CN112642485B - Tert-butyl acetoacetate catalyst and preparation method thereof - Google Patents

Tert-butyl acetoacetate catalyst and preparation method thereof Download PDF

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CN112642485B
CN112642485B CN202011540457.3A CN202011540457A CN112642485B CN 112642485 B CN112642485 B CN 112642485B CN 202011540457 A CN202011540457 A CN 202011540457A CN 112642485 B CN112642485 B CN 112642485B
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acetoacetate
butyl
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methyl
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CN112642485A (en
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张春雨
蓝俊杰
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Shenzhen Prechem New Materials Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/128—Mixtures of organometallic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a tert-butyl acetoacetate catalyst and a preparation method thereof, wherein the formula comprises the following components: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 60-80 parts of methyl acetoacetate, 10-20 parts of tert-butyl acetate and 1-3 parts of high-efficiency catalyst; the method comprises the following steps of firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating; according to the invention, methyl acetoacetate and tert-butyl acetate are used as raw materials, and tert-butyl acetoacetate is produced by transesterification in the presence of a high-efficiency catalyst, so that the problems of difficult reaction and low yield of the conventional catalyst are solved; the invention has the advantages of high yield of tert-butyl acetoacetate up to 90%, less catalyst consumption, short reaction time, high conversion rate, mild reaction condition, no corrosion and no environmental pollution, easy product separation and purification, simple process, low energy consumption, etc.

Description

Tert-butyl acetoacetate catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of t-butyl acetoacetate catalysts, in particular to a t-butyl acetoacetate catalyst and a preparation method thereof.
Background
Tert-butyl acetoacetate is colorless liquid, has a boiling point of 190 ℃, is an efficient and safe environment-friendly organic solvent, is widely used as raw materials of medicines, pesticides and pigments, is used as an organic synthesis intermediate, and is mainly used as an acetoacetylating agent, and in the paint industry, the acetoacetylated polyester used for high-curing paint and other hydroxyl-containing resins are prepared by a non-catalyst method, so that the hydroxyl in the resin is replaced by the acetoacetyl, and the effect can reduce the viscosity of the resin, increase the solubility, reduce the glass transition point, increase the crosslinking property, improve the adhesion with metals, improve the corrosion resistance and improve the flexibility;
the prior art mainly has the following routes: the first method is to synthesize the product by adopting an ester exchange method, and to perform ester exchange reaction with tert-butyl alcohol under a reflux state by adopting ethyl acetoacetate or methyl acetoacetate as a raw material to obtain finished tert-butyl acetoacetate, wherein the process has long reaction time, low yield and 68% of the highest yield, and the process relates to recovery of solvent toluene and has high cost; the second is a Claisen ester condensation route, wherein tertiary butanol is firstly prepared into sodium alkoxide, and then ester condensation is carried out to obtain the tert-butyl acetoacetate, and the route needs to use expensive metal sodium, has low synthesis yield and has no mature industrial report; thirdly, the esterification reaction is carried out by adopting diketene and tertiary butanol, the highest yield reported in the prior literature is 87%, the yield is low, the quality is poor, the byproduct tertiary butyl ether is generated in the reaction process, the influence on the reaction yield is large, the raw materials are expensive, the yield is low, the acid corrosion is generated on equipment, and the preparation cost is high; in order to overcome the defects, it is necessary to design a tert-butyl acetoacetate catalyst and a preparation method thereof.
Disclosure of Invention
The invention aims to provide an acetoacetic acid tert-butyl ester catalyst and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a tert-butyl acetoacetate catalyst comprises the following components in percentage by weight: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 60-80 parts of methyl acetoacetate, 10-20 parts of tert-butyl acetate and 1-3 parts of high-efficiency catalyst.
A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating;
wherein in the first step, the contents of the components are as follows: 60-80 parts of methyl acetoacetate, 10-20 parts of tert-butyl acetate and 1-3 parts of high-efficiency catalyst are selected and weighed;
in the second step, the mixed heating comprises the following steps:
1) Adding the high-efficiency catalyst, the tertiary butyl acetate and the methyl acetoacetate into a distillation kettle with a rectifying tower and a stirrer according to the mol ratio of 0.0001-0.002:1:0.5-1.2;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 5-10:1, and continuously adding the rest methyl acetoacetate;
in the third step, the feeding processing comprises the following steps:
1) The total addition amount of the tert-butyl acetate is 3.5-5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept at 90-100 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of the tower kettle, and the adding time lasts for 1-2h;
in the fourth step, the reaction extraction comprises the following steps:
1) After the charging is completed, continuing to react and extracting until the temperature of the tower kettle is raised to 170 ℃ for 3-5 hours;
2) The tower bottom is tert-butyl acetoacetate and methyl acetoacetate which is not completely reacted, wherein the acetoacetate
The content of the tertiary butyl ester is more than 90%;
in the fifth step, the tower bottom material is decompressed, rectified and separated to obtain tert-butyl acetoacetate with the content of more than 98 percent, the tert-butyl acetate is extracted from the tower top, and the rectifying and separating tower is pressurized by 0.1-0.4Mpa, heated and rectified to obtain methyl acetoacetate with the content of more than 99 percent; tertiary butyl acetate and methyl acetoacetate are returned to the reaction again.
According to the technical scheme, the contents of the components are respectively as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of a high-efficiency catalyst.
According to the technical scheme, the high-efficiency catalyst is dibutyl tin oxide and tributyl tin chloride loaded on Al2O 3.
According to the technical scheme, the catalyst in the step two 1) can be recycled.
According to the technical scheme, the reaction in the step three 2) is followed by filtration and direct rectification.
According to the technical scheme, methyl acetate in the step five is sold or used for other purposes.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, methyl acetoacetate and tert-butyl acetate are used as raw materials, tert-butyl acetoacetate is produced through transesterification in the presence of a high-efficiency catalyst, and the byproduct is methyl acetate, so that the problems of difficult reaction and low yield of the conventional catalyst are solved; the invention has the advantages of high yield of tert-butyl acetoacetate up to 90%, less catalyst consumption, short reaction time, high conversion rate, mild reaction condition, no corrosion and no environmental pollution, easy product separation and purification, simple process, low energy consumption, etc.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
fig. 1 is a flow chart of the method of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the present invention provides a technical solution: a tert-butyl acetoacetate catalyst and a preparation method thereof are provided:
example 1:
a tert-butyl acetoacetate catalyst comprises the following components in percentage by weight: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of a high-efficiency catalyst.
A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating;
wherein in the first step, the contents of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of high-efficiency catalyst are selected and weighed;
in the second step, the mixed heating comprises the following steps:
1) Adding the high-efficiency catalyst, tert-butyl acetate and methyl acetoacetate into a distillation kettle with a rectifying tower and a stirrer according to the molar ratio of 0.0001-0.002:1:0.5-1.2, wherein the catalyst can be recycled;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 5-10:1, and continuously adding the rest methyl acetoacetate;
in the third step, the feeding processing comprises the following steps:
1) The total addition amount of the tert-butyl acetate is 3.5-5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept at 90-100 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of the tower kettle, the adding time lasts for 1-2h, and the methyl acetoacetate is directly rectified by filtration after reaction;
in the fourth step, the reaction extraction comprises the following steps:
1) After the charging is completed, continuing to react and extracting until the temperature of the tower kettle is raised to 170 ℃ for 3-5 hours;
2) The tower bottom is tert-butyl acetoacetate and methyl acetoacetate which is not completely reacted, wherein the content of the tert-butyl acetoacetate is more than 90 percent;
in the fifth step, the tower bottom material is decompressed, rectified and separated to obtain tert-butyl acetoacetate with the content of more than 98 percent, the tert-butyl acetate is extracted from the tower top, and the rectifying and separating tower is pressurized by 0.1-0.4Mpa, heated and rectified to obtain methyl acetoacetate with the content of more than 99 percent; tertiary butyl acetate, methyl acetoacetate is returned to the reaction for further reaction, and methyl acetate is sold or otherwise used.
Wherein the high-efficiency catalyst is dibutyl tin oxide and tributyl tin chloride loaded on Al2O 3.
Example 2:
a tert-butyl acetoacetate catalyst comprises the following components in percentage by weight: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of a high-efficiency catalyst.
A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating;
wherein in the first step, the contents of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of high-efficiency catalyst are selected and weighed;
in the second step, the mixed heating comprises the following steps:
1) Adding the high-efficiency catalyst, tert-butyl acetate and methyl acetoacetate into a distillation kettle with a rectifying tower and a stirrer according to the mol ratio of 0.003:1:0.5, wherein the catalyst can be recycled;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 6:1, and adding the rest methyl acetoacetate for 3 times at the same time;
in the third step, the feeding processing comprises the following steps:
1) The total adding amount of the tertiary butyl acetate is 3.5-5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept at 110-130 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of a tower kettle, the adding time lasts for 3 hours and is divided into three times, meanwhile, the temperature of the top of a rectifying tower is adjusted to be between 90 and 100 ℃, so that methyl acetate slowly comes out of the top of the rectifying tower, the balancing is carried out in the direction of generating tert-butyl acetoacetate, and the rectifying is directly carried out after the reaction and filtration;
in the fourth step, the reaction extraction comprises the following steps:
1) After the feeding is completed, continuing the reaction and extraction until the temperature of the tower kettle is raised to 170 ℃ for 5 hours;
2) The tower bottom is tert-butyl acetoacetate and incompletely reacted tert-butyl acetate, wherein the content of the tert-butyl acetoacetate is 90%;
in the fifth step, methyl acetate can be obtained by filtering, decompressing, rectifying and separating tower kettle materials, and finally tert-butyl acetoacetate with the content of more than 99% is obtained in the tower kettle; in the pressurizing, separating and rectifying process, methyl acetate extracted from the tower top slowly rises to over 100 deg.c, the pressure is regulated to 0.4MPa gradually, total reflux is carried out for 1 hr, the reflux ratio is regulated to 5 to 1, tert-butyl acetoacetate with the content of over 99% is obtained successively, methyl acetate can be sold or used for other purposes, and the mixture of methyl acetoacetate and tert-butyl acetate with small amount is returned to transesterification for reuse.
Wherein the high-efficiency catalyst is dibutyl tin oxide and tributyl tin chloride loaded on Al2O 3.
Example 3:
a tert-butyl acetoacetate catalyst comprises the following components in percentage by weight: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of K 2 CO 3 。
A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating;
wherein in the first step, the contents of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of K 2 CO 3 Selecting and weighing;
in the second step, the mixed heating comprises the following steps:
1) Will K 2 CO 3 Adding the tert-butyl acetate and methyl acetoacetate into a distillation kettle with a rectifying tower and a stirrer according to the mol ratio of 0.02:1:0.7, and recycling the catalyst;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 7:1, and simultaneously adding the rest methyl acetoacetate for 3 times in 5 hours;
in the third step, the feeding processing comprises the following steps:
1) The total adding amount of the tert-butyl acetate is 4.5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept between 110 and 130 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of the tower kettle, the adding time lasts for 3 hours, and the methyl acetoacetate is directly rectified by filtration after reaction;
in the fourth step, the reaction extraction comprises the following steps:
1) After the feeding is completed, continuing to react and extracting until the temperature of the tower kettle is raised to 170 ℃ for 3 hours;
2) The tower bottom is tert-butyl acetoacetate and incompletely reacted tert-butyl acetate, wherein the content of the tert-butyl acetoacetate is 72%;
in the fifth step, methyl acetate can be obtained by filtering, decompressing, rectifying and separating tower kettle materials, and finally tert-butyl acetoacetate with the content of more than 90% is obtained in the tower kettle; in the pressurizing, separating and rectifying process, methyl acetate extracted from the tower top slowly rises to over 100 deg.c, the pressure is regulated to 0.4MPa gradually, total reflux is carried out for 1 hr, the reflux ratio is regulated to 5 to 1, tert-butyl acetoacetate with the content of over 99% is obtained successively, methyl acetate can be sold or used for other purposes, and the mixture of methyl acetoacetate and tert-butyl acetate with small amount is returned to transesterification for reuse.
Example 4:
a tert-butyl acetoacetate catalyst comprises the following components in percentage by weight: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of C 2 H 5 ONa。
A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating;
wherein in the first step, the contents of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of C 2 H 5 ONa is selectedWeighing;
in the second step, the mixed heating comprises the following steps:
1) C is C 2 H 5 ONa, tert-butyl acetate and methyl acetoacetate are added into a distillation still with a rectifying tower and a stirrer according to the mol ratio of 0.02:1:1.0, and the catalyst can be recycled;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 6:1, and continuously adding the rest methyl acetoacetate;
in the third step, the feeding processing comprises the following steps:
1) The total adding amount of the tert-butyl acetate is 4.5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept between 110 and 130 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of the tower kettle, the adding time lasts for 3-5h, and the methyl acetoacetate is directly rectified by filtration after reaction;
in the fourth step, the reaction extraction comprises the following steps:
1) After the feeding is completed, continuing the reaction and extraction until the temperature of the tower kettle is raised to 170 ℃ for 4 hours;
2) The tower bottom is tert-butyl acetoacetate and incompletely reacted tert-butyl acetate, wherein the content of the tert-butyl acetoacetate is 83%;
in the fifth step, methyl acetate is obtained by filtering, decompressing, rectifying and separating tower kettle materials, finally tert-butyl acetoacetate with the content of more than 91% is obtained in a tower kettle, methyl acetate extracted from the tower top is slowly heated to more than 100 ℃ in pressurizing, separating and rectifying, the pressure is gradually regulated to 0.4Mpa, then the total reflux is carried out for 1h, the reflux ratio is regulated to 5:1, tert-butyl acetoacetate with the content of more than 99% is sequentially obtained, the methyl acetate can be sold or used, and the mixture of the methyl acetoacetate with a small amount of tert-butyl acetate is returned to transesterification for recycling.
Example 5:
a tert-butyl acetoacetate catalyst comprises the following components in percentage by weight: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of a high-efficiency catalyst.
A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating;
wherein in the first step, the contents of the components are as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of high-efficiency catalyst are selected and weighed;
in the second step, the mixed heating comprises the following steps:
1) Adding the high-efficiency catalyst, tert-butyl acetate and methyl acetoacetate into a distillation kettle with a rectifying tower and a stirrer according to the mol ratio of 0.005:1:1.2, wherein the catalyst can be recycled;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 8:1, and continuously adding the rest methyl acetoacetate;
in the third step, the feeding processing comprises the following steps:
1) The total adding amount of the tert-butyl acetate is 4.5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept between 110 and 130 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of the tower kettle, and the adding time lasts for 3-5h;
in the fourth step, the reaction extraction comprises the following steps:
1) After the feeding is completed, continuing the reaction and extraction until the temperature of the tower kettle is increased to 200 ℃ and the duration time is 4 hours;
2) The tower bottom is tert-butyl acetate which is not completely reacted with tert-butyl acetoacetate, wherein the content of the tert-butyl acetoacetate is 93 percent;
in the fifth step, methyl acetate is obtained by filtering, decompressing, rectifying and separating tower kettle materials, finally tert-butyl acetoacetate with the content of more than 99% is obtained in a tower kettle, methyl acetate extracted from the tower top is slowly heated to more than 100 ℃ in pressurizing, separating and rectifying, the pressure is gradually regulated to 0.4Mpa, then the total reflux is carried out for 1h, the reflux ratio is regulated to 5:1, tert-butyl acetoacetate with the content of more than 99% is sequentially obtained, the methyl acetate can be sold or used, and the mixture of the methyl acetoacetate with a small amount of tert-butyl acetate is returned to transesterification for recycling.
Wherein the high-efficiency catalyst is dibutyl tin oxide and tributyl tin chloride loaded on Al2O 3.
The properties of the above examples are compared in the following table:
based on the above, the invention has the advantages that methyl acetoacetate and tert-butyl acetate are used as raw materials, tert-butyl acetoacetate is produced by transesterification in the presence of a high-efficiency catalyst, and the byproduct is methyl acetate, so that the problems of difficult reaction and low yield of the conventional catalyst are solved; the invention has the advantages of high yield of tert-butyl acetoacetate up to 90%, less catalyst consumption, short reaction time, high conversion rate, mild reaction condition, no corrosion and no environmental pollution, easy product separation and purification, simple process, low energy consumption, etc.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A tert-butyl acetoacetate catalyst is characterized in that: the formula comprises: methyl acetoacetate, tert-butyl acetate and a high-efficiency catalyst, wherein the mass percentages of the components are as follows: 60-80 parts of methyl acetoacetate, 10-20 parts of tert-butyl acetate and 1-3 parts of high-efficiency catalyst, wherein the high-efficiency catalyst is C 2 H 5 ONa, the tert-butyl acetoacetate catalyst is prepared by reacting a high-efficiency catalyst, tert-butyl acetate and methyl acetoacetate in a distillation kettle with a rectifying tower and a stirrer, wherein after heating to the temperature of the top of the tower to be stable, methyl acetate is extracted at a reflux ratio of 8:1, and the rest methyl acetoacetate is continuously added; when the reaction is extracted, the reflux ratio is adjusted to be 5:1.
2. A preparation method of an acetoacetic acid tert-butyl ester catalyst comprises the following steps of, firstly, selecting materials; step two, mixing and heating; step three, feeding and processing; step four, reaction and extraction; step five, rectifying and separating; the method is characterized in that:
wherein in the first step, the contents of the components are as follows: 60-80 parts of methyl acetoacetate, 10-20 parts of tert-butyl acetate and 1-3 parts of high-efficiency catalyst are selected and weighed;
in the second step, the mixed heating comprises the following steps:
1) Adding the high-efficiency catalyst, the tertiary butyl acetate and the methyl acetoacetate into a distillation kettle with a rectifying tower and a stirrer according to the mol ratio of 0.0001-0.002:1:0.5-1.2;
2) Heating until the temperature of the tower top is stable, extracting methyl acetate at a reflux ratio of 8:1, and continuously adding the rest methyl acetoacetate;
in the third step, the feeding processing comprises the following steps:
1) The total addition amount of the tert-butyl acetate is 3.5-5 times of the molar ratio of the methyl acetoacetate, and the temperature of the tower kettle is kept at 90-100 ℃ in the feeding process of the methyl acetoacetate;
2) The adding speed of methyl acetoacetate is controlled by the temperature of the tower kettle, and the adding time lasts for 1-2h;
in the fourth step, the reaction extraction comprises the following steps:
1) After the charging is completed, continuing to react and extracting until the temperature of the tower kettle is raised to 170 ℃ for 3-5 hours;
2) The tower bottom is tert-butyl acetoacetate and methyl acetoacetate which is not completely reacted, wherein the content of the tert-butyl acetoacetate is more than 90 percent;
in the fifth step, the tower bottom material is decompressed, rectified and separated to obtain tert-butyl acetoacetate with the content of more than 98 percent, the tert-butyl acetate extracted from the tower top is pressurized by 0.1-0.4Mpa, then rectified, and when the materials are extracted by reaction, the reflux ratio is adjusted to be 5:1, so that methyl acetoacetate with the content of more than 99 percent can be obtained; tertiary butyl acetate and methyl acetoacetate are returned to the reaction again.
3. A t-butyl acetoacetate catalyst according to claim 1, characterized in that: the contents of the components are respectively as follows: 80 parts of methyl acetoacetate, 18 parts of tert-butyl acetate and 2 parts of a high-efficiency catalyst.
4. A t-butyl acetoacetate catalyst according to claim 1, characterized in that: the high-efficiency catalyst is dibutyl tin oxide and tributyl tin chloride loaded on Al2O 3.
5. The method for preparing the tert-butyl acetoacetate catalyst according to claim 2, which is characterized in that: the catalyst in the step two 1) can be recycled.
6. The method for preparing the tert-butyl acetoacetate catalyst according to claim 2, which is characterized in that: and step three), filtering and directly rectifying after the reaction in the step 2).
7. The method for preparing the tert-butyl acetoacetate catalyst according to claim 2, which is characterized in that: methyl acetate is sold or otherwise used in the fifth step.
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