CN115490593A - Acetoacetoxyethyl methacrylate, preparation method and application thereof - Google Patents

Acetoacetoxyethyl methacrylate, preparation method and application thereof Download PDF

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CN115490593A
CN115490593A CN202211166664.6A CN202211166664A CN115490593A CN 115490593 A CN115490593 A CN 115490593A CN 202211166664 A CN202211166664 A CN 202211166664A CN 115490593 A CN115490593 A CN 115490593A
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acetoacetoxyethyl methacrylate
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preparing
acetoacetic acid
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CN115490593B (en
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袁世刚
邢晓华
崔佳惠
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Weifang Kemai Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C07C69/72—Acetoacetic acid esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses acetoacetoxyethyl methacrylate, a preparation method and application thereof, and belongs to the technical field of preparation of methacrylic acid monomers. The preparation method comprises the following steps: firstly, taking ethylene glycol and diethyl ketene as raw materials, carrying out esterification reaction under the action of a catalyst I, and rectifying to collect acetoacetic acid monoethylene glycol ester; then mixing the acetoacetic acid monoethylene glycol ester, a solvent, a catalyst II and a polymerization inhibitor, adding methacrylic acid chloride into the mixture for esterification reaction, and distilling and rectifying filtrate obtained by the reaction to obtain the product. The preparation method has the advantages of high yield, mild reaction process, simple and convenient post-treatment and the like, and through detection and analysis, the product prepared by the method conforms to the component characteristics of the acetoacetoxyethyl methacrylate, and the yield of the acetoacetoxyethyl methacrylate prepared by the method is over 80 percent.

Description

Acetoacetoxyethyl methacrylate, preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of methacrylic acid monomers, and particularly relates to a preparation method and application of acetoacetoxyethyl methacrylate.
Background
Acetoacetoxyethyl methacrylate (AAEM) is used as a novel methacrylate functional monomer and can be used for synthesizing high-solid-content liquid acrylic resin and acrylic emulsion for low-VOC industrial and building coatings. The special property of AAEM to react with amine and hydrazine makes it an ideal monomer for self-crosslinking, room temperature curing acrylic emulsions. AAEM can also be applied to an acetoacetic acid polymer, can be crosslinked through the chelating action of metal ions, can also be used for producing an acetoacetic acid polymer for non-fading fibers (azo dyes), and has excellent application performance.
The prior known synthesis method of AAEM mainly comprises an addition method and an ester exchange method, wherein the addition method mainly takes hydroxyethyl methacrylate and ketene dimer as main raw materials, and AAEM is generated through reaction in the presence of a polymerization inhibitor; the latter is mainly made up by using hydroxyethyl methacrylate and ethyl acetoacetate or methyl acetoacetate as main raw material, and making them produce ester exchange reaction under the catalysis of concentrated sulfuric acid or other solid acid.
Although both of the above two synthetic methods can prepare AAEM, the following technical problems still exist:
(1) The addition method has violent reaction and high temperature control requirement, thus causing more side reactions and lower yield which is about 70 percent generally;
(2) In the ester exchange method, along with the production of ethanol or methanol, the reaction quickly reaches a balance and prevents the further progress of the reaction, so the ester exchange method has the defects of low yield and long reaction time, and the reaction system is easy to generate side reactions such as hydrolysis or polymerization along with the extension of the reaction time, so that more impurities, complex post-treatment and poor product quality are caused.
Therefore, the technical problems of low yield and more side reactions in the above method are to be solved.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of acetoacetoxyethyl methacrylate, which is characterized in that a brand-new method, namely a two-step esterification method, is adopted to prepare the acetoacetoxyethyl methacrylate, and the method has the advantages of high yield, mild reaction process, simple and convenient post-treatment and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of acetoacetoxyethyl methacrylate mainly adopts a two-step method to prepare:
firstly, taking ethylene glycol and diethylenone as raw materials, carrying out esterification reaction under the action of a catalyst I, and rectifying to collect acetoacetic acid monoethylene glycol ester;
and secondly, mixing the acetoacetic acid monoethylene glycol ester, a solvent, a catalyst II and a polymerization inhibitor, adding methacrylic acid chlorine into the mixture for esterification reaction, and distilling and rectifying filtrate obtained by the reaction to obtain the product.
In the technical scheme, the ethylene glycol is excessive, and the ketene dimer and the excessive ethylene glycol are subjected to esterification reaction under the action of the catalyst I.
The beneficial technical effect that above-mentioned technical scheme directly brought does:
the method is characterized in that ethylene glycol, ketene dimer and methacrylic acid chloride are used as main raw materials, acetoacetoxyethyl methacrylate is prepared by a two-step esterification method, the addition of a catalyst I and a catalyst II in the esterification reaction promotes the reaction to proceed in the positive reaction direction, the yield is improved, in addition, the reaction process of the esterification method is milder, and the reaction system is more stable. The experiments related to the examples prove that the yield of the acetoacetoxyethyl methacrylate obtained by the two-step esterification method is over 80 percent.
In a preferred embodiment of the present invention, in the first step, the first catalyst is selected from morpholine, cyclohexylamine or piperazine, and the mass of the first catalyst is 0.1-0.5% of the mass of the diethylenone.
The reaction is accelerated and the esterification reaction is controlled to proceed in the forward reaction direction under the action of the catalyst I.
In the above technical solution, the mass of the first catalyst is preferably 0.2% to 0.3% of the mass of the diketene.
In another preferred embodiment of the present invention, the mass ratio of ethylene glycol to diethylenone is 50 to 75.
In the above technical scheme, the mass ratio of ethylene glycol to diethylenone is preferably 65 to 75, and when the ethylene glycol is excessive, the reaction yield is higher.
Further, the first specific step is as follows: adding ethylene glycol and a first catalyst into a reaction container, heating to 80-100 ℃, adding diethylenone under a heat preservation state, continuing to react for 3-6 hours at 80-100 ℃ after the addition is finished, finishing the esterification reaction, and collecting the acetoacetic acid monoethylene glycol ester through rectification.
In the technical scheme, the esterification reaction is ensured to be smoothly carried out by further limiting the temperature and the reaction time.
Further, in the second step, the solvent is selected from dichloromethane, chloroform, toluene or benzene.
Further, the solvent is dichloromethane; the second catalyst is selected from pyridine, 2-methylpyridine or 3-methylpyridine, and the ratio of the dosage of the second catalyst to the dosage of the substance of the acetoacetic acid monoethylene glycol ester is 1.0-1.5.
In the above technical solution, the solvent is preferably dichloromethane because: the solubility of pyridine hydrochloride which is a byproduct generated by the esterification reaction in dichloromethane is low, and by utilizing the property, the filtration separation can be realized without washing with water, so that the dichloromethane is the best choice; and other solvents such as trichloromethane, toluene or benzene are selected, so that the subsequent separation effect is poor, and the yield of the product is influenced.
Further, the polymerization inhibitor is a mixture of ZJ-705 and hydroquinone, p-methylphenol or 2, 6-di-tert-butyl-p-cresol respectively, and the total consumption of the polymerization inhibitor is 0.1 per mill to 0.3 per mill of the weight of methacryloyl chloride; the mass ratio of the methacryloyl chloride to the acetoacetic acid monoethylene glycol ester is 0.57-0.86.
The polymerization inhibitor prevents polymerization reaction in esterification reaction, and the yield of the product can be improved by adding the polymerization inhibitor in the proportion.
Further, in the second step, after mixing the acetoacetic acid monoethylene glycol ester, the solvent, the catalyst II and the polymerization inhibitor, heating to 40-50 ℃, dropwise adding methacryloyl chloride, keeping the dropwise adding time for 1-2 hours, continuing to perform heat preservation reaction for 1-3 hours after the dropwise adding is finished, cooling to 0-5 ℃ after the reaction is finished, filtering, distilling the collected filtrate at normal pressure to 40-60 ℃ to recover dichloromethane, performing reduced pressure rectification on the residual material, and collecting fractions at 20-30 Pa and 105-110 ℃ to obtain the acetoacetoxyethyl methacrylate.
In the technical scheme, the reaction temperature, the reaction time, the distillation and the rectification conditions are further limited, so that a product with high yield can be obtained, and the reaction process is mild.
Another object of the present invention is to provide acetoacetoxyethyl methacrylate, which is prepared by the above-mentioned preparation method of acetoacetoxyethyl methacrylate.
The acetoacetoxyethyl methacrylate prepared by the preparation method is in a light yellow liquid state, and the detection of the embodiment shows that the acetoacetoxyethyl methacrylate accords with all the characteristics of the acetoacetoxyethyl methacrylate.
Still another object of the present invention is to provide use of the acetoacetoxyethyl methacrylate in an intermediate for agricultural chemicals, a reactive monomer for photocuring, and a polymer for cosmetics.
The acetoacetoxyethyl methacrylate prepared by the method can react with amine and hydrazine, and can also become an ideal monomer for self-crosslinking and room-temperature curing of acrylic emulsion, so that the method is widely applied to a plurality of fields.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a brand new method to prepare the acetoacetoxy ethyl methacrylate, wherein, the first step is to prepare the acetoacetic acid monoethylene glycol ester by an esterification method, and the intermediate is mixed with a solvent, a catalyst II and a polymerization inhibitor and then prepared into the acetoacetoxy ethyl methacrylate by the esterification method. The preparation method has the advantages of high raw material yield, mild reaction process, simple and convenient post-treatment, good product quality and the like, and has good industrialization prospect.
The acetoacetoxy ethyl methacrylate prepared by the method disclosed by the invention is verified to accord with the component characteristics of the acetoacetoxy ethyl methacrylate by related detection, and the yield of the acetoacetoxy ethyl methacrylate prepared by the method disclosed by the invention is more than 80%.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of the preparation of acetoacetoxyethyl methacrylate according to the present invention;
Detailed Description
The invention provides acetoacetoxyethyl methacrylate, a preparation method and application thereof, and in order to make the advantages and technical scheme of the invention clearer and clearer, the invention is further explained by combining specific examples.
The raw materials required by the invention can be purchased from commercial sources.
Acetoacetoxyethyl methacrylate, referred to in the present invention, is hereinafter abbreviated as AAEM.
The catalyst I comprises morpholine, cyclohexylamine or piperazine;
the second catalyst mentioned in the invention comprises pyridine, 2-methylpyridine or 3-methylpyridine;
depending on the type of catalyst one and catalyst two, embodiments may have different combinations, such as:
the combination is as follows: morpholine and pyridine;
combining two: morpholine and 2-methylpyridine;
combining three components: cyclohexylamine and 3-methylpyridine.
Other combinations of embodiments will be apparent to those skilled in the art in light of the above combinations.
The preparation of the AAEM of the present invention will be described in detail with reference to examples.
Example 1:
as shown in fig. 1, the preparation method of the AAEM of the present invention comprises:
firstly, adding 341g of ethylene glycol and 1g of morpholine into a 1L reaction bottle, heating to 85 ℃ under stirring, then dropwise adding 420g of diethylketene, continuing to react for 5 hours after dropwise adding is finished, rectifying and collecting fractions at 95-100 ℃ under 1330Pa, and collecting 671.2g of crude product of acetoacetic acid monoethylene glycol ester;
and secondly, adding 671.2g of acetoacetic acid monoethylene glycol ester into a 3L reaction bottle, adding 1340g of dichloromethane, 570g of pyridine, 0.08g of hydroquinone and 0.04g of ZJ-705 polymerization inhibitor, heating to 40 ℃, dropwise adding 570g of methacryloyl chloride, keeping the dropwise adding time for 1.5h, continuing to perform heat preservation reaction for 2h after the dropwise adding is finished, cooling to 5 ℃ after the reaction is finished, filtering, distilling the filtrate at normal pressure, recovering dichloromethane within the range of 40-60 ℃, then performing reduced pressure rectification on the residual material, collecting 20Pa, and the fraction of 105-107 ℃ which is AAEM, weighing 905.1g, GC =96.13%, and calculating the total yield by diethyl ketene of 84.59%.
The AAEM prepared in this example was analyzed by gas chromatography, and the analysis results are shown in table 1, and the number of components and the names of components of the AAEM were satisfied.
TABLE 1
Figure BDA0003861791050000041
Figure BDA0003861791050000051
Stopping the report
The reaction mechanism of the invention is as follows:
in the first step, diethyl ketene and excessive glycol are subjected to chemical reaction to generate the acetoacetic acid monoethylene glycol ester, and the chemical reaction equation is as follows:
Figure BDA0003861791050000052
secondly, the acetoacetic acid monoethylene glycol ester obtained in the first step and methacryloyl chloride are subjected to chemical reaction to generate AAEM; the pyridine is taken as an example of a catalyst, and the reaction equation is as follows:
Figure BDA0003861791050000053
example 2:
the preparation method of the AAEM comprises the following steps:
adding 186g of ethylene glycol and 0.5g of cyclohexylamine into a 500ML reaction bottle, heating to 95 ℃ under stirring, then dropwise adding 210g of diethylenone, continuing to react for 4 hours after the dropwise adding is finished, then rectifying and collecting fractions at the temperature of 95-100 ℃ and under the condition of 1330Pa, and collecting 334.2g of crude product of the acetoacetic acid monoethylene glycol ester;
adding 334.2g of monoethylene glycol acetoacetate into a 2L reaction bottle, adding 394g of dichloromethane, 354g of 2-methylpyridine, 0.04g of p-methylphenol and 0.02g of a polymerization inhibitor (mixture of hydroquinone and ZJ-705), heating to 42-45 ℃, dropwise adding 263 of methacryloyl chloride, keeping the dropwise adding time for 2 hours, continuing to perform heat preservation reaction for 3 hours after the dropwise adding is finished, cooling to 0 ℃ after the reaction is finished, filtering, distilling filtrate at normal pressure, recovering dichloromethane within the range of 40-60 ℃, then performing reduced pressure rectification on the residual material, collecting 30Pa, and collecting a fraction at 108-110 ℃ which is AAEM, weighing 450.6g, GC =95.91%, and the total yield is 84.22% in terms of diethylketene.
The AAEM prepared in this example was analyzed by gas chromatography, and the analysis results are shown in table 2, which correspond to the number of components and names of components of the AAEM.
TABLE 2
Figure BDA0003861791050000061
End of report
Example 3:
the preparation method of the AAEM comprises the following steps:
firstly, adding 335.9g of ethylene glycol and 0.98g of cyclohexylamine into a 1L reaction bottle, heating to 85 ℃ under stirring, then dropwise adding 413.7g of diethylenone, continuing to react for 5 hours after dropwise adding is finished, rectifying to collect fractions at 95-100 ℃ and 1330Pa, and collecting 657.7g of crude product of acetoacetic acid monoethylene glycol ester;
secondly, 657.7g of acetoacetic acid monoethylene glycol ester is added into a 3L reaction bottle, 1320g of trichloromethane, 561.5g of pyridine, 0.08g of hydroquinone and 0.04g of ZJ-705 polymerization inhibitor are added, 561.4g of methacryloyl chloride is dropwise added after the temperature is raised to 40 ℃, the dropwise adding time lasts for 1.5h, the heat preservation reaction is continued for 2h after the dropwise adding is finished, the temperature is reduced to 5 ℃ after the reaction is finished, the temperature is reduced to 5 ℃, the filtration is carried out, the filtrate is distilled at normal pressure, dichloromethane is recovered within the range of 40-60 ℃, then the residual material is rectified under reduced pressure, the fraction of 20Pa and 105-107 ℃ is collected to be AAEM, 868.8g is weighed, 95.50% of GC is=, and the total yield is 81.20% based on diethylketene.
Example 4:
the preparation method of the AAEM comprises the following steps:
firstly, 336.9g of glycol and 0.99g of piperazine are added into a 1L reaction bottle, the temperature is raised to 85 ℃ under the stirring, 415g of diethyl ketene is dropwise added, the reaction is continued for 5 hours after the dropwise addition is finished, then fractions under the conditions of 95-100 ℃ and 1330Pa are collected by rectification, and 655.2g of crude product of the monoethylene glycol acetoacetate are collected;
secondly, 655.2g of monoethylene glycol acetoacetate are added into a 3L reaction bottle, 1307.8g of dichloromethane, 556.3g of 2-methylpyridine, 0.08g of hydroquinone and 0.04g of ZJ-705 polymerization inhibitor are added, 556.3g of methacryloyl chloride is added dropwise after the temperature is raised to 40 ℃, the dropwise addition lasts for 1.5h, the reaction is continued for 2h after the dropwise addition is finished, the temperature is reduced to 5 ℃ after the reaction is finished, the filtration is carried out, the filtrate is distilled under normal pressure, dichloromethane is recovered within the range of (40-60 ℃), then the residual materials are rectified under reduced pressure, the fraction of 20Pa and 105-107 ℃ is AA0EM, 882.g of the weight is weighed, GC =95.89%, and the total yield is 82.43% in terms of diethylketene.
Example 5:
the preparation method of the AAEM comprises the following steps:
firstly, 347.8 ethylene glycol and 1g of morpholine are added into a 1L reaction bottle, the temperature is raised to 100 ℃ under the condition of stirring, 428.4 diethyl ketene is dropwise added, the reaction is continued for 6 hours after the dropwise addition is finished, then the distillation is carried out to collect the fraction at the temperature of 95-100 ℃ and the pressure of 1330Pa, and 677.8g of crude product of the acetoacetic acid monoethylene glycol ester is collected;
secondly, 677.8g of monoethylene glycol acetoacetate are added into a 3L reaction bottle, 1366g of dichloromethane, 581g of pyridine, 0.08g of hydroquinone and 0.04g of ZJ-705 polymerization inhibitor are added, 581g of methacryloyl chloride is dropwise added after the temperature is raised to 50 ℃, the dropwise addition time lasts for 1.5h, the heat preservation reaction is continued for 2h after the dropwise addition is finished, the temperature is reduced to 5 ℃ after the reaction is finished, the filtration is carried out, the filtrate is distilled at normal pressure, dichloromethane is recovered within the range of (40-60 ℃), then the residual materials are rectified under reduced pressure, the fraction of 20Pa and 105-107 ℃ is collected as AAEM, the weight is 908.0g, GC =95.88%, and the yield is 83.20% in terms of diketene.
Example 6:
the preparation method of the AAEM comprises the following steps:
firstly, adding 340g of ethylene glycol and 1g of morpholine into a 1L reaction bottle, heating to 85 ℃ under stirring, then dropwise adding 419g of diethylenone, continuing to react for 5 hours after dropwise adding is finished, rectifying to collect fractions at 95-100 ℃ under 1330Pa, and collecting 669g of crude acetoacetate monoethylene glycol ester;
secondly, adding 669g of monoethylene glycol acetoacetate into a 3L reaction bottle, adding 1338g of toluene, 570g of pyridine, 0.08g of hydroquinone and 0.04g of ZJ-705 polymerization inhibitor, heating to 40 ℃, dropwise adding 570g of methacryloyl chloride, keeping the dropwise adding time for 1.5h, continuing to perform heat preservation reaction for 2h after the dropwise adding is finished, cooling to 5 ℃ after the reaction is finished, filtering, distilling the filtrate at normal pressure, recovering dichloromethane within the range of 40-60 ℃, then performing reduced pressure rectification on the residual material, collecting 20Pa and the fraction of 105-107 ℃ which is AAEM, weighing 861.3g, GC =95.77%, and calculating the total yield by diethylketene of 80.50%.
The above examples 1 to 6 are illustrative of the present invention and are not intended to be limiting. Under the guidance of the above examples 1 to 6, different combinations of examples can be obtained as will be apparent to those skilled in the art according to the types of the first catalyst and the second catalyst.
The AAEM prepared by the invention can be applied to pesticide intermediates, reaction monomers for photocuring and polymers for cosmetics.
The parts which are not described in the invention can be realized by taking the prior art as reference.
It is intended that any equivalents, or obvious variations, which may be made by those skilled in the art in light of the teachings herein, be within the scope of the present invention.

Claims (10)

1. The preparation method of acetoacetoxyethyl methacrylate is characterized by mainly adopting a two-step method to prepare the following components:
firstly, taking ethylene glycol and diethylketene as raw materials, carrying out esterification reaction under the action of a catalyst I, and rectifying to collect acetoacetic acid monoethylene glycol ester;
and secondly, mixing the acetoacetic acid monoethylene glycol ester, a solvent, a catalyst II and a polymerization inhibitor, adding methacrylic acid chlorine into the mixture for esterification reaction, and distilling and rectifying filtrate obtained by the reaction to obtain the product.
2. The method for preparing acetoacetoxyethyl methacrylate according to claim 1, which comprises the following steps: in the first step, a first catalyst is selected from morpholine, cyclohexylamine or piperazine, and the mass of the first catalyst is 0.1-0.5% of the mass of the diethylenone.
3. The method for preparing acetoacetoxyethyl methacrylate according to claim 1, wherein: in the first step, the mass ratio of ethylene glycol to ketene dimer is 50-75.
4. The method for preparing acetoacetoxyethyl methacrylate according to claim 2 or 3, which comprises: the first step comprises the following specific steps: adding ethylene glycol and a first catalyst into a reaction container, heating to 80-100 ℃, adding diethylenone under a heat preservation state, continuing to react for 3-6 hours at 80-100 ℃ after the addition is finished, finishing the esterification reaction, and collecting the acetoacetic acid monoethylene glycol ester through rectification.
5. The method for preparing acetoacetoxyethyl methacrylate according to claim 1, which comprises the following steps: in the second step, the solvent is selected from dichloromethane, trichloromethane, toluene or benzene.
6. The method for preparing acetoacetoxyethyl methacrylate according to claim 5, which comprises the following steps: the solvent is dichloromethane; the second catalyst is selected from pyridine, 2-methylpyridine or 3-methylpyridine, and the ratio of the dosage of the second catalyst to the dosage of the substance of the acetoacetic acid monoethylene glycol ester is 1.0-1.5.
7. The method for preparing acetoacetoxyethyl methacrylate according to claim 1, wherein: the polymerization inhibitor is a mixture of ZJ-705 and hydroquinone, p-methylphenol or 2, 6-di-tert-butyl-p-cresol respectively, and the total consumption of the polymerization inhibitor is 0.1-0.3 per mill of the weight of methacryloyl chloride; the mass ratio of the methacrylic chloride to the acetoacetic acid monoethylene glycol ester is 0.57-0.86.
8. The method for preparing acetoacetoxyethyl methacrylate according to claim 1, wherein: and in the second step, mixing the acetoacetic acid monoethylene glycol ester, a solvent, a catalyst II and a polymerization inhibitor, heating to 40-50 ℃, dropwise adding methacryloyl chloride, keeping the dropwise adding time for 1-2 hours, continuing to perform heat preservation reaction for 1-3 hours after the dropwise adding is finished, cooling to 0-5 ℃ after the reaction is finished, filtering, distilling the collected filtrate at normal pressure at 40-60 ℃ to recover dichloromethane, performing reduced pressure rectification on the residual material, and collecting fractions at 20-30 Pa and 105-110 ℃ to obtain the acetoacetoxyethyl methacrylate.
9. An acetoacetoxyethyl methacrylate, which is prepared by the method for preparing acetoacetoxyethyl methacrylate according to claim 1.
10. The acetoacetoxyethyl methacrylate as claimed in claim 9, wherein the acetoacetoxyethyl methacrylate is used as a pesticide intermediate, a reaction monomer for photocuring and a polymer for cosmetics.
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