CN113893875A - Preparation method of double-bond epoxidation phase transfer catalyst with high recovery rate - Google Patents
Preparation method of double-bond epoxidation phase transfer catalyst with high recovery rate Download PDFInfo
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- 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
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- 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
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
Abstract
The invention discloses a preparation method of a double-bond epoxidation phase transfer catalyst with high recovery rate. At a certain temperature, reacting tungstic acid (molybdic acid) with hydrogen peroxide to generate peroxy acid, adding a phosphorus source into a peroxy acid solution to react for a period of time to generate peroxyphosphotungstic acid (peroxyphosphomolybdic acid), dissolving long-chain alkylamine into a solvent, dropwise adding the solution into the peroxyphosphotungstic acid (peroxyphosphomolybdic acid) solution to react for a period of time, adding a certain amount of recovery agent into the solution, stirring uniformly, removing the solvent and drying to obtain the double-bond epoxidation phase transfer catalyst. The double-bond epoxidation phase transfer catalyst prepared by the invention has the characteristics of high catalytic activity, high recovery rate, reusability, environmental friendliness and the like, and therefore, the double-bond epoxidation phase transfer catalyst has good application value in the fields of olefin epoxidation catalysis, oxidative desulfurization technology and the like.
Description
Technical Field
The invention relates to the field of organic chemical catalysts, in particular to a preparation method of a double-bond epoxidation phase transfer catalyst with high recovery rate.
Background
The epoxy resin is an organic polymer compound containing two or more than two epoxy groups in a molecular structure, and is an important thermosetting resin. It is known for its outstanding mechanical, adhesion and electrical properties, and it has been widely used in the manufacture of adhesion between various metals and non-metallic materials, corrosion-resistant coatings, electrical insulating materials, glass fiber reinforced plastic composite materials, etc., playing an important role in the fields of electronics, electrical and mechanical manufacture, chemical corrosion protection, aerospace shipping and many other industries, and it is one of the important basic materials in every industrial field. Currently, epoxy compounds are mainly prepared by the oxidation of olefins. The industrial production of epoxy compounds mainly adopts a halohydrin method and a peracid oxidation method, however, the halohydrin method has the disadvantages of complex synthesis process, difficult separation and treatment of byproducts, easy severe corrosion of equipment, and generation of a large amount of chlorine-containing sewage in the production process, thereby causing severe environmental pollution; the peroxyacid method for synthesizing the epoxy compound has the advantages of reliable process and high efficiency, but the peroxyacid is expensive, the peroxyacid oxidation method has potential safety hazards, the epoxy compound is easy to open and decompose in an acid environment, and the product yield is low. Therefore, the application of peroxy acid oxidation to generate epoxy compounds is always limited, and the peroxy acid oxidation is only used for the production of epoxy compounds with higher added value and small tonnage.
The hydrogen peroxide is called as a green oxidant, and natural hydrogen peroxide becomes an ideal oxygen source for olefin epoxidation. However, the epoxidation efficiency of the olefin is extremely low due to incompatibility of the hydrogen peroxide and the olefin, so that the catalyst catalysis of the hydrogen peroxide to epoxidize the olefin becomes a research hotspot. The peroxyphosphotungstic acid quaternary ammonium salt has structural particularity, and the catalytic epoxidation performance of the peroxyphosphotungstic acid quaternary ammonium salt can be changed by regulating and controlling the types of heteropoly acid and quaternary ammonium salt at the molecular level by using H2O2When used as an oxygen source, has the characteristic of controlling phase transfer in reaction when H2O2Can be precipitated from the reaction system after being used up, and is receiving wide attention.
Non-patent literature (Gaowelin, Zhukai, daily chemical industry, 2019,049(002): 108-. Chinese patent application CN111036293A reports a preparation process of heteropoly acid catalyst. However, these methods have the following disadvantages: (1) when ethanol/water is used as a solvent, the peroxyphosphotungstic acid solution and the long-chain alkylamine solution form solids on the surfaces of liquid drops once being contacted, so that the reacted catalyst is not uniform, and the catalytic effect is not stable due to non-uniform results. (2) The method has high requirements on equipment conditions, and the solid prepared by the method has strong wall adhesion, thereby being not beneficial to industrial production. (3) In the method, the catalyst can be discharged from the system after the catalytic reaction is finished theoretically, however, in the actual catalytic process, the hydrolysis of the catalyst inevitably causes a small amount of the catalyst to be dissolved in an oil layer and a water layer, and the recovery rate of the catalyst and the quality of a product are influenced. Therefore, how to prepare the catalyst with simple process and high recovery rate has great technical challenge.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a preparation method of a double-bond epoxidation phase transfer catalyst with high recovery rate.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a double-bond epoxidation phase transfer catalyst with high recovery rate comprises the following steps and conditions:
(1) adding 25 parts (18 parts) of tungstic acid (molybdic acid) into 6-12 parts of hydrogen peroxide at the temperature of 30-70 ℃ for reaction for 10-60 min to obtain a peroxytungstic acid (peroxymolybdic acid) solution, then adding 2-3 parts of phosphoric acid into the peroxytungstic acid (peroxymolybdic acid) solution, and continuing stirring and reacting for 20-60 min to prepare a peroxyphosphotungstic acid (peroxyphosphomolybdic acid) solution;
(2) dissolving 15-30 parts by weight of long-chain alkylamine in 30-60 parts by weight of solvent to prepare long-chain alkylamine solution;
(3) under the condition of stirring, dropwise adding the long-chain alkylamine solution into a peroxyphosphotungstic acid (peroxyphosphomolybdic acid) solution by using a constant-pressure funnel within a certain time, reacting at the temperature of between 30 and 60 ℃ for 20 to 60 minutes, standing, and separating to obtain the long-chain alkylamine solution of the peroxyphosphotungstic acid (peroxyphosphomolybdic acid) solution;
(4) adding 4-7 parts of a recycling agent into a long-chain alkylamine solution of peroxyphosphotungstic acid (peroxyphosphomolybdic acid), stirring and mixing uniformly, removing the solvent by reduced pressure distillation, and drying to obtain the double-bond epoxidation phase transfer catalyst.
Preferably, the tungstic acid in the step (1) is one of newly prepared tungstic acid, yellow tungstic acid, white tungstic acid and metatungstic acid prepared by the reaction of sodium tungstate and hydrochloric acid; the molybdic acid is one of fresh molybdic acid obtained by reacting ammonium tetramolybdate/ammonium dimolybdate with hydrochloric acid, pure molybdic acid or a combination thereof.
Preferably, the mass fraction of the hydrogen peroxide in the step (1) is 25-50%, and the mass fraction of the phosphoric acid is 85%.
Preferably, the long-chain alkylamine in step (2) is one or a combination of dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, chlorododecylpyridine, bromododecylpyridine, cetrimide, tetradecyltrimethylammonium chloride, chlorotetradecylpyridine, bromotetradecylpyridine, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, chlorohexadecylpyridine, bromohexadecylpyridine, octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, chlorooctadecylpyridine, bromooctadecylpyridine, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine, N-dimethyloctadecylamine, etc.
Preferably, the solvent in step (2) is one or a combination of water, ethyl acetate, dichloromethane, 1, 2-dichloroethane, chloroform, toluene and ethanol.
Preferably, the recycling agent in step (3) is one or a combination of dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, chlorododecylpyridine, bromododecylpyridine, cetrimide, tetradecyltrimethylammonium chloride, chlorotetradecylpyridine, bromotetradecylpyridine, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, chlorohexadecylpyridine, bromohexadecylpyridine, octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, chlorooctadecylpyridine, bromooctadecylpyridine, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine, N-dimethyloctadecylamine, etc.
Preferably, the double bond epoxidation phase transfer catalyst is a compound of the following general formula:
wherein Q is3Represents a long-chain alkylamine.
According to the technical scheme, tungstic acid or molybdic acid reacts with hydrogen peroxide to generate peroxy acid at a certain temperature, a phosphorus source is added into a peroxy acid solution to react for a period of time to generate peroxyphosphotungstic acid (peroxyphosphomolybdic acid), long-chain alkylamine is dissolved in a solvent, the solution is dropwise added into the peroxyphosphotungstic acid (peroxyphosphomolybdic acid) solution to react for a period of time, a certain amount of recovery agent is added into the separated liquid, the mixture is uniformly stirred, the solvent is removed, and the double-bond epoxidation phase transfer catalyst is obtained after drying. Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst is dissolved in the solvent in the presence of hydrogen peroxide, and compared with the existing method of separating out the catalyst by using water as the solvent, the method has the advantages of uniform reaction, simple post-treatment process, high production efficiency, no wall adhesion, no pipeline blockage, simple requirement on equipment and capability of realizing large-scale production.
2. The invention adds the reclaiming agent in the post-treatment, so that the catalyst can enter the organic phase for catalysis more quickly, and can inhibit the hydrolysis of the catalyst, thereby not only improving the reaction activity, but also ensuring that the catalyst has high recovery rate.
Drawings
FIG. 1 shows a double bond epoxidation phase transfer catalyst [ C ] prepared in example 1 of the present invention16H33N(CH3)3]3PW4O24An infrared spectrum of (1).
FIG. 2 shows a double bond epoxidation phase transfer catalyst [ C ] prepared in example 1 of the present invention16H33N(CH3)3]3PW4O24XRD profile of (a).
FIG. 3 shows a double bond epoxidation phase transfer catalyst [ C ] prepared in example 1 of the present invention16H33N(CH3)3]3PW4O24Catalyzing and synthesizing 3, 4-epoxy cyclohexyl methyl-3 ', 4' -epoxy cyclohexyl formic ether.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
(1) Adding 3.4g of sodium tungstate into a constant-temperature water bath jacket three-necked bottle provided with a reflux condenser and a magnetic stirrer, dissolving the sodium tungstate into 20ml of deionized water, and stirring to completely dissolve the sodium tungstate; 2g of HCl (aq) was added and stirred to react well to give a white or pale yellow suspension. Adding 10g H in portions2O2(aq) solution, the precipitate quickly dissolved to give a colorless or yellow solution. Accurately add 0.3gH3PO4(aq), and reacting at 65 ℃ for 30min to obtain a peroxyphosphotungstic acid solution.
(2) Cetyl trimethylammonium bromide (2.8 g) was accurately weighed and dissolved in 20g CH2Cl2And fully stirring to dissolve the mixture for later use.
(3) Under the condition of stirring, dropwise adding the prepared long-chain alkylamine solution into the peroxyphosphotungstic acid solution by using a constant-pressure funnel within a certain time, continuously reacting for 30min at the temperature of 35 ℃, standing at room temperature, and separating to obtain the peroxyphosphotungstic acid long-chain alkylamine solution.
(4) Adding 0.6g of recovery agent cetyl trimethyl ammonium bromide into the peroxyphosphotungstic acid long-chain alkylamine solution, uniformly mixing, and distilling to remove the solvent to obtain the double-bond epoxidation phase transfer catalyst [ C16H33N(CH3)3]3PW4O24The yield was 99.8%.
Referring to FIG. 1, there is shown a double bond epoxidation phase transfer catalyst [ C ] prepared in accordance with example 1 of the present invention16H33N(CH3)3]3PW4O24An infrared spectrum of (1). 1070cm-1Is PO4 3-The absorption peak of skeleton stretching vibration of middle P-O bond is 964cm-1An absorption peak at W ═ O of 895cm-1The absorption peak is antisymmetric stretching vibration of W-O-W, 821cm-1Absorption peak at 595cm of O-O bond-1And 547cm-1An absorption peak at W-O-O bond of 2930cm-1，2860cm-1，1640cm-1The absorption peak is the characteristic absorption peak of C-H in the quaternary ammonium salt.
Referring to FIG. 2, there is shown a double bond epoxidation phase transfer catalyst [ C ] prepared in accordance with example 1 of the present invention16H33N(CH3)3]3PW4O24XRD profile of (a). Three clusters of characteristic peaks appear at 8.26 degrees, 20.24 degrees and 30.27 degrees in the figure, and the characteristic peaks belong to Keggin type structures of quaternary ammonium phosphotungstate.
Referring to FIG. 3, there is shown a double bond epoxidation phase transfer catalyst [ C ] prepared in accordance with example 1 of the present invention16H33N(CH3)3]3PW4O24Catalyzing and synthesizing 3, 4-epoxy cyclohexyl methyl-3 ', 4' -epoxy cyclohexyl formic ether. The resin yield is 99.0%, the resin purity is 99.5%, the resin appearance is colorless and transparent, and the catalyst recovery rate is 99.7%.
Example 2
(1) Adding 3.4g of sodium tungstate into a constant-temperature water bath jacket three-necked bottle provided with a reflux condenser and a magnetic stirrer, dissolving the sodium tungstate into 20ml of deionized water, and stirring to completely dissolve the sodium tungstate; 2g of HCl (aq) was added and stirred to react well to give a white or pale yellow suspension. Adding 10g H in portions2O2(aq) solution, the precipitate quickly dissolved to give a colorless or yellow solution. Accurately add 0.3gH3PO4(aq), and reacting for 60min at 45 ℃ to obtain a peroxyphosphotungstic acid solution.
(2) Octadecyl trimethyl ammonium Bromide 3g was accurately weighed and dissolved in 25g CHCl3And fully stirring to dissolve the mixture for later use.
(3) And (3) under the condition of stirring, dropwise adding the long-chain alkylamine solution prepared in the step (2) into the peroxyphosphotungstic acid solution within a certain time by using a constant-pressure funnel, continuously reacting for 20min at the temperature of 60 ℃, standing at room temperature, and separating to obtain the peroxyphosphotungstic/molybdic acid long-chain alkylamine solution.
(4) Adding 0.7g of octadecyl trimethyl ammonium bromide as a recycling agent into the peroxyphosphotungstic acid long-chain alkylamine solution, uniformly mixing, and distilling to remove the solvent to obtain the double-bond epoxidation phase transfer catalyst [ C18H37N(CH3)3]3PW4O24The yield was 99.6%.
Example 3
(1) Adding 3.4g of sodium tungstate into a constant-temperature water bath jacket three-necked bottle provided with a reflux condenser and a magnetic stirrer, dissolving the sodium tungstate into 20ml of deionized water, and stirring to completely dissolve the sodium tungstate; 2g of HCl (aq) was added and stirred to react well to give a white or pale yellow suspension. Adding 10g H in portions2O2(aq) solution, the precipitate quickly dissolved to give a colorless or yellow solution. Accurately add 0.3gH3PO4(aq), and reacting at 70 ℃ for 20min to obtain the peroxyphosphotungstic acid solution.
(2) Cetylpyridinium chloride 2.6g was accurately weighed and dissolved in 20g CH2Cl2And fully stirring to dissolve the mixture for later use.
(3) Under the condition of stirring, dropwise adding the prepared long-chain alkylamine solution into the peroxyphosphotungstic acid solution by using a constant-pressure funnel within a certain time, continuously reacting for 30min at the temperature of 35 ℃, standing at room temperature, and separating to obtain the peroxyphosphotungstic acid long-chain alkylamine solution.
(4) Adding 0.5g of recovery agent cetyl pyridine chloride into the peroxyphosphotungstic acid long-chain alkylamine solution, uniformly mixing, and distilling to remove the solvent to obtain the double-bond epoxidation phase transfer catalyst [ pi-C5H5NC16H33]3PW4O24The yield was 98.6%.
Example 4
(1) Adding 2g of ammonium molybdate into a constant-temperature water bath jacket three-necked bottle provided with a reflux condenser and a magnetic stirrer, dissolving the ammonium molybdate into 20ml of deionized water, and stirring to completely dissolve the ammonium molybdate; 2g of HCl (aq) was added and stirred to react well to give a white or pale yellow suspension. Adding 10g H in portions2O2(aq) solution, the precipitate quickly dissolved to give a colorless or yellow solution. Accurately add 0.3gH3PO4(aq), and reacting at 65 ℃ for 30min to obtain a phosphomolybdic acid solution.
(2) Cetyl trimethylammonium bromide (2.8 g) was accurately weighed and dissolved in 20g CH2Cl2And fully stirring to dissolve the mixture for later use.
(3) Under the condition of stirring, the prepared long-chain alkylamine solution is dropwise added into the peroxyphosphomolybdic acid solution by using a constant-pressure funnel within a certain time, the reaction is continued for 30min at the temperature of 35 ℃, and after standing at room temperature, liquid separation is carried out to obtain the peroxyphosphomolybdic acid long-chain alkylamine solution.
(4) Adding 0.6g of hexadecyl trimethyl ammonium bromide as a recovery agent into the long-chain alkylamine solution of the phosphomolybdic acid peroxide, uniformly mixing, and distilling to remove the solvent to obtain the double-bond epoxidation phase transfer catalyst [ C16H33N(CH3)3]3PMo4O24The yield was 99.4%.
Example 5
(1) Adding 2g of ammonium molybdate into a constant-temperature water bath jacket three-necked bottle provided with a reflux condenser and a magnetic stirrer, dissolving the ammonium molybdate into 20ml of deionized water, and stirring to completely dissolve the ammonium molybdate; 2g of HCl (aq) was added and stirred to react wellTo obtain white or light yellow suspension. Adding 10g H in portions2O2(aq) solution, the precipitate quickly dissolved to give a colorless or yellow solution. Accurately add 0.3gH3PO4(aq), and reacting at 70 ℃ for 20min to obtain a phosphomolybdic acid solution.
(2) Cetylpyridinium chloride 2.6g was weighed accurately and dissolved in 20g CHCl3And fully stirring to dissolve the mixture for later use.
(3) Under the condition of stirring, the prepared long-chain alkylamine solution is dropwise added into the peroxyphosphomolybdic acid solution by using a constant-pressure funnel within a certain time, the reaction is continued for 30min at the temperature of 35 ℃, and after standing at room temperature, liquid separation is carried out to obtain the peroxyphosphomolybdic acid long-chain alkylamine solution.
(4) Adding 0.5g of recovery agent cetyl pyridine chloride into the long-chain alkylamine solution of the phosphomolybdic acid peroxide, uniformly mixing, and distilling to remove the solvent to obtain the double-bond epoxidation phase transfer catalyst [ pi-C5H5NC16H33]3PMo4O24The yield was 98.6%.
Example 6
(1) Adding 3.4g of sodium tungstate into a constant-temperature water bath jacket three-necked bottle provided with a reflux condenser and a magnetic stirrer, dissolving the sodium tungstate into 20ml of deionized water, and stirring to completely dissolve the sodium tungstate; 2g of HCl (aq) was added and stirred to react well to give a white or pale yellow suspension. Adding 10g H in portions2O2(aq) solution, the precipitate quickly dissolved to give a colorless or yellow solution. Accurately add 0.3gH3PO4(aq), and reacting at 65 ℃ for 30min to obtain a peroxyphosphotungstic acid solution.
(2) Cetyl trimethylammonium bromide (2.8 g) was weighed out accurately, dissolved in 30g of water, and stirred well to dissolve it for use.
(3) Under the condition of stirring, the prepared long-chain alkylamine solution is dropwise added into the peroxyphosphotungstic acid solution by a constant-pressure funnel within a certain period of time, and the reaction is continued for 30min at the temperature of 35 ℃.
(4) Filtering the solid, washing with water and drying at 60 ℃ to obtain the solid catalyst [ C16H33N(CH3)3]3PW4O24The yield was 95.1%.
Claims (7)
1. A preparation method of a double-bond epoxidation phase transfer catalyst with high recovery rate is characterized by comprising the following steps and conditions:
(1) adding 6-12 parts of hydrogen peroxide into 25 parts of tungstic acid or 18 parts of molybdic acid at 30-70 ℃ by weight for reaction for 10-60 min to obtain a peroxytungstic acid or peroxymolybdic acid solution, then adding 2-3 parts of phosphoric acid into the peroxytungstic acid or peroxymolybdic acid solution, and continuing stirring and reacting for 20-60 min to prepare a peroxyphosphotungstic acid solution or a peroxyphosphomolybdic acid solution;
(2) dissolving 15-30 parts by weight of long-chain alkylamine in 30-60 parts by weight of solvent to prepare long-chain alkylamine solution;
(3) under the condition of stirring, dropwise adding the long-chain alkylamine solution into the peroxyphosphotungstic acid or peroxyphosphomolybdic acid solution by using a constant-pressure funnel within a certain time, reacting at the temperature of 30-60 ℃ for 20-60 min, standing, and separating to obtain the peroxyphosphotungstic acid long-chain alkylamine solution or the peroxyphosphomolybdic acid long-chain alkylamine solution;
(4) adding 4-7 parts of a recycling agent into a peroxyphosphotungstic acid long-chain alkylamine solution or a peroxyphosphomolybdic acid long-chain alkylamine solution, stirring and mixing uniformly, removing the solvent by reduced pressure distillation, and drying to obtain the double-bond epoxidation phase transfer catalyst.
2. The method for preparing the double bond epoxidation phase transfer catalyst with high recovery rate according to claim 1, characterized in that the tungstic acid in the step (1) is one of the new tungstic acid, the yellow tungstic acid, the white tungstic acid and the metatungstic acid prepared by the reaction of sodium tungstate and hydrochloric acid; the molybdic acid is one of fresh molybdic acid prepared by reacting ammonium tetramolybdate/ammonium dimolybdate with hydrochloric acid, pure molybdic acid or a combination thereof.
3. The method for preparing the double bond epoxidation phase transfer catalyst with high recovery rate as claimed in claim 1, wherein the mass fraction of the hydrogen peroxide in the step (1) is 25% -50%, and the mass fraction of the phosphoric acid is 85%.
4. The method for preparing the double bond epoxidation phase transfer catalyst with high recovery rate according to claim 1, the method is characterized in that the long-chain alkylamine in the step (2) is one or a combination of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, chloro dodecyl pyridine, bromo dodecyl pyridine, cetrimide, tetradecyl trimethyl ammonium chloride, chloro tetradecyl pyridine, bromo tetradecyl pyridine, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, chloro hexadecyl pyridine, bromo hexadecyl pyridine, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, chloro octadecyl pyridine, bromo octadecyl pyridine, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine, and N, N-dimethyloctadecylamine.
5. The method for preparing the double bond epoxidation phase transfer catalyst with high recovery rate according to claim 1, wherein the solvent in step (2) is one or a combination of water, ethyl acetate, dichloromethane, 1, 2-dichloroethane, chloroform, toluene and ethanol.
6. The method for preparing the double bond epoxidation phase transfer catalyst with high recovery rate according to claim 1, the method is characterized in that the recycling agent in the step (3) is one or a combination of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, chloro dodecyl pyridine, bromo dodecyl pyridine, cetrimide, tetradecyl trimethyl ammonium chloride, chloro tetradecyl pyridine, bromo tetradecyl pyridine, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, chloro hexadecyl pyridine, bromo hexadecyl pyridine, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, chloro octadecyl pyridine, bromo octadecyl pyridine, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine, and N, N-dimethyloctadecylamine.
7. The method for preparing a double bond epoxidation phase transfer catalyst with high recovery rate according to claim 1, wherein the double bond epoxidation phase transfer catalyst is a compound of the following general formula:
wherein Q is3Represents a long-chain alkylamine.
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| CN114591268A (en) * | 2022-04-01 | 2022-06-07 | 福州大学 | Method for synthesizing alpha-epoxy pinane by epoxidation of alpha-pinene |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
| CN104529934A (en) * | 2014-12-17 | 2015-04-22 | 江苏中旗作物保护股份有限公司 | Synthesis method of chloronicotinyl insecticide clothianidin |
| CN107824219A (en) * | 2017-11-22 | 2018-03-23 | 山东玉皇化工有限公司 | A kind of phase transfer catalyst and preparation method thereof and a kind of method that glutaric acid is prepared using cyclopentene |
| CN109467623A (en) * | 2018-10-29 | 2019-03-15 | 浙江大学 | A kind of epoxidizing method of high molecular weight conjugated diene polymer |
| CN110252413A (en) * | 2019-06-27 | 2019-09-20 | 石河子开发区汇智元科技有限责任公司 | One kind being used for C9 resin raw material oil oxidation desulfurization catalyst |
| CN110548542A (en) * | 2019-09-20 | 2019-12-10 | 济南大学 | Reaction control phase transfer catalyst for chloropropene epoxidation and preparation method thereof |
| CN111029578A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Modified hard carbon negative electrode material and preparation method thereof |
| CN111068781A (en) * | 2020-01-02 | 2020-04-28 | 江苏扬农化工集团有限公司 | Preparation of heteropolyacid catalyst and application of heteropolyacid catalyst in chloropropene epoxidation |
-
2021
- 2021-11-12 CN CN202111354313.3A patent/CN113893875A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
| CN104529934A (en) * | 2014-12-17 | 2015-04-22 | 江苏中旗作物保护股份有限公司 | Synthesis method of chloronicotinyl insecticide clothianidin |
| CN107824219A (en) * | 2017-11-22 | 2018-03-23 | 山东玉皇化工有限公司 | A kind of phase transfer catalyst and preparation method thereof and a kind of method that glutaric acid is prepared using cyclopentene |
| CN109467623A (en) * | 2018-10-29 | 2019-03-15 | 浙江大学 | A kind of epoxidizing method of high molecular weight conjugated diene polymer |
| CN110252413A (en) * | 2019-06-27 | 2019-09-20 | 石河子开发区汇智元科技有限责任公司 | One kind being used for C9 resin raw material oil oxidation desulfurization catalyst |
| CN110548542A (en) * | 2019-09-20 | 2019-12-10 | 济南大学 | Reaction control phase transfer catalyst for chloropropene epoxidation and preparation method thereof |
| CN111029578A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Modified hard carbon negative electrode material and preparation method thereof |
| CN111068781A (en) * | 2020-01-02 | 2020-04-28 | 江苏扬农化工集团有限公司 | Preparation of heteropolyacid catalyst and application of heteropolyacid catalyst in chloropropene epoxidation |
Non-Patent Citations (1)
| Title |
|---|
| 王睿: "杂多化合物的氧化还原性能及其应用", 海南大学学报自然科学版 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591268A (en) * | 2022-04-01 | 2022-06-07 | 福州大学 | Method for synthesizing alpha-epoxy pinane by epoxidation of alpha-pinene |
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