | 2018-10-09 | 2018-10-09 | Method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109096143A CN109096143A (en) | 2018-12-28 |
| CN109096143B true CN109096143B (en) | 2021-08-27 |
Family
ID=64868527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811172982.7A Active CN109096143B (en) | 2018-10-09 | 2018-10-09 | Method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109096143B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892586A (en) * | 2021-01-20 | 2021-06-04 | 济宁学院 | Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336387A (en) * | 1964-02-28 | 1967-08-15 | Shell Oil Co | Tertiary amine oxides |
| CS155859B1 (en) * | 1970-01-22 | 1974-06-24 | ||
| RO72580A2 (en) * | 1977-12-02 | 1981-07-30 | Combinatul Petrochimic,Ro | PROCEDURE FOR PREPARATION OF N, N-DIETIHYDROXYLAMINE |
| EP0092862A1 (en) * | 1982-04-21 | 1983-11-02 | THE PROCTER & GAMBLE COMPANY | Process for the oxidation of tertiary amines to amine oxides |
| JPH08157443A (en) * | 1994-12-08 | 1996-06-18 | Lion Akzo Kk | Production of amine oxide aqueous solution |
| CN1157816A (en) * | 1995-12-19 | 1997-08-27 | 埃勒夫阿托化学有限公司 | Process for obtaining N-monosubstituted hydroxylamine |
| EP0688322B1 (en) * | 1993-03-13 | 1998-01-07 | Solvay Interox Limited | Oxidation of ketones |
| EP1209148A1 (en) * | 2000-11-22 | 2002-05-29 | Council of Scientific and Industrial Research | Process for the preparation of amine oxides |
| JP2002234867A (en) * | 2000-11-22 | 2002-08-23 | Council Scient Ind Res | Process for producing amine oxide |
| CN1089753C (en) * | 1997-03-20 | 2002-08-28 | 通用电气公司 | Synthesis of tertiary amine oxides |
| JP2003081932A (en) * | 2001-09-05 | 2003-03-19 | Lion Akzo Kk | Method for producing amine oxide |
| EP1348692A1 (en) * | 2002-03-28 | 2003-10-01 | Council of Scientific and Industrial Research | Process for the preparation of amine oxides |
| JP2003286243A (en) * | 2002-01-24 | 2003-10-10 | Sumitomo Chem Co Ltd | Method for producing n-oxide and catalyst therefor |
| JP2004307473A (en) * | 2003-03-25 | 2004-11-04 | Sumitomo Chem Co Ltd | Method for producing tungsten complex |
| CN103012219A (en) * | 2012-12-20 | 2013-04-03 | 北京桑普生物化学技术有限公司 | Preparation method for trimethylamine oxide |
| CN103570617A (en) * | 2013-11-15 | 2014-02-12 | 浙江荣凯化工科技有限公司 | Preparation method of 3-cyano-pyridine N-oxide |
| CN104974088A (en) * | 2015-06-29 | 2015-10-14 | 周口师范学院 | High efficient heterogeneous catalytic preparation method of pyridine oxynitride |
| CN106349003A (en) * | 2016-08-26 | 2017-01-25 | 济宁康德瑞化工科技有限公司 | Byproduct comprehensive utilization method in diethyl hydroxylamine production |
| CN107265420A (en) * | 2017-06-29 | 2017-10-20 | 河北工业大学 | A kind of method that azanol is prepared by cyclohexanone oxime hydrolysis |
-
2018
- 2018-10-09 CN CN201811172982.7A patent/CN109096143B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336387A (en) * | 1964-02-28 | 1967-08-15 | Shell Oil Co | Tertiary amine oxides |
| CS155859B1 (en) * | 1970-01-22 | 1974-06-24 | ||
| RO72580A2 (en) * | 1977-12-02 | 1981-07-30 | Combinatul Petrochimic,Ro | PROCEDURE FOR PREPARATION OF N, N-DIETIHYDROXYLAMINE |
| EP0092862A1 (en) * | 1982-04-21 | 1983-11-02 | THE PROCTER & GAMBLE COMPANY | Process for the oxidation of tertiary amines to amine oxides |
| EP0688322B1 (en) * | 1993-03-13 | 1998-01-07 | Solvay Interox Limited | Oxidation of ketones |
| JPH08157443A (en) * | 1994-12-08 | 1996-06-18 | Lion Akzo Kk | Production of amine oxide aqueous solution |
| CN1157816A (en) * | 1995-12-19 | 1997-08-27 | 埃勒夫阿托化学有限公司 | Process for obtaining N-monosubstituted hydroxylamine |
| CN1089753C (en) * | 1997-03-20 | 2002-08-28 | 通用电气公司 | Synthesis of tertiary amine oxides |
| JP2002234867A (en) * | 2000-11-22 | 2002-08-23 | Council Scient Ind Res | Process for producing amine oxide |
| EP1209148A1 (en) * | 2000-11-22 | 2002-05-29 | Council of Scientific and Industrial Research | Process for the preparation of amine oxides |
| JP2003081932A (en) * | 2001-09-05 | 2003-03-19 | Lion Akzo Kk | Method for producing amine oxide |
| JP2003286243A (en) * | 2002-01-24 | 2003-10-10 | Sumitomo Chem Co Ltd | Method for producing n-oxide and catalyst therefor |
| EP1348692A1 (en) * | 2002-03-28 | 2003-10-01 | Council of Scientific and Industrial Research | Process for the preparation of amine oxides |
| JP2004307473A (en) * | 2003-03-25 | 2004-11-04 | Sumitomo Chem Co Ltd | Method for producing tungsten complex |
| CN103012219A (en) * | 2012-12-20 | 2013-04-03 | 北京桑普生物化学技术有限公司 | Preparation method for trimethylamine oxide |
| CN103570617A (en) * | 2013-11-15 | 2014-02-12 | 浙江荣凯化工科技有限公司 | Preparation method of 3-cyano-pyridine N-oxide |
| CN104974088A (en) * | 2015-06-29 | 2015-10-14 | 周口师范学院 | High efficient heterogeneous catalytic preparation method of pyridine oxynitride |
| CN106349003A (en) * | 2016-08-26 | 2017-01-25 | 济宁康德瑞化工科技有限公司 | Byproduct comprehensive utilization method in diethyl hydroxylamine production |
| CN107265420A (en) * | 2017-06-29 | 2017-10-20 | 河北工业大学 | A kind of method that azanol is prepared by cyclohexanone oxime hydrolysis |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and applications of a polymer supported peroxotungstate complex as a novel polymeric oxidizing agent;Bahman Tamami;《Reactive & Functional Polymers》;20021231;表1 * |
| 二乙基羟胺的合成;王存德;《广东化工》;19991231;合成步骤 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109096143A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109096144B (en) | Method for synthesizing diethylhydroxylamine | |
| CN109096143B (en) | Method for synthesizing diethylhydroxylamine by adopting peroxyacetic acid | |
| CN111871432A (en) | Preparation method of mesoporous solid acid catalyst and application of mesoporous solid acid catalyst in antioxidant BHT synthesis | |
| Hoff et al. | Acid-catalyzed addition of phosphine to olefins | |
| EP0051328B1 (en) | Process for the preparation of alcohols | |
| US2734086A (en) | Production of aromatic hydroperoxides | |
| Chodák et al. | Crosslinking of polypropylene in the presence of polyfunctional monomers | |
| CN108003096B (en) | Method for preparing ethoxyquinoline through WO3/AC/SO3H concerted catalysis | |
| CN102153473A (en) | Method for preparing perfluor alkyl ethyl acrylate | |
| Hermans et al. | The reaction of benzoyl peroxide with cyclohexane and cyclohexene. Contribution to the mechanism of the catalyzing action of peroxides in the polymerization of vinyl derivatives | |
| US3429936A (en) | Novel polyalkyl alcohols | |
| JPH01199936A (en) | Production of partial ester of pentaerythritol | |
| TW201615690A (en) | Hydrophilic antioxidant and process for the preparation of the same | |
| US3427348A (en) | Preparation of glycols and glycol esters by oxidation of olefins with selenium dioxide | |
| FR2753446A1 (en) | PROCESS FOR THE MANUFACTURE OF ALKYLIMIDAZOLIDONE (METH) ACRYLATES | |
| US3970532A (en) | 2-Hydroxyethylphosphines | |
| Morin et al. | Catalytic Esterification of Olefins with Organic Acids | |
| RU2805146C1 (en) | Method for obtaining thiomethylphenol derivative | |
| CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
| US2513558A (en) | Treatment of hydrocarbon type dry | |
| KR100392279B1 (en) | Process for the preparation of 1,2,3,6-tetrahydro-2,2,6,6- tetramethylpyridine N-oxide | |
| CN114524721A (en) | Synthesis process of methacrolein | |
| CN110655533B (en) | Preparation method of 4- (diethoxy-phosphoryl) -2-methyl-butyl-2-olefine acid ester | |
| CN114849679B (en) | Solid super acid supported catalyst and preparation method of beta-phenethyl alcohol | |
| NO790099L (en) | PROCEDURE FOR PREPARING ESTERES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |