CN113200855B - Preparation method of ethyl benzoylacetate - Google Patents
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Abstract
The invention discloses a preparation method of ethyl benzoylacetate, belonging to the technical field of chemical synthesis, wherein sodium bicarbonate is added into carbon tetrachloride, ethyl acetoacetate is slowly added, benzoyl chloride is dropwise added for reaction, sodium hydroxide is added for reaction, after the reaction is finished, ethyl benzoylacetate is obtained by filtering, a microporous filter membrane is used in the preparation process of ethyl benzoylacetate, a reinforcing filler is prepared in the preparation process of the microporous filter membrane, nano silicon dioxide and aniline are treated by the reinforcing filler, polyaniline is grafted on the surface of the nano silicon dioxide, the reinforcing filler and modified graphene are subjected to ultrasonic treatment to prepare a reinforcing substrate, 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone and epoxy chloropropane are reacted to prepare epoxy resin, and the epoxy resin is further cured with amino groups on the reinforcing substrate, the reinforcing filler can enhance the corrosion resistance of the microporous filter membrane, and the microporous filter membrane cannot be corroded after long-time use.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of ethyl benzoylacetate.
Background
Ethyl benzoylacetate is an important starting material for the synthesis of colour photographic couplers and certain pharmaceutical intermediates. The synthesis method generally comprises the following three methods: benzaldehyde is used as an initial raw material and reacts with ethyl bromoacetate under the action of metal zinc, and an intermediate is oxidized to obtain: ② reacting benzoyl which is used as raw material with ethyl acetoacetate under the action of sodium hydride, then processing with concentrated alkali liquor to obtain benzoylacetic acid, and then esterifying; and thirdly, preparing the product by taking ethyl benzoate and ethyl acetoacetate as raw materials under the action of sodium ethoxide.
In the existing preparation method of ethyl benzoylacetate, filtration is needed after the reaction is finished, and the surface of the traditional microporous filter membrane is obviously corroded after being used for several times, so that the filtration efficiency and the product quality are influenced.
Disclosure of Invention
The invention aims to provide a preparation method of ethyl benzoylacetate.
The technical problems to be solved by the invention are as follows:
in the existing preparation method of ethyl benzoylacetate, filtration is needed after the reaction is finished, and the surface of the traditional microporous filter membrane is obviously corroded after being used for several times, so that the filtration efficiency and the product quality are influenced.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the ethyl benzoylacetate comprises the following steps:
step S1: adding carbon tetrachloride and sodium bicarbonate into a reaction kettle, stirring and adding ethyl acetoacetate under the conditions that the rotating speed is 150-200r/min and the temperature is 15-25 ℃, adding benzoyl chloride after stirring for 10-15min, heating to 50-60 ℃, and continuing to react for 3-5 h;
step S2: adding sodium hydroxide into a reaction kettle, reacting for 10-15h under the conditions that the rotation speed is 200-plus-300 r/min and the temperature is 100-plus-120 ℃, cooling to the temperature of 25-30 ℃, filtering by using a microporous filter membrane, and distilling the filtrate to obtain the benzoyl ethyl acetate.
The microporous filter membrane is prepared by the following steps:
uniformly mixing polypropylene, kerosene and reinforcing filler, blending and extruding at the temperature of 40-60 ℃, calendering at the roller temperature of 190-200 ℃, the roller linear speed of 25m/min and the upper and lower roller speed difference of 5m/min to obtain a film with the thickness of 0.8mm, and drying the film to obtain the microporous filter membrane.
Further, the reinforcing filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotation speed is 150 plus materials/min and the temperature is 0-5 ℃, reacting for 2-3h, heating to the temperature of 30-40 ℃, stirring for 3-5h, adding deionized water, reacting for 30-40min under the temperature of 90-95 ℃, adding hydrogen peroxide,until no bubble is generated, washing the reaction solution until the reaction solution is free from SO4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: adding 2-methyl-1, 3-propane diamine, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, potassium carbonate, deionized water and tetraethylammonium bromide, performing reflux reaction for 2-3h to obtain an intermediate 2, adding graphene oxide, the intermediate 2 and concentrated sulfuric acid into the reaction kettle, reacting for 6-8h at the temperature of 120-150 ℃, and filtering to remove filtrate to obtain modified graphene;
the reaction process is as follows:
step A3: adding ammonia water, deionized water and ethanol into a reaction kettle, stirring and adding ethyl orthosilicate under the condition that the rotating speed is 200 plus materials and 300r/min, stirring for 1-1.5h, performing ultrasonic treatment for 30-40min under the condition that the frequency is 3-5MHz to prepare nano silicon dioxide, dispersing the nano silicon dioxide into phosphoric acid, adding aniline, adding ammonium persulfate under the condition that the rotating speed is 150 plus materials and 200r/min, reacting for 9-12h, adding modified graphene, performing ultrasonic treatment for 3-5h under the condition that the frequency is 5-8MHz, filtering to remove filtrate, and drying a filter cake to prepare a reinforced substrate;
step A4: adding 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one and epichlorohydrin into a reaction kettle, introducing nitrogen for protection, stirring and dropwise adding a sodium hydroxide solution under the conditions that the rotation speed is 150-200r/min and the temperature is 65-70 ℃, reacting for 6-8h, adding a reinforcing substrate, continuing to react for 3-5h, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
The reaction process is as follows:
further, the use amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 4 g/2 g/98 mL/25 g/100 mL/15 mL, and the mass fraction of the concentrated sulfuric acid is 95%.
Further, the dosage ratio of the 2-methyl-1, 3-propane diamine, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride in the step A2 is 0.1mol:0.1mol:0.2g:300mL, the dosage ratio of the intermediate 1, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 4g:9g:80mL:3mL, and the dosage ratio of the graphene oxide, the intermediate 2 and the concentrated sulfuric acid is 1.2g:0.3g:20 mL.
Further, the using amount volume ratio of the ammonia water, the deionized water, the ethanol and the ethyl orthosilicate in the step A3 is 9:16:45:15, the mass fraction of the ammonia water is 28%, and the using amount ratio of the nano silicon dioxide, the aniline and the ammonium persulfate is 1g:1mL:2.5 g.
Further, the amount ratio of the 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one, the epichlorohydrin, the sodium hydroxide solution and the reinforcing substrate in the step A4 is 0.01mol:0.08mol:0.2mol:5g, and the mass fraction of the sodium hydroxide solution is 25-30%.
The invention has the beneficial effects that: the invention uses a microporous filter membrane in the process of preparing ethyl benzoylacetate, prepares a reinforcing filler in the process of preparing the microporous filter membrane, uses graphite as a raw material to oxidize to prepare graphene oxide, then reacts 2-methyl-1, 3-propane diamine with nitrogen-bromosuccinimide to prepare an intermediate 1, further processes the intermediate 1 to prepare an intermediate 2, reacts the graphene oxide with the intermediate 2 to enable carboxyl on the surface of the graphene oxide and hydroxyl on the intermediate 2 to generate esterification reaction to prepare modified graphene, uses ethyl orthosilicate as a raw material to prepare nano silicon dioxide, then processes the nano silicon dioxide and aniline to enable polyaniline to be grafted on the surface of the nano silicon dioxide, and then carries out ultrasonic treatment with the modified graphene to prepare a reinforcing substrate, and uses 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone and epoxy chloropropane react to prepare epoxy resin, and the epoxy resin is further cured with amino groups on a reinforcing substrate to prepare a reinforcing filler, wherein the reinforcing filler can enhance the corrosion resistance of the microporous filter membrane, the microporous filter membrane cannot be corroded after long-term use, and the service life of the microporous filter membrane is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the ethyl benzoylacetate comprises the following steps:
step S1: adding carbon tetrachloride and sodium bicarbonate into a reaction kettle, stirring and adding ethyl acetoacetate under the conditions that the rotating speed is 150r/min and the temperature is 15 ℃, stirring for 10min, adding benzoyl chloride, heating to 50 ℃, and continuing to react for 3 h;
step S2: adding sodium hydroxide into a reaction kettle, reacting for 10 hours at the rotation speed of 200r/min and the temperature of 100 ℃, cooling to the temperature of 25 ℃, filtering by using a microporous filter membrane, and distilling the filtrate to obtain the benzoyl ethyl acetate.
The microporous filter membrane is prepared by the following steps:
uniformly mixing polypropylene, kerosene and reinforcing filler, blending and extruding at 40 ℃, calendering at 190 ℃ of a roller, 25m/min of roller linear speed and 5m/min of upper and lower roller speed difference to obtain a film with the thickness of 0.8mm, and drying the film to obtain the microporous filter membrane.
The reinforcing filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150r/min and the temperature is 0 ℃, reacting for 2 hours, heating to 30 ℃, stirring for 3 hours, adding deionized water, and reacting at the temperatureReacting at 90 deg.C for 30min, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no SO is generated in the reaction solution4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: adding 2-methyl-1, 3-propane diamine, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, potassium carbonate, deionized water and tetraethylammonium bromide, performing reflux reaction for 2 hours to obtain an intermediate 2, adding graphene oxide, the intermediate 2 and concentrated sulfuric acid into the reaction kettle, reacting for 6 hours at the temperature of 120 ℃, and filtering to remove filtrate to obtain modified graphene;
step A3: adding ammonia water, deionized water and ethanol into a reaction kettle, stirring and adding tetraethoxysilane under the condition of a rotating speed of 200r/min, stirring for 1h, carrying out ultrasonic treatment for 30min under the condition of a frequency of 3MHz to prepare nano-silicon dioxide, dispersing the nano-silicon dioxide into phosphoric acid, adding aniline, adding ammonium persulfate under the condition of a rotating speed of 150r/min, reacting for 9h, adding modified graphene, carrying out ultrasonic treatment for 3h under the condition of a frequency of 5MHz, filtering to remove filtrate, and drying a filter cake to prepare a reinforced substrate;
step A4: adding 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one and epichlorohydrin into a reaction kettle, introducing nitrogen for protection, stirring and dropwise adding a sodium hydroxide solution under the conditions that the rotating speed is 150r/min and the temperature is 65 ℃, reacting for 6 hours, adding a reinforcing substrate, continuing to react for 3 hours, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Example 2
The preparation method of the ethyl benzoylacetate comprises the following steps:
step S1: adding carbon tetrachloride and sodium bicarbonate into a reaction kettle, stirring and adding ethyl acetoacetate under the conditions that the rotating speed is 150r/min and the temperature is 25 ℃, stirring for 10min, adding benzoyl chloride, heating to 60 ℃, and continuing to react for 3 h;
step S2: adding sodium hydroxide into a reaction kettle, reacting for 15 hours at the rotation speed of 300r/min and the temperature of 100 ℃, cooling to the temperature of 25 ℃, filtering by using a microporous filter membrane, and distilling the filtrate to obtain the benzoyl ethyl acetate.
The microporous filter membrane is prepared by the following steps:
uniformly mixing polypropylene, kerosene and reinforcing filler, blending and extruding at the temperature of 60 ℃, calendering at the roller temperature of 190 ℃, the roller linear speed of 25m/min and the difference of the upper roller speed and the lower roller speed of 5m/min to obtain a film with the thickness of 0.8mm, and drying the film to obtain the microporous filter membrane.
The reinforcing filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 200r/min and the temperature is 0 ℃, reacting for 3 hours, heating to the temperature of 30 ℃, stirring for 5 hours, adding deionized water, reacting for 40 minutes under the condition that the temperature is 90 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no SO is generated in the reaction solution4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: adding 2-methyl-1, 3-propane diamine, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 10 hours at the temperature of 80 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, potassium carbonate, deionized water and tetraethylammonium bromide, performing reflux reaction for 2 hours to obtain an intermediate 2, adding graphene oxide, the intermediate 2 and concentrated sulfuric acid into the reaction kettle, reacting for 6 hours at the temperature of 150 ℃, and filtering to remove filtrate to obtain modified graphene;
step A3: adding ammonia water, deionized water and ethanol into a reaction kettle, stirring and adding tetraethoxysilane under the condition that the rotating speed is 300r/min, stirring for 1h, carrying out ultrasonic treatment for 30min under the condition that the frequency is 5MHz to prepare nano silicon dioxide, dispersing the nano silicon dioxide into phosphoric acid, adding aniline, adding ammonium persulfate under the condition that the rotating speed is 200r/min, reacting for 9h, adding modified graphene, carrying out ultrasonic treatment for 3h under the condition that the frequency is 8MHz, filtering to remove filtrate, and drying a filter cake to prepare a reinforced substrate;
step A4: adding 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one and epichlorohydrin into a reaction kettle, introducing nitrogen for protection, stirring and dropwise adding a sodium hydroxide solution under the conditions that the rotating speed is 200r/min and the temperature is 65 ℃, reacting for 8 hours, adding a reinforcing substrate, continuing to react for 3 hours, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Example 3
The preparation method of the ethyl benzoylacetate comprises the following steps:
step S1: adding carbon tetrachloride and sodium bicarbonate into a reaction kettle, stirring and adding ethyl acetoacetate under the conditions that the rotating speed is 200r/min and the temperature is 25 ℃, stirring for 15min, adding benzoyl chloride, heating to 60 ℃, and continuing to react for 5 h;
step S2: adding sodium hydroxide into a reaction kettle, reacting for 15 hours at the rotating speed of 300r/min and the temperature of 120 ℃, cooling to the temperature of 30 ℃, filtering by using a microporous filter membrane, and distilling the filtrate to obtain the benzoyl ethyl acetate.
The microporous filter membrane is prepared by the following steps:
uniformly mixing polypropylene, kerosene and reinforcing filler, blending and extruding at the temperature of 60 ℃, calendering at the roller temperature of 200 ℃, the roller linear speed of 25m/min and the speed difference of an upper roller and a lower roller of 5m/min to obtain a film with the thickness of 0.8mm, and drying the film to obtain the microporous filter membrane.
The reinforcing filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 5 ℃, reacting for 3 hours, heating to 40 ℃, stirring for 5 hours, adding deionized water, and reacting at the temperature of 9 DEG CReacting at 5 deg.C for 40min, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no SO is generated in the reaction solution4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: adding 2-methyl-1, 3-propane diamine, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, potassium carbonate, deionized water and tetraethylammonium bromide, performing reflux reaction for 3 hours to obtain an intermediate 2, adding graphene oxide, the intermediate 2 and concentrated sulfuric acid into the reaction kettle, reacting for 8 hours at the temperature of 150 ℃, and filtering to remove filtrate to obtain modified graphene;
step A3: adding ammonia water, deionized water and ethanol into a reaction kettle, stirring and adding tetraethoxysilane under the condition that the rotating speed is 300r/min, stirring for 1.5 hours, carrying out ultrasonic treatment for 40 minutes under the condition that the frequency is 5MHz to prepare nano silicon dioxide, dispersing the nano silicon dioxide into phosphoric acid, adding aniline, adding ammonium persulfate under the condition that the rotating speed is 200r/min, reacting for 12 hours, adding modified graphene, carrying out ultrasonic treatment for 5 hours under the condition that the frequency is 8MHz, filtering to remove filtrate, and drying a filter cake to prepare a reinforced substrate;
step A4: adding 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one and epichlorohydrin into a reaction kettle, introducing nitrogen for protection, stirring and dropwise adding a sodium hydroxide solution under the conditions that the rotation speed is 200r/min and the temperature is 70 ℃, reacting for 8 hours, adding a reinforcing substrate, continuing to react for 5 hours, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Comparative example 1
The comparative example compares with example 1 without adding reinforcing filler, the rest of the procedure is the same.
Comparative example 2
This comparative example is a microfiltration membrane as disclosed in chinese patent CN 107096396A.
The microporous filter membranes obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to further corrosion tests, and the results are shown in Table 1 below;
TABLE 1
As can be seen from Table 1 above, the microporous filter membranes obtained in examples 1 to 3 have excellent corrosion resistance.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (5)
1. The preparation method of the benzoyl ethyl acetate is characterized by comprising the following steps: the method comprises the following steps:
step S1: adding carbon tetrachloride and sodium bicarbonate into a reaction kettle, stirring and adding ethyl acetoacetate under the conditions that the rotating speed is 150-200r/min and the temperature is 15-25 ℃, adding benzoyl chloride after stirring for 10-15min, heating to 50-60 ℃, and continuing to react for 3-5 h;
step S2: adding sodium hydroxide into a reaction kettle, reacting for 10-15h at the rotation speed of 200-;
the microporous filter membrane is prepared by the following steps:
uniformly mixing polypropylene, kerosene and a reinforcing filler, blending and extruding at the temperature of 40-60 ℃, calendering at the roller temperature of 190-200 ℃, the roller linear speed of 25m/min and the speed difference of 5m/min between an upper roller and a lower roller to obtain a film with the thickness of 0.8mm, and drying the film to obtain the microporous filter membrane;
the reinforcing filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotation speed is 150 plus materials at 200r/min and the temperature is 0-5 ℃, reacting for 2-3h, heating to the temperature of 30-40 ℃, stirring for 3-5h, adding deionized water, reacting for 30-40min under the temperature of 90-95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction liquid until the reaction liquid has no SO 42-ions, filtering and drying the filter cake to obtain graphene oxide;
step A2: adding 2-methyl-1, 3-propane diamine, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, potassium carbonate, deionized water and tetraethylammonium bromide, performing reflux reaction for 2-3h to obtain an intermediate 2, adding graphene oxide, the intermediate 2 and concentrated sulfuric acid into the reaction kettle, reacting for 6-8h at the temperature of 120-150 ℃, and filtering to remove filtrate to obtain modified graphene;
step A3: adding ammonia water, deionized water and ethanol into a reaction kettle, stirring and adding ethyl orthosilicate under the condition that the rotating speed is 200 plus materials and 300r/min, stirring for 1-1.5h, performing ultrasonic treatment for 30-40min under the condition that the frequency is 3-5MHz to prepare nano silicon dioxide, dispersing the nano silicon dioxide into phosphoric acid, adding aniline, adding ammonium persulfate under the condition that the rotating speed is 150 plus materials and 200r/min, reacting for 9-12h, adding modified graphene, performing ultrasonic treatment for 3-5h under the condition that the frequency is 5-8MHz, filtering to remove filtrate, and drying a filter cake to prepare a reinforced substrate;
step A4: adding 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one and epichlorohydrin into a reaction kettle, introducing nitrogen for protection, stirring and dropwise adding a sodium hydroxide solution under the conditions that the rotation speed is 150-200r/min and the temperature is 65-70 ℃, reacting for 6-8h, adding a reinforced substrate, continuing to react for 3-5h, filtering to remove filtrate, and drying a filter cake to obtain the reinforced filler.
2. The process for the preparation of ethyl benzoylacetate according to claim 1, wherein: the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 4g to 2g to 98mL to 25g to 100mL to 15mL, and the mass fraction of the concentrated sulfuric acid is 95%.
3. The process for the preparation of ethyl benzoylacetate according to claim 1, wherein: the dosage ratio of the 2-methyl-1, 3-propane diamine, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride in the step A2 is 0.1mol:0.1mol:0.2g:300mL, the dosage ratio of the intermediate 1, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 4g:9g:80mL:3mL, and the dosage ratio of the graphene oxide, the intermediate 2 and the concentrated sulfuric acid is 1.2g:0.3g:20 mL.
4. The process for the preparation of ethyl benzoylacetate according to claim 1, wherein: the using amount volume ratio of the ammonia water, the deionized water, the ethanol and the ethyl orthosilicate in the step A3 is 9:16:45:15, the mass fraction of the ammonia water is 28%, and the using amount ratio of the nano silicon dioxide, the aniline and the ammonium persulfate is 1g:1mL:2.5 g.
5. The process for the preparation of ethyl benzoylacetate according to claim 1, wherein: the dosage ratio of the 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one, the epichlorohydrin, the sodium hydroxide solution and the reinforced substrate in the step A4 is 0.01mol:0.08mol:0.2mol:5g, and the mass fraction of the sodium hydroxide solution is 25-30%.
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