CN114436845B - Method for synthesizing methyl methoxyacetate by carbonylation of formaldehyde - Google Patents

Method for synthesizing methyl methoxyacetate by carbonylation of formaldehyde Download PDF

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CN114436845B
CN114436845B CN202011125805.0A CN202011125805A CN114436845B CN 114436845 B CN114436845 B CN 114436845B CN 202011125805 A CN202011125805 A CN 202011125805A CN 114436845 B CN114436845 B CN 114436845B
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carbonylation
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rhodium
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CN114436845A (en
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王迪
吕建刚
刘波
周海春
金萍
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • 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
    • C07C51/145—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide with simultaneous oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

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Abstract

The invention relates to a method for synthesizing methyl methoxyacetate by formaldehyde carbonylation, which adopts a rhodium carbonyl catalyst and comprises the following steps: (1) Mixing rhodium carbonyl catalyst with methyl tertiary butyl ether and/or ethyl tertiary butyl ether as solvent to obtain mixture; (2) Fully contacting formaldehyde monomer source substances, CO, organic carboxylic acid and the mixture obtained in the step (1) to carry out carbonylation reaction; after the reaction is finished, separating the solvent and the catalyst to obtain a carbonylation product; (3) Methanol is added into the carbonylation product to carry out esterification reaction, thus generating methoxy methyl acetate. The invention is characterized in that the catalyst has no corrosiveness to the reaction equipment, realizes the direct separation of the product and the catalyst, and the direct recycling of the catalyst and the solvent, and effectively reduces the energy consumption and the production cost of the separation procedure.

Description

Method for synthesizing methyl methoxyacetate by carbonylation of formaldehyde
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for synthesizing methoxy methyl acetate by formaldehyde carbonyl.
Background
Carbonylation of formaldehyde and its derivatives is an important research direction for C1 chemistry. The route adopts formaldehyde and derivatives thereof which take coal, natural gas or biomass as sources as raw materials to produce glycol, and is one of important substitutes of the prior glycol process. Methyl methoxyacetate, one of carbonylation products, is a valuable intermediate, can be used for kinetic resolution of chiral amine compounds, synthesis of vitamin B6, sulfanilamide-5-pyrimidine and the like, is used as a catalyst in polymerization reaction, and can also be hydrogenated and hydrolyzed to prepare ethylene glycol.
At present, carbonylation reactions have two routes, a homogeneous catalysis method and a heterogeneous catalysis method. The traditional homogeneous phase method mainly adopts inorganic liquid acid as a catalyst, such as concentrated sulfuric acid, hydrofluoric acid, fluorine-containing sulfonic acid and the like. DuPont in USP2152852 and USP2285448 disclosed the use of sulfuric acid as a catalyst for the carbonylation of formaldehyde and CO at 200 ℃ and 90MPa for the commercial production of ethylene glycol was stopped in 1968. Chevron in USP3911003 discloses formaldehyde carbonylation at 22-50℃and 6.89-13.78MPa using HF as a catalyst. Because inorganic acid has strong corrosiveness and serious pollution, the production is stopped after the production is put into operation. EP19820305617 uses a strong acid catalyst to catalyze methylal to carry out carbonylation under a liquid condition to produce methoxy methyl acetate, and the problems of difficult separation of products, corrosion of a device by liquid acid and the like exist. The heterogeneous process usually uses solid acid as catalyst, and various developed solid acids (such as molecular sieve, heteropolyacid, ion exchange resin, etc.) have the advantages of low corrosiveness and easy separation, but the catalytic activity, the cycle performance, etc. of the heterogeneous process still need to be improved.
The main technical difficulty of the carbonylation reaction is that the reaction speed is low and the selectivity is low. The slow reaction rate is due to two reasons: (1) lack of efficient catalyst system, (2) low concentration of CO in solution or at reaction sites, and difficult mass transfer. Because of the difficulty in developing high-activity catalysts, the reaction effect is generally improved by adopting a method of increasing the temperature and the pressure and prolonging the reaction time, and the conditions of more side reactions and low selectivity are aggravated by severe reaction conditions. Therefore, the heart of the carbonylation study is in two aspects: catalyst development and reaction process enhancement, and optimization of the reaction is achieved by adopting a novel catalyst with high activity and adjusting a reaction system.
In summary, since the inorganic acid catalyst is seriously polluted, and the liquid-phase carbonylation reaction of formaldehyde needs to be performed under high pressure, the separation of the catalyst and the product is difficult, the separation cost is high, and the problems of corrosion devices and the like exist, the development of a new catalyst and a new process becomes a key point of research on the carbonylation of formaldehyde.
Patent CN1064040C proposes the possibility of metal carbonyls as catalysts, with sulfuric acid/metal carbonyls (H 2 SO 4 /Cu(CO) n + 、H 2 SO 4 /Ag(CO) n + Etc.) are catalysts, formaldehyde is carbonylated and esterified in a strong acid system to obtain methyl glycolate. The reaction conditions are relatively mild, but the problems of corrosion of sulfuric acid to the device, difficulty in product separation and the like still exist.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for synthesizing methyl methoxyacetate by carbonylation of formaldehyde, which is characterized in that a catalyst is non-corrosive to reaction equipment, direct separation of a carbonylation product and the catalyst and recycling of the catalyst and a solvent can be realized through liquid layering after carbonylation reaction, so that the energy consumption of a separation process is effectively reduced, and the production cost is saved.
The invention provides a method for preparing methoxy methyl acetate by formaldehyde carbonylation, which adopts a rhodium carbonyl catalyst and comprises the following steps:
(1) Uniformly mixing a rhodium carbonyl catalyst and a solvent to obtain a mixture;
(2) Fully contacting formaldehyde monomer source substances, CO, organic carboxylic acid and the mixture obtained in the step (1) to carry out carbonylation reaction; after the reaction is finished, separating the solvent and the catalyst to obtain a carbonylation product;
(3) Adding methanol into the carbonylation product to carry out esterification reaction to generate methoxy methyl acetate;
the solvent in the step (1) is methyl tertiary butyl ether and/or ethyl tertiary butyl ether.
In the above technical scheme, the rhodium carbonyl catalyst is preferably one or more of rhodium dicarbonyl acetylacetonate, bis (triphenylphosphine) rhodium carbonyl chloride, tris (triphenylphosphine) rhodium carbonyl hydride, tetracarbonyl rhodium dichloride and rhodium acetylacetonate triphenylphosphine carbonyl.
In the technical scheme, the rhodium carbonyl catalyst is used in an amount of 0.05-0.5 mol% of the formaldehyde monomer source substance in terms of mol. The molar ratio of the feeding amount of the organic carboxylic acid to the feeding amount of the formaldehyde monomer source substance is 1:2-1:1, and the molar ratio of the organic carboxylic acid to the solvent is 1:1-1:10.
In the above technical scheme, the rhodium carbonyl catalyst and the solvent in the step (1) may be fresh rhodium carbonyl catalyst and solvent or rhodium carbonyl catalyst and solvent recovered from the reaction process. The solvent and the catalyst separated in the step (2) can be directly used as the catalyst and the solvent in the step (1) for recycling.
In the above technical scheme, the formaldehyde monomer source material in the step (2) is trioxymethylene and/or paraformaldehyde. The organic carboxylic acid includes one or more of acetic acid, propionic acid, and isobutyric acid.
In the technical scheme, the temperature of the carbonylation reaction in the step (2) is 70-120 ℃; the pressure of the carbonylation reaction is 5-10MPa. The reaction time is 2-6h.
In the technical scheme, the reaction temperature of the esterification reaction in the step (3) is 80-120 ℃ and the reaction time is 1-4h. The molar excess of the methanol addition relative to the formaldehyde addition is sufficient.
The invention has the beneficial effects that:
the method is used for synthesizing methyl methoxyacetate by formaldehyde carbonylation, and the rhodium carbonyl catalyst is adopted, so that the catalyst has no corrosiveness to reaction equipment. The invention further adopts a specific solvent, and can realize the direct separation of the carbonylation product and the catalyst through liquid layering after the carbonylation reaction, and the recycling of the catalyst and the solvent, thereby effectively reducing the energy consumption of the separation procedure and saving the production cost. The invention has the characteristics of high product yield, no corrosion to reaction equipment, easy separation of catalyst and solvent, cyclic utilization and the like.
Drawings
FIG. 1 is a schematic diagram of the layering of the product after the carbonylation reaction and before the esterification reaction in example 1;
FIG. 2 is a schematic diagram of the layering of the product after the carbonylation reaction and before the esterification reaction in example 2;
FIG. 3 is a schematic diagram showing the reaction product of comparative example 1 after the carbonylation reaction and before the esterification reaction.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The yield of the methoxyl methyl acetate obtained by the product in the invention is expressed, the byproducts are methyl glycolate and methyl formate, and the method for calculating the yield of the product is as follows:
yield of methyl methoxyacetate (%) =molar yield of methyl methoxyacetate/molar yield of raw formaldehyde x 100%.
[ example 1 ]
1. Catalyst treatment
0.459g (0.5 mmol) of rhodium tris (triphenylphosphine) carbonyl hydride was weighed into 44g of methyl tert-butyl ether and dispersed ultrasonically for 1 hour to give a homogeneous pale yellow liquid.
2. Carbonylation reaction
The homogeneous mixture was placed in a 100mL stainless steel autoclave, 7.5g of acetic acid, 6.1g of water, and 7.5g of paraformaldehyde (0.25 mol, CAT/HCHO=0.2 mol%) were sequentially added, the autoclave was sealed, the air in the autoclave was replaced with CO 3 times, high-pressure CO was introduced to 8MPa, and the reaction was carried out at 110℃under vigorous stirring for 3 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, all the reaction liquid is taken out and placed in a separating funnel, and the reaction kettle is kept stand until layering. As shown in figure 1, the liquid is divided into an upper layer and a lower layer, and the lower layer liquid is filtered by a microporous filter membrane to obtain a yellowish transparent clarified carbonylation product for standby.
3. Esterification reaction
The lower layer carbonylation product after filtration was put into a reaction kettle, 20mL of methanol and 1g of Amberlyst-36 resin were added, the reaction kettle was sealed, the reaction was carried out for 2 hours under stirring at 100 ℃, after the reaction was completed, the reaction kettle was cooled to room temperature, the feed liquid in the kettle was taken out, and the feed liquid was analyzed by gas chromatography and high performance liquid chromatography to obtain the product yield (Table 1).
Referring to fig. 1, the liquid is divided into an upper layer and a lower layer, and the method can be used for directly separating a carbonylation reaction product (a lower layer) from a catalyst-solvent mixture (an upper layer), so that the processing amount of the operation of the next esterification link, the subsequent rectification and the like is greatly reduced, and the separation and recovery of the catalyst can be realized.
[ example 2 ]
1. Catalyst recovery
The upper layer of the liquid after the carbonylation reaction of example 1 was taken out to obtain a homogeneous mixture of catalyst and solvent, which was sealed for further use.
2. Carbonylation reaction
The homogeneous mixture was placed in a 100mL stainless steel autoclave, 7.5g of acetic acid, 6.1g of water, and 7.5g of paraformaldehyde (0.25 mol, CAT/HCHO=0.2 mol%) were sequentially added, the autoclave was sealed, the air in the autoclave was replaced with CO 3 times, high-pressure CO was introduced to 8MPa, and the reaction was carried out at 110℃under vigorous stirring for 3 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, all the reaction liquid is taken out and placed in a separating funnel, and the reaction kettle is kept stand until layering. As shown in figure 2, the liquid is divided into an upper layer and a lower layer, and the lower layer liquid is filtered by a microporous filter membrane to obtain a yellowish transparent clarified carbonylation product for standby.
3. Esterification reaction
The lower layer carbonylation product after filtration was put into a reaction kettle, 20mL of methanol and 1g of Amberlyst-36 resin were added, the reaction kettle was sealed, the reaction was carried out for 2 hours under stirring at 100 ℃, after the reaction was completed, the reaction kettle was cooled to room temperature, the feed liquid in the kettle was taken out, and the feed liquid was analyzed by gas chromatography and high performance liquid chromatography to obtain the product yield (Table 1).
Comparing fig. 1 and fig. 2, it can be seen that the carbonylation upper liquid recovered in example 1 is used as a catalyst and reused under the same reaction conditions, and the reaction process is similar to that of a fresh catalyst, namely, obvious layering phenomenon of a carbonylation product (lower layer) and a catalyst-solvent (upper layer) occurs.
As can be seen from Table 1, the yield of the methoxymethyl acetate product in example 2 is comparable to that in example 1, i.e., efficient recovery and utilization of the catalyst and solvent is achieved.
[ example 3 ]
1. Catalyst treatment
Rhodium dicarbonyl acetylacetonate 0.131g (0.5 mmol) was weighed into 82g ethyl tert-butyl ether and dispersed ultrasonically for 1 hour to give a homogeneous pale yellow liquid.
2. Carbonylation reaction
The homogeneous mixture was placed in a 100mL stainless steel autoclave, 7.4g of propionic acid, 6.1g of water, 9.0g of trioxymethylene (0.1 mol, cat/hcho=0.5 mol%) were added in sequence, the autoclave was sealed, the air in the autoclave was replaced with CO 3 times, high-pressure CO was introduced to 6MPa, and the reaction was carried out under vigorous stirring at 100 ℃ for 5 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, all the reaction liquid is taken out and placed in a separating funnel, and the reaction kettle is kept stand until layering. The liquid is divided into an upper layer and a lower layer, and the lower layer liquid is filtered by a microporous filter membrane to obtain a yellowish transparent clarified carbonylation product for standby.
3. Esterification reaction
The lower layer carbonylation product after filtration was put into a reaction kettle, 20mL of methanol and 1g of Amberlyst-36 resin were added, the reaction kettle was sealed, and reacted for 1.5 hours under stirring at 120 ℃, after the reaction was completed, the reaction kettle was cooled to room temperature, and the feed liquid in the kettle was taken out, and analyzed by gas chromatography and high performance liquid chromatography to obtain the product yield (Table 1).
The liquid after the carbonylation reaction is divided into an upper layer and a lower layer, and the method can realize the direct separation of the carbonylation reaction product (the lower layer) and the catalyst-solvent mixture (the upper layer), so that the processing amount of the operation of the next esterification link, the subsequent rectification and the like is greatly reduced, and the separation and recovery of the catalyst can be realized.
[ example 4 ]
1. Catalyst treatment
0.346g (0.5 mmol) of rhodium bis (triphenylphosphine) carbonyl chloride was weighed into 22g of methyl tert-butyl ether and dispersed ultrasonically for 1 hour to give a homogeneous pale yellow liquid.
2. Carbonylation reaction
The homogeneous mixture was placed in a 100mL stainless steel autoclave, 11.2g of isobutyric acid, 6.1g of water, 3.8g of paraformaldehyde (0.127 mol, CAT/HCHO=0.4 mol%) were added in sequence, the autoclave was sealed, the air in the autoclave was replaced with CO 3 times, high-pressure CO was introduced to 9MPa, and the reaction was carried out under vigorous stirring at 80℃for 3 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, all the reaction liquid is taken out and placed in a separating funnel, and the reaction kettle is kept stand until layering. The liquid is divided into an upper layer and a lower layer, and the lower layer liquid is filtered by a microporous filter membrane to obtain a yellowish transparent clarified carbonylation product for standby.
3. Esterification reaction
The lower layer carbonylation product after filtration was put into a reaction kettle, 20mL of methanol and 1g of Amberlyst-36 resin were added, the reaction kettle was sealed, the reaction was carried out for 4 hours under stirring at 80 ℃, after the reaction was completed, the reaction kettle was cooled to room temperature, the feed liquid in the kettle was taken out, and the feed liquid was analyzed by gas chromatography and high performance liquid chromatography to obtain the product yield (Table 1).
The liquid after the carbonylation reaction is divided into an upper layer and a lower layer, and the method can realize the direct separation of the carbonylation reaction product (the lower layer) and the catalyst-solvent mixture (the upper layer), so that the processing amount of the operation of the next esterification link, the subsequent rectification and the like is greatly reduced, and the separation and recovery of the catalyst can be realized.
Comparative example 1 p-toluenesulfonic acid Using homogeneous catalyst
1. Carbonylation reaction
Into a 100mL stainless steel autoclave, 3g of paraformaldehyde and sulfolane were added: after 50mL of acetic acid=5:1 mixed solvent and p-toluenesulfonic acid as a homogeneous catalyst are fully and uniformly stirred and mixed, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 7MPa, and the reaction is carried out for 3 hours at 110 ℃. After the reaction was completed, the reaction vessel was cooled to room temperature, and the product was as shown in FIG. 3, without delamination of the liquid.
2. Esterification reaction
Adding all liquid after carbonylation reaction into a reaction kettle, adding 20mL of methanol, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the product yield (table 1).
As can be seen from FIG. 3, the products are not layered after the carbonylation reaction, and the products such as methoxyacetic acid and the like and the solvent all enter the next esterification reaction together, and the processing amount of the operations such as esterification link, subsequent rectification and the like is about 3-4 times that of the embodiment 1. In addition, after purification steps such as rectification and methanol washing, part of methanol is mixed into the solvent (acetic acid, propionic acid and isobutyric acid), which makes recycling of the solvent difficult.
[ comparative example 2 ] molecular sieves employing heterogeneous catalysts H-MOR
1. Carbonylation reaction
Into a 100mL stainless steel autoclave, 3g of paraformaldehyde and cyclohexane were added: acetic acid=10:1 mixed solvent 50mL and H-MOR molecular sieve 2g, sealing the reaction kettle, replacing air in the kettle with CO 3 times, introducing high-pressure CO to 8MPa, and reacting at 120 ℃ for 3H. After the reaction was completed, the reaction vessel was cooled to room temperature. Filtering and recovering the catalyst after reaction.
2. Esterification reaction
The carbonylation reaction product (except for the solid catalyst) was put into a reaction kettle, 20mL of methanol and 1g of Amberlyst-36 resin were added, the reaction kettle was sealed, the reaction was carried out at 100℃under stirring for 2 hours, after the reaction was completed, the reaction kettle was cooled to room temperature, and the feed liquid in the kettle was taken out, and analyzed by gas chromatography and high performance liquid chromatography to obtain the product yield (Table 1).
[ comparative example 3 ] use of recovered H-MOR molecular sieves
1. Catalyst recovery
The product of the carbonylation reaction of comparative example 2 was filtered and the H-MOR catalyst after the reaction was recovered.
2. Carbonylation reaction
Into a 100mL stainless steel autoclave, 3g of paraformaldehyde and cyclohexane were added: acetic acid=10:1 mixed solvent 50mL and recovered H-MOR catalyst, sealing the reaction kettle, replacing air in the kettle with CO 3 times, introducing high-pressure CO to 8MPa, and reacting at 120 ℃ for 3H. After the reaction was completed, the reaction vessel was cooled to room temperature. Filtering and recovering the catalyst after reaction.
3. Esterification reaction
The carbonylation reaction product (except for the solid catalyst) was put into a reaction kettle, 20mL of methanol and 1g of Amberlyst-36 resin were added, the reaction kettle was sealed, the reaction was carried out at 100℃under stirring for 2 hours, after the reaction was completed, the reaction kettle was cooled to room temperature, and the feed liquid in the kettle was taken out, and analyzed by gas chromatography and high performance liquid chromatography to obtain the product yield (Table 1).
As is clear from table 1, the yield of the product of comparative example 3 is significantly reduced as compared with comparative example 2, indicating that the separation of the catalyst and the product can be achieved by using the solid acid catalyst, but the solid catalyst is rapidly deactivated due to the polymerization of formaldehyde on the catalyst surface, and thus the efficient recycling cannot be achieved.
TABLE 1 reaction conditions and product yields
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (9)

1. A method for preparing methyl methoxyacetate by carbonylation of formaldehyde, which is characterized by adopting a rhodium carbonyl catalyst and comprising the following steps:
(1) Uniformly mixing a rhodium carbonyl catalyst and a solvent to obtain a mixture;
(2) Fully contacting formaldehyde monomer source substances, CO, organic carboxylic acid and the mixture obtained in the step (1) to carry out carbonylation reaction; after the reaction is finished, separating the solvent and the catalyst to obtain a carbonylation product;
(3) Adding methanol into the carbonylation product to carry out esterification reaction to generate methoxy methyl acetate;
the solvent in the step (1) is methyl tertiary butyl ether and/or ethyl tertiary butyl ether;
the rhodium carbonyl catalyst is one or more of rhodium dicarbonyl acetylacetonate, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) carbonyl hydride, rhodium tetracarbonyl dichloride and rhodium acetylacetonate triphenylphosphine carbonyl.
2. The method according to claim 1, wherein the rhodium carbonyl catalyst is used in an amount of 0.05mol% to 0.5mol% of the amount of the formaldehyde monomer source substance charged on a molar basis.
3. The method according to claim 1, wherein the molar ratio of the amount of the organic carboxylic acid to the amount of the formaldehyde monomer source substance is 1:2 to 1:1, and the molar ratio of the organic carboxylic acid to the solvent is 1:1 to 1:10.
4. The process of claim 1, wherein the rhodium carbonyl catalyst and solvent in step (1) is fresh rhodium carbonyl catalyst and solvent or is from rhodium carbonyl catalyst and solvent recovered during the reaction.
5. The process of claim 1, wherein the solvent and catalyst separated in step (2) are recycled directly as the catalyst and solvent in step (1).
6. The method according to claim 1, wherein the formaldehyde monomer source material in step (2) is trioxymethylene and/or paraformaldehyde.
7. The method of claim 1, wherein the organic carboxylic acid is one or more of acetic acid, propionic acid, and isobutyric acid.
8. The process of claim 1, wherein the temperature of the carbonylation reaction in step (2) is 70-120 ℃; the pressure of the carbonylation reaction is 5-10MPa.
9. The process according to claim 1, wherein the esterification reaction in step (3) is carried out at a reaction temperature of 80 to 120 ℃ for a reaction time of 1 to 4h.
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