CN113480423A - Method for synthesizing succinate - Google Patents
Method for synthesizing succinate Download PDFInfo
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- CN113480423A CN113480423A CN202110940165.7A CN202110940165A CN113480423A CN 113480423 A CN113480423 A CN 113480423A CN 202110940165 A CN202110940165 A CN 202110940165A CN 113480423 A CN113480423 A CN 113480423A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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Abstract
The invention discloses a method for synthesizing succinate, which mainly comprises the following steps: s1, adding palladium salt, 1, 2-di (di-tert-butylphosphinomethyl) benzene, methanesulfonic acid and acrylic acid or acrylic ester into a solvent, and stirring to form a uniform solution; s2, transferring the solution obtained in the step S1 to a high-pressure reaction kettle, sealing the reaction kettle, and replacing air in the kettle with nitrogen; s3, heating the solution, introducing carbon monoxide, and starting stirring reaction at the rotating speed of 600 rpm; continuously supplementing carbon monoxide into the reaction kettle in the reaction process, so that the pressure of the carbon monoxide in the reaction kettle is kept unchanged; s4, after the reaction is finished, analyzing the product by gas chromatography. The raw materials of the synthesis method adopted by the invention are not limited to petroleum raw materials any more, the conversion rate of the raw materials is excellent, and the selectivity of the succinate is excellent.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing succinate by carbonylation of acrylate.
Background
Succinic acid and esters thereof are monomers for synthesizing biodegradable resin poly (butylene succinate) (PBS), and compared with the traditional biodegradable polyester, the PBS has low price and the cost is only 1/3 of polycaprolactone or poly (hydroxytyrosic acid). And the PBS has higher mechanical property, is close to Polyethylene (PE) and polypropylene (PP), and can meet the use requirement of general plastic.
The prior succinic acid production method mainly comprises a paraffin oxidation method, a catalytic hydrogenation method, a light oil oxidation method, a succinonitrile hydrolysis method and an electrochemical synthesis method, and the succinic acid is prepared by a biological method abroad. Wherein, the catalytic hydrogenation method of maleic acid is the main method for producing succinic acid. The method comprises the steps of extracting benzene from petroleum, then generating maleic acid under the catalysis of vanadium pentoxide, and finally obtaining succinic acid through catalytic hydrogenation. The method is based on petroleum raw materials, has the problem of low atom utilization rate, and is limited by the basic national conditions of 'rich coal, lean oil and little gas' in China. Therefore, the development of non-petroleum routes for producing succinic acid and esters thereof has important significance.
Generally, the main method for producing succinic acid at present is a catalytic hydrogenation method of maleic acid. The process is based on petroleum feedstocks, which are limited to our country. And the method for preparing succinic acid by maleic acid catalytic hydrogenation has the problem of low atom utilization rate, and the method for synthesizing succinic acid by taking acrylic acid (ester) as a raw material has the problem of low yield.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for synthesizing succinate by carbonylation of acrylate, which comprises the following steps:
s1, adding palladium salt, 1, 2-di (di-tert-butylphosphinomethyl) benzene, methanesulfonic acid and acrylic acid or acrylic ester into a solvent, and stirring to form a uniform solution;
s2, transferring the solution obtained in the step S1 to a high-pressure reaction kettle, sealing the reaction kettle, and replacing air in the kettle with nitrogen;
s3, heating the solution, introducing carbon monoxide, and starting stirring reaction at the rotating speed of 600 rpm; continuously supplementing carbon monoxide into the reaction kettle in the reaction process, so that the pressure of the carbon monoxide in the reaction kettle is kept unchanged;
s4, after the reaction is finished, analyzing the product by gas chromatography.
Further, the palladium salt in step S1 is one or more of tris (dibenzylidene-base acetone) dipalladium (0), palladium acetate or palladium chloride, the acrylate is one or more of methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate, and the solvent is one of methanol, ethanol, cyclohexane, benzene or dichloromethane.
Furthermore, the molar amount of the 1, 2-bis (di-tert-butylphosphinomethyl) benzene in the step S1 is 1/4 to 3/4 times that of the methanesulfonic acid, the molar amount of the palladium salt is 0.03 to 0.08 times that of the methanesulfonic acid, the molar amount of the acrylate is 400 to 5000 times that of the palladium salt, and the molar amount of the solvent is 1 to 15 times that of the acrylate.
Further, the reaction temperature in step S2 is 40-70 ℃, and the pressure of carbon monoxide is 2-4 MPa.
Further, the gas chromatography conditions in step S4 are: the chromatographic column is KB-624 type capillary chromatographic column, the detector is FID detector, the vaporization chamber temperature is 240 ℃, the detection chamber temperature is 260 ℃, the column temperature program heating program is 80 ℃ and is reserved for 3min, and then the temperature is raised to 220 ℃ at the heating rate of 30 ℃/min and is kept for 10 min.
By adopting the method for synthesizing the succinate, the conversion rate of the acrylate can reach 99.35%, the conversion rate of the acrylic acid can reach 98.1%, and the selectivity of the succinate can reach 95.7-97.9%.
Wherein, the calculation method of the conversion rate and the selectivity is as follows:
compared with the prior art, the method for synthesizing the succinate provided by the invention has the following beneficial effects:
1. the invention adopts acrylic acid (ester) as raw material, synthesizes succinic acid (ester) by carbonyl, avoids using petroleum raw material, and accords with the current situation of rich coal and lean oil in China.
2. The invention uses the palladium salt catalytic system in the acrylic acid (ester) carbonylation reaction process, and the reaction conversion rate and the selectivity are both better than those of the prior method.
Drawings
FIG. 1 chromatogram of the product obtained in example 2
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1, a method of synthesizing a succinate ester comprising the steps of:
s1, adding palladium salt, 1, 2-di (di-tert-butylphosphinomethyl) benzene, methanesulfonic acid and acrylic acid into a solvent, and stirring to form a uniform solution;
s2, transferring the solution obtained in the step S1 to a high-pressure reaction kettle, sealing the reaction kettle, and replacing air in the kettle with nitrogen;
s3, heating the solution, introducing carbon monoxide, and starting stirring reaction at the rotating speed of 600 rpm; continuously supplementing carbon monoxide into the reaction kettle in the reaction process, so that the pressure of the carbon monoxide in the reaction kettle is kept unchanged;
s4, after the reaction is finished, analyzing the product by gas chromatography.
Wherein the palladium salt in step S1 is tris (dibenzylidene-base acetone) dipalladium (0), the acrylate is methyl acrylate, and the solvent is methanol.
The molar amount of the 1, 2-bis (di-tert-butylphosphinomethyl) benzene used in the step S1 is 1/4 times that of the methanesulfonic acid, the molar amount of the palladium salt is 0.03 times that of the methanesulfonic acid, the molar amount of the acrylate is 400 times that of the palladium salt, and the molar amount of the solvent is 1 time that of the acrylate.
The reaction temperature in step S2 was 40 ℃ and the pressure of carbon monoxide was 2 MPa.
The gas chromatography conditions in step S4 were: the chromatographic column is KB-624 type capillary chromatographic column, the detector is FID detector, the vaporization chamber temperature is 240 ℃, the detection chamber temperature is 260 ℃, the column temperature program heating program is 80 ℃ and is reserved for 3min, and then the temperature is raised to 220 ℃ at the heating rate of 30 ℃/min and is kept for 10 min.
Example 2 a method for synthesizing succinate, which is different from example 1 in that palladium salt in step S1 is palladium acetate, acrylate is ethyl acrylate, and solvent is ethanol.
The molar amount of the 1, 2-bis (di-tert-butylphosphinomethyl) benzene used in the step S1 is 2/4 times that of the methanesulfonic acid, the molar amount of the palladium salt is 0.05 times that of the methanesulfonic acid, the molar amount of the acrylate is 1000 times that of the palladium salt, and the molar amount of the solvent is 10 times that of the acrylate.
The reaction temperature in step S2 was 60 ℃ and the pressure of carbon monoxide was 3 MPa.
The rest is similar to example 1.
Example 3 a method for synthesizing succinate differs from example 1 in that the palladium salt in step S1 is palladium chloride, the acrylate is propyl acrylate, and the solvent is cyclohexane.
The molar amount of the 1, 2-bis (di-tert-butylphosphinomethyl) benzene used in the step S1 is 3/4 times that of the methanesulfonic acid, the molar amount of the palladium salt is 0.08 times that of the methanesulfonic acid, the molar amount of the acrylate is 5000 times that of the palladium salt, and the molar amount of the solvent is 15 times that of the acrylate.
The reaction temperature in step S2 was 70 ℃ and the pressure of carbon monoxide was 4 MPa.
The rest is similar to example 1.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A method of synthesizing a succinate ester comprising the steps of:
s1, adding palladium salt, 1, 2-di (di-tert-butylphosphinomethyl) benzene, methanesulfonic acid and acrylic acid or acrylic ester into a solvent, and stirring to form a uniform solution;
s2, transferring the solution obtained in the step S1 to a high-pressure reaction kettle, sealing the reaction kettle, and replacing air in the kettle with nitrogen;
s3, heating the solution, introducing carbon monoxide, and starting stirring reaction at the rotating speed of 600 rpm; continuously supplementing carbon monoxide into the reaction kettle in the reaction process, so that the pressure of the carbon monoxide in the reaction kettle is kept unchanged;
s4, after the reaction is finished, analyzing the product by gas chromatography.
2. The method of claim 1, wherein the palladium salt in step S1 is one or more of tris (dibenzylidene-base acetone) dipalladium (0), palladium acetate or palladium chloride, the acrylate is one or more of methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate, and the solvent is one of methanol, ethanol, cyclohexane, benzene or dichloromethane.
3. The method for synthesizing succinic acid ester according to claim 1, wherein the molar amount of 1, 2-bis (di-tert-butylphosphinomethyl) benzene used in step S1 is 1/4 to 3/4 times that of methanesulfonic acid, the molar amount of palladium salt is 0.03 to 0.08 times that of methanesulfonic acid, the molar amount of acrylic acid ester is 400 to 5000 times that of palladium salt, and the molar amount of solvent is 1 to 15 times that of acrylic acid ester.
4. The method for synthesizing succinic acid ester according to claim 1, wherein the reaction temperature in step S2 is 40 to 70 ℃ and the pressure of the carbon monoxide is 2 to 4 MPa.
5. The method for synthesizing succinate according to claim 1, wherein the gas chromatography conditions in the step S4 are as follows: the chromatographic column is KB-624 type capillary chromatographic column, the detector is FID detector, the vaporization chamber temperature is 240 ℃, the detection chamber temperature is 260 ℃, the column temperature program heating program is 80 ℃ and is reserved for 3min, and then the temperature is raised to 220 ℃ at the heating rate of 30 ℃/min and is kept for 10 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241024A (en) * | 2019-06-13 | 2019-09-17 | 西北农林科技大学 | The screening technique of one type succinate production bacterium |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241024A (en) * | 2019-06-13 | 2019-09-17 | 西北农林科技大学 | The screening technique of one type succinate production bacterium |
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