CN103242264B - Method for synthesizing bisphenol A diglycidyl ethers through halogen-free epoxidation - Google Patents
Method for synthesizing bisphenol A diglycidyl ethers through halogen-free epoxidation Download PDFInfo
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Abstract
The invention discloses a method for synthesizing bisphenol A diglycidyl ethers through halogen-free epoxidation, which is characterized by comprising the following steps of: adding bisphenol A diallyl ethers, a solvent I and a phosphotungstic acid quaternary ammonium salt catalyst into a reactor, adding a hydrogen peroxide solution into the reactor while stirring, raising the temperature of a reactant to 30-80 DEG C, and reacting the obtained object for 5-24 hours at a temperature of 30-80 DEG C so as to obtain a reacted material; cooling the reacted material to room temperature, separating an organic phase, after the separated organic phase is subjected to distillation recycling so as to obtain an organic solvent, uniformly stirring and mixing the rest material and ethyl acetate, carrying out filtering on the obtained product, and after filter liquor is subjected to distillation recycling so as to obtain ethyl acetate, obtaining a coarse product; and carrying out column chromatography on the coarse product by using a solvent III so as to obtain bisphenol A diglycidyl ethers. After the method disclosed by the invention is adopted, no organic chlorine ion contains in the process of synthesis, a synthesized target product not only has no organochlorine heterogeneous client base, but also is low in product viscosity, good in performance, simple in process, easy to operate, high in safety, low in pollution and strong in practicability.
Description
Technical field
The invention belongs to the preparation of organic epoxy compound thing, relate to the method for a kind of epoxidation synthesis bisphenol A diglycidyl ether.Bisphenol A diglycidyl ether prepared by the present invention is applicable to high-grade electronic devices and components, as the casting of photodiode (LED), silicon wafer etc., embedding, potting resin, and the Application Areass such as dipping (VPI) resin that high-grade high-voltage motor manufactures.
Background technology
Bisphenol A type epoxy resin is that polycondensation under basic catalyst effect forms by dihydroxyphenyl propane and epoxy chloropropane, the bisphenol A type epoxy resin after polycondensation be by different polymerization degree "
n" value form aggregate, the polymerization degree "
n" value difference causes epoxy resin to have different forms and characteristic, can be divided into liquid and solid-state, wherein "
n=0 " bisphenol A diglycidyl ether has low viscosity, can realize the solvent free that epoxy resin uses; Simultaneously, due to the complicacy of reaction, epoxy chloropropane participates in the macromolecular end group of epoxy resin after polycondensation except epoxy group(ing), also can form a small amount of heterogeneous end group, containing part organochlorine in heterogeneous end group, this kind of impurity will reduce electrical property and the erosion resistance of cured article.In recent years, along with electrician, electron trade development, more and more higher to the requirement of epoxy resin, particularly to future developments that becomes more meticulous such as high purity, low viscosity, low chlorine ion contents, as being applied to pure epoxy acid anhydrides type vacuum pressure impregnation (VPI) resin of high-voltage motor and high purity, the low viscosity epoxy resin in electrically casting, electronic industry, high-grade photodiode (LED) sealing resin.In order to reduce the chloride ion content in epoxy resin, patent (4017526, US, 4499255, US, 4684701, US) report by improving synthesis of bisphenol A and the synthesis route of epoxy chloropropane and the method for aftertreatment purifying, but still a small amount of impurity containing organochlorine can be formed, and technique is loaded down with trivial details, aftertreatment is complicated; In order to obtain high purity, low viscous bisphenol A type epoxy resin, Chinese patent application (201210213683.X) discloses " a kind of method of purification of bisphenol A diglycidyl ether ", and this invention is also based on a kind of physical purification method being raw material with the condensation resin of dihydroxyphenyl propane and epoxy chloropropane.Therefore, in prior art, prepare low chlorine ion content or/and low viscous bisphenol A type epoxy resin is all based on the resin of the polycondensation under basic catalyst effect by dihydroxyphenyl propane and epoxy chloropropane, and then after adopting, the technical matters of a step is carried out purifying and obtains.Therefore, the inevitable heterogeneous end group generated containing organochlorine in synthesized bisphenol A diglycidyl ether, the viscosity of resin is bigger than normal simultaneously, and product performance are poor, are difficult to meet service requirements.
Summary of the invention
Object of the present invention is intended to solve above-mentioned shortcoming of the prior art, provides a kind of method of the epoxidation synthesis bisphenol A diglycidyl ether without the heterogeneous end group generation of organochlorine.
Content of the present invention is: a kind of method of epoxidation synthesis bisphenol A diglycidyl ether, is characterized in that comprising the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:9 ~ 16 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 2 ~ 6 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2 ~ 3 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 15 ~ 70%;
Described solvent I is one or more the mixture in methylene dichloride, methyl iso-butyl ketone (MIBK), trichloromethane, 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation add aqueous hydrogen peroxide solution, temperature of charge is raised to 30 ~ 80 DEG C, react 5 ~ 24 hours at 30 ~ 80 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed (dissolving to solvend), filter, the solids obtained after filtration is quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer (recyclable recycling), then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.5 ~ 2;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 4% ~ 10% and the sherwood oil of 90% ~ 96% are mixed into.
In content of the present invention: the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:8 ~ 11, at 60 DEG C, stirring reaction is after 1 ~ 4 hour, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 17 ~ 21% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:3 ~ 5, then 7 ~ 10 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 0.5 ~ 1 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.07 ~ 0.14mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:1 ~ 3, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 1 ~ 3 hour, static 3 ~ 5 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 50 DEG C ~ 80 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Described quaternary ammonium salt can be at least one in octadecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, TPC and tetradecyl pyridinium bromide.
The preparation method of described catalyzer phosphorus heteropoly tungstic acid quaternary ammonium also can be additive method of the prior art.
Compared with prior art, the present invention has features and beneficial effect:
(1) the present invention adopts the method for " Direct Epoxidation ", and namely in reaction process, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer double bond that is direct and tetrabutyl ammonium bromide under the effect of hydrogen peroxide carries out epoxidation reaction synthesis of bisphenol A diglycidylether; Monomolecular substance is converted into the reaction of monomolecular substance, and synthesized target product is not only without the heterogeneous end group of organochlorine, and viscosity is low, and product performance are good; The Application Areass such as bisphenol A diglycidyl ether product prepared by the present invention is specially adapted to the casting of the components and parts such as high-grade photodiode, silicon wafer in electronic industry, embedding and potting resin, dipping (VPI) resin that high-grade high-voltage motor manufactures.
(2) the present invention is adopted, fundamentally solve in prior art because epoxy chloropropane participates in bisphenol A diglycidyl ether building-up reactions, make all there is organic chlorion in the whole process of synthesizing, thus inevitably there is the heterogeneous end group of organochlorine in target product, the technical barrier of subsequent purification difficulty;
(3) preparation technology of the present invention is simple, and operation is easy, and required equipment is simple, and processing ease, security is high, pollutes little, practical.
Embodiment
Embodiment given below is intended so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is prepared by first part
Quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is prepared for cetyl trimethylammonium bromide etc.:
Hydrogen peroxide (795.6mmol) aqueous solution that 20 grams of wolframic acids (80mmol) and 90.2 gram mass percentage concentrations are 30% is added in reactor, stir and be heated to 60 DEG C, reaction 80 minutes, be cooled to room temperature, by 2.48 gram mass percentage concentrations be again 85% phosphoric acid (21.5mmol) be dissolved in after in 10ml water and add in reaction soln, continue stirring 60 minutes with after this reaction solution of 200ml distilled water diluting; 11.7 grams of tetradecyl trimethyl ammonium chlorides (40mmol) are dissolved in 500ml trichloromethane, join in above-mentioned reaction soln by the mode dripped, and continue stirring 90 minutes, static layering, separate the solvent in organic phase underpressure distillation removing organic phase, residuum is vacuum-drying i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer at 60 DEG C again, and this catalyzer is hereinafter referred to as catalyzer 5.
According to identical ratio and the identical method such as mol ratio, solvent volume ratio of above-mentioned each material, tetradecyl trimethyl ammonium chloride is replaced to prepare quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer with other quaternary ammonium salt, be that the quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 1 with octadecyl trimethyl ammonium chloride, the catalyzer prepared for quaternary ammonium salt with octadecyl trimethyl bromine ammonium is hereinafter referred to as catalyzer 2, be that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 3 with palmityl trimethyl ammonium chloride, be that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 4 with palmityl trimethyl ammonium chloride, be that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 6 with Tetradecyl Trimethyl Ammonium Bromide, be that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 7 with Dodecyl trimethyl ammonium chloride, be that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 8 with Trimethyllaurylammonium bromide, TPC is that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 9, tetradecyl pyridinium bromide is that the catalyzer prepared of quaternary ammonium salt is hereinafter referred to as catalyzer 10.
second section prepares Halogen epoxidation synthesis bisphenol A diglycidyl ether
Embodiment 1:
280ml trichloromethane is added, 68ml (0.222mol) tetrabutyl ammonium bromide, 5.48 gram (2.8 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 3, the hydrogen peroxide of 33.22 gram weight percentage concentrations 50% (0.488mol) is added in reaction flask, heat gradually and stir, react 8 hours under 50 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery trichloromethane, then filter with 136 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Sherwood oil and ethyl acetate volume ratio is adopted to be that the mixed solvent column chromatography of 90:10 obtains product subsequently.Analyze product, epoxy equivalent (weight) testing method adopts the tetraethyl-ammonium bromide method of GB4612-84, and viscosity (25 DEG C, mPa.s) value, by LVDV-II Brookfiel viscometer determining, the results are shown in Table 1.
Embodiment 2:
120ml 1,2-ethylene dichloride is added, 36 ml (0.1176mol) tetrabutyl ammonium bromide, 2.0 gram (1.1 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 5, the hydrogen peroxide of 30.14 gram weight percentage concentrations 30% (0.2660mol) is added in reaction flask, heat gradually and stir, react 5 hours under 80 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and distillating recovering solvent 1, after 2-ethylene dichloride, filter with 60 ml acetic acid ethyl dissolution residuums again, obtain catalyzer, by after filtrate Distillation recovery ethyl acetate thick product.Sherwood oil and ethyl acetate volume ratio is adopted to be that the mixed solvent column chromatography of 96:4 obtains product subsequently.Other residue subsequent process with embodiment 1(slightly).
Embodiment 3:
260ml solvent I (methylene dichloride: methyl iso-butyl ketone (MIBK): trichloromethane=1:2:1) is added, 50 ml grams of (0.1662mol) tetrabutyl ammonium bromides, 4.144 gram (2.2 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 1, the hydrogen peroxide of 22.60 gram weight percentage concentrations 50% (0.3324mol), heat gradually and stir, react 12 hours under 45 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery trichloromethane, then filter with 80 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Sherwood oil and ethyl acetate volume ratio is adopted to be that the mixed solvent column chromatography of 95:5 obtains product subsequently.Other residue subsequent process with embodiment 1(slightly).
Embodiment 4:
300ml hexone is added, 50 ml (0.1662mol) tetrabutyl ammonium bromide, 4.926 gram (2.526 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 10, (0.422mol) hydrogen peroxide of 28.70 gram weight percentage concentrations 50%, heat gradually and stir, react 15 hours under 55 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery hexone, then filter with 90 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Sherwood oil and ethyl acetate volume ratio is adopted to be that the mixed solvent column chromatography of 93:7 obtains product subsequently.Other residue subsequent process with embodiment 1(slightly).
Embodiment 5:
206ml methylene dichloride is added, 68 ml (0.222mol) tetrabutyl ammonium bromide, 4.788 gram (2.46 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 8, the hydrogen peroxide of 241.6 gram weight percentage concentrations 15% (1.064mol), heat gradually and stir, react 6 hours under 70 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery methylene dichloride, then filter with 115 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Other residue subsequent process with embodiment 2(slightly).
Embodiment 6:
150ml solvent I (methyl iso-butyl ketone (MIBK): 1,2-ethylene dichloride=3:2) is added, 25ml (0.0831mol) tetrabutyl ammonium bromide, 2.268 gram (1.16 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 4, the hydrogen peroxide of 11.84 gram weight percentage concentrations 70% (0.244mol), heat gradually and stir, react 21 hours under 35 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery ethyl acetate, then filter with 50 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Other residue subsequent process with embodiment 4(slightly).
Embodiment 7:
200ml 1,2-ethylene dichloride is added, 68ml (0.222mol) tetrabutyl ammonium bromide, 6.84 gram (3.5 × 10 in 1000ml four-hole boiling flask
-4mol) catalyzer 7, the hydrogen peroxide of 65.4 gram weight percentage concentrations 30% (0.578mol), heat gradually and stir, react 13 hours under 55 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery methylene dichloride, then filter with 110 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Other residue subsequent process with embodiment 3(slightly).
Embodiment 8:
160ml trichloromethane is added, 80ml (0.262mol) tetrabutyl ammonium bromide, 5.66 gram (2.9 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 6, the hydrogen peroxide of 35.68 gram weight percentage concentrations 50% (0.524mol), heat gradually and stir, react 18 hours under 45 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery trichloromethane, then filter with 140ml acetic acid ethyl dissolution residuum, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Other residue subsequent process with embodiment 4(slightly).
Embodiment 9:
180ml methylene dichloride is added, 60ml (0.197mol) tetrabutyl ammonium bromide, 5.16 gram (2.64 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 9, the hydrogen peroxide of 58.00 gram weight percentage concentrations 30% (0.512mol), heat gradually and stir, react 24 hours under 30 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery methylene dichloride, then filter with 90ml acetic acid ethyl dissolution residuum, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Other residue subsequent process with embodiment 3(slightly).
Embodiment 10:
220ml solvent I (methylene dichloride: methyl iso-butyl ketone (MIBK)=1:3) is added, 64ml (0.210mol) tetrabutyl ammonium bromide, 3.88 gram (1.98 × 10 in 1000ml four-hole boiling flask
-3mol) catalyzer 2, the hydrogen peroxide of 34.4 gram weight percentage concentrations 50% (0.504mol), heat gradually and stir, react 12 hours under 50 DEG C of conditions, after being cooled to room temperature, in separating funnel, separate organic phase and after Distillation recovery ethyl acetate, then filter with 100 ml acetic acid ethyl dissolution residuums, obtain catalyzer, obtain thick product by after filtrate Distillation recovery ethyl acetate.Other residue subsequent process with embodiment 2(slightly).
Table 1: the epoxy equivalent (weight) of the bisphenol A diglycidyl ether of Halogen epoxidation synthesis and viscosity:
Embodiment 11:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:9 ~ 16 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 2 ~ 6 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2 ~ 3 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 15 ~ 70%;
Described solvent I is one or more the mixture in methylene dichloride, methyl iso-butyl ketone (MIBK), trichloromethane, 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation add aqueous hydrogen peroxide solution, temperature of charge is raised to 30 ~ 80 DEG C, react 5 ~ 24 hours at 30 ~ 80 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed to solvend and dissolve, filter, the solids obtained after filtration is quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer (recyclable recycling), then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.5 ~ 2;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 4% ~ 10% and the sherwood oil of 90% ~ 96% are mixed into.
Embodiment 12:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:16 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 6 times of volume and gets solvent I by the volume that adds of solvent I; Be that 3 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 15%;
Described solvent I is methylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 80 DEG C, react 5 hours at 80 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed to solvend and dissolve, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:2;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 10% and the sherwood oil of 90% are mixed into.
Embodiment 13:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:9 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 2 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 70%;
Described solvent I is methyl iso-butyl ketone (MIBK);
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 30 DEG C, react 24 hours at 30 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed to solvend and dissolve, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.5;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 4% and the sherwood oil of 96% are mixed into.
Embodiment 14:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:13 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 4 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2.5 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 43%;
Described solvent I is 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 55 DEG C, react 15 hours at 55 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed to solvend and dissolve, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.8;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 7% and the sherwood oil of 93% are mixed into.
Embodiment 15:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:10 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 3 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2.3 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 25%;
Described solvent I is trichloromethane;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 40 DEG C, react 10 hours at 40 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.6;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 5% and the sherwood oil of 95% are mixed into.
Embodiment 16:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer be 12 mol ratio get tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer, be that tetrabutyl ammonium bromide adds 5 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2.6 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 30%;
Described solvent I is the mixture of methylene dichloride and trichloromethane;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 50 DEG C, react 13 hours at 50 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.7;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 6% and the sherwood oil of 94% are mixed into.
Embodiment 17:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:14 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 5 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2.7 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 40%;
Described solvent I is the mixture of trichloromethane and 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 60 DEG C, react 15 hours at 60 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.8;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 7% and the sherwood oil of 93% are mixed into.
Embodiment 18:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:15 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 5 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2.9 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 50%;
Described solvent I is the mixture of methylene dichloride and trichloromethane;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 70 DEG C, react 8 hours at 70 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:2;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 8% and the sherwood oil of 92% are mixed into.
Embodiment 19:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:16 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 5 times of volume and gets solvent I by the volume that adds of solvent I; Be that 3 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 60%;
Described solvent I is the mixture of methylene dichloride, trichloromethane and 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 70 DEG C, react 10 hours at 70 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:2;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 9% and the sherwood oil of 91% are mixed into.
Embodiment 20:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, comprises the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:12 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 5 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 70%;
Described solvent I is the mixture of methylene dichloride, methyl iso-butyl ketone (MIBK), trichloromethane and 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are joined in reactor, under agitation adds aqueous hydrogen peroxide solution, temperature of charge is raised to 65 DEG C, react 20 hours at 65 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.7;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 6% and the sherwood oil of 94% are mixed into.
Embodiment 21:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:8 ~ 11, at 60 DEG C, stirring reaction is after 1 ~ 4 hour, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 17 ~ 21% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:3 ~ 5, then 7 ~ 10 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 0.5 ~ 1 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.07 ~ 0.14mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:1 ~ 3, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 1 ~ 3 hour, static 3 ~ 5 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 50 DEG C ~ 80 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Embodiment 22:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:8, at 60 DEG C, stirring reaction is after 1 hour, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 17% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:3, then 7 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 0.5 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.07mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:1, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 1 hour, static 3 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 50 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Arbitrary in the other the same as in Example 11 ~ 20, omit.
Embodiment 23:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:11, at 60 DEG C, stirring reaction is after 4 hours, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 21% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:5, then 10 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 1 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.14mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:3, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 3 hours, static 5 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 80 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Arbitrary in the other the same as in Example 11 ~ 20, omit.
Embodiment 24:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:9, at 60 DEG C, stirring reaction is after 2.5 hours, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 19% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:4, then 9 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 0.7 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.11mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:2, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 2 hours, static 4 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 70 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Arbitrary in the other the same as in Example 11 ~ 20, omit.
Embodiment 25:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:10, at 60 DEG C, stirring reaction is after 3 hours, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 20% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:4.5, then 9 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 0.8 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.12mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:2.5, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 2.5 hours, static 4 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 60 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Arbitrary in the other the same as in Example 11 ~ 20, omit.
Embodiment 26:
A method for Halogen epoxidation synthesis bisphenol A diglycidyl ether, the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
Be the aqueous hydrogen peroxide solution of 30%(weight percent concentration more than 30% by wolframic acid and weight percent concentration, can thin up to 30%) aqueous hydrogen peroxide solution join in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:11, at 60 DEG C, stirring reaction is after 3 hours, be cooled to room temperature, the phosphate aqueous solution (can be that 85% phosphoric acid dilute with water obtains by weight percent concentration) that weight percent concentration is 18% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:3.5, then 8 times are added to the deionized water of wolframic acid weight, diluting reaction material stirring reaction 0.7 hour,
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.09mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:1.8, at room temperature, quaternary ammonium salt solution is added (being preferably dropping) in reactor, add rear continuation reaction 2 hours, static 4 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 80 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
Arbitrary in the other the same as in Example 11 ~ 20, omit.
In above-described embodiment 21 ~ 26: described quaternary ammonium salt can be any one in octadecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, TPC and tetradecyl pyridinium bromide.
In above-described embodiment: the preparation method of described catalyzer phosphorus heteropoly tungstic acid quaternary ammonium also can be additive method of the prior art.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage; In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described weight part can be all gram or kilogram.
In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described starting material are commercially available prod.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (3)
1. a method for epoxidation synthesis bisphenol A diglycidyl ether, is characterized in that comprising the following steps:
A, batching: by tetrabutyl ammonium bromide: quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is that the mol ratio of 1000:9 ~ 16 gets tetrabutyl ammonium bromide and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer are that tetrabutyl ammonium bromide adds 2 ~ 6 times of volume and gets solvent I by the volume that adds of solvent I; Be that 2 ~ 3 times of tetrabutyl ammonium bromide molar weight get aqueous hydrogen peroxide solution by the molar weight that adds of hydrogen peroxide, the weight percent concentration of aqueous hydrogen peroxide solution is 15 ~ 70%;
Described solvent I is one or more the mixture in methylene dichloride, methyl iso-butyl ketone (MIBK), trichloromethane, 1,2-ethylene dichloride;
B, epoxidation reaction:
Tetrabutyl ammonium bromide, solvent I, quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer and aqueous hydrogen peroxide solution are joined in reactor, under agitation temperature of charge is raised to 30 ~ 80 DEG C, react 5 ~ 24 hours at 30 ~ 80 DEG C, namely reacted, obtained reacting rear material;
C, aftertreatment:
Reacting rear material is cooled to room temperature, isolate organic phase, by isolated organic phase after Distillation recovery organic solvent, remaining material and solvent II ethyl acetate are uniformly mixed, filter, then filtrate is obtained thick product after distillating recovering solvent II ethyl acetate; With solvent III, thick product is carried out column chromatography again, i.e. obtained bisphenol A diglycidyl ether;
The consumption volume of described solvent II ethyl acetate and the ratio of raw materials bisphenol A diallyl ether consumption volume are: tetrabutyl ammonium bromide: ethyl acetate=1:1.5 ~ 2;
Described solvent III is: volume percent is the mixed solution that the ethyl acetate of 4% ~ 10% and the sherwood oil of 90% ~ 96% are mixed into.
2., by the method for epoxidation synthesis bisphenol A diglycidyl ether described in claim 1, it is characterized in that: the preparation method of described quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer comprises the following steps:
The aqueous hydrogen peroxide solution being 30% by wolframic acid and weight percent concentration joins in reactor, the molar ratio of wolframic acid and hydrogen peroxide use is 1:8 ~ 11, at 60 DEG C, stirring reaction is after 1 ~ 4 hour, be cooled to room temperature, the phosphate aqueous solution that weight percent concentration is 17 ~ 21% is added again in reactor, the molar ratio of phosphoric acid and wolframic acid consumption is 1:3 ~ 5, then adds 7 ~ 10 times of deionized waters to wolframic acid weight, diluting reaction material stirring reaction 0.5 ~ 1 hour;
At room temperature, quaternary ammonium salt is dissolved in solvent IV trichloromethane and is mixed with the quaternary ammonium salt solution that volumetric molar concentration is 0.07 ~ 0.14mol/L, the molar ratio of quaternary ammonium salt and wolframic acid consumption is 1:1 ~ 3, at room temperature, quaternary ammonium salt solution is joined in reactor, add rear continuation reaction 1 ~ 3 hour, static 3 ~ 5 little layereds again, isolate organic phase, remove solvent IV trichloromethane in organic phase through underpressure distillation, residuum is dried to constant weight again at 50 DEG C ~ 80 DEG C, i.e. obtained quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst product.
3., by the method for epoxidation synthesis bisphenol A diglycidyl ether described in claim 2, it is characterized in that: described quaternary ammonium salt is at least one in octadecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, TPC and tetradecyl pyridinium bromide.
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| CN111686813A (en) * | 2020-07-23 | 2020-09-22 | 辽宁石化职业技术学院 | Industrialized recovery method of inactivated phosphotungstic heteropoly acid catalyst |
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