CN118638008B - Trifluoroethyl methacrylate and synthesis method thereof - Google Patents
Trifluoroethyl methacrylate and synthesis method thereof Download PDFInfo
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- CN118638008B CN118638008B CN202411111136.XA CN202411111136A CN118638008B CN 118638008 B CN118638008 B CN 118638008B CN 202411111136 A CN202411111136 A CN 202411111136A CN 118638008 B CN118638008 B CN 118638008B
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- trifluoroethyl methacrylate
- chlorotrifluoroethane
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- 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
- C07C67/287—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 halogen; by substitution of halogen atoms by other halogen atoms
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- 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
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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Abstract
The invention belongs to the technical field of fluorine chemical industry, and particularly relates to trifluoroethyl methacrylate and a synthesis method thereof. The synthesis method of the trifluoroethyl methacrylate comprises the following steps of firstly mixing a solvent, methyl methacrylate, a catalyst and a polymerization inhibitor, heating to 25-70 ℃, then introducing byproduct chlorotrifluoroethane, reacting for 4-6h after the addition, and finally carrying out aftertreatment on the reaction liquid to obtain the trifluoroethyl methacrylate. The optimal reaction temperature is in the range of 25-50 ℃. The synthesis method of the trifluoroethyl methacrylate provided by the invention utilizes the waste gas chlorotrifluoroethane, has high conversion rate, is environment-friendly, and can realize industrialized synthesis. The trifluoro ethyl methacrylate synthesized by the invention has high yield and high content.
Description
Technical Field
The invention belongs to the technical field of fluorine chemical industry, and particularly relates to trifluoroethyl methacrylate and a synthesis method thereof.
Background
Trifluoroethyl methacrylate is an important organic synthesis intermediate and has wide application in the fields of fluorine-containing paint, optical fibers, contact lenses and the like. At present, the preparation method of trifluoroethyl methacrylate has some defects such as harsh reaction conditions, high cost, low yield and the like.
2-Chloro-1, 1-trifluoroethane, also known as chlorotrifluoroethane, freon 133a, is an organic compound of the formula. Chlorotrifluoroethane is also generally discharged as a by-product. At present, the general treatment mode of the waste gas of the 2-chloro-1, 1-trifluoroethane is direct discharge, but the direct discharge causes serious damage to an ozone layer and has great influence on the environment.
Chinese patent CN108774134A discloses a production method of trifluoroethyl methacrylate, which comprises the steps of reacting trifluoroethanol, methacryloyl chloride and a polymerization inhibitor for 12 hours at 40-50 ℃, and collecting the trifluoroethyl methacrylate from a reaction product, wherein although production raw materials such as methacrylic acid, trifluoroethanol and the like are easily obtained in the chemical industry field, the production raw materials are solid phosgene, have higher toxicity and danger, have higher safety risks, and have problems in the aspects of yield, polymerization inhibitor selection, waste treatment and the like.
U.S. patent No. 2005085661A1 discloses that trifluoroethyl methacrylate is prepared from methacrylic acid and trifluoroethanol by using a pervaporation composite membrane, although the conversion rate of trifluoroethyl methacrylate is improved, for industrial production, the preparation and maintenance cost of the pervaporation composite membrane in the method are high, and the selectivity and stability of the membrane may have certain challenges, which are not beneficial to realizing industrial preparation of trifluoroethyl methacrylate.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for synthesizing trifluoroethyl methacrylate, which utilizes waste gas chlorotrifluoroethane, has high conversion rate, is environment-friendly and can realize industrialized synthesis.
The trifluoro ethyl methacrylate synthesized by the invention has high yield and high content.
The synthesis method of the trifluoroethyl methacrylate comprises the following steps of firstly mixing a solvent, methyl methacrylate, a catalyst and a polymerization inhibitor, heating to 25-70 ℃, then introducing byproduct chlorotrifluoroethane, reacting for 4-6h after the addition, and finally carrying out aftertreatment on the reaction liquid to obtain the trifluoroethyl methacrylate. The optimal reaction temperature is in the range of 25-50 ℃.
The solvent is one of water, methanol, ethyl acetate, diethyl ether, tetrahydrofuran and dichloromethane. The amount of the solvent is not limited any more, and the purpose of the solvent is to make the reaction proceed in solution, so long as the reaction is completely performed, and the less the solvent, the better the material is.
The catalyst is one of triethylamine, trimethylamine and N, N-diethyl aniline.
The polymerization inhibitor is 2, 6-di-tert-butyl-p-cresol or p-methoxyphenol.
The post-treatment of the reaction solution is to remove the solvent by distillation.
The molar quantity of the polymerization inhibitor is 2-3% of the molar quantity of methyl methacrylate.
The molar quantity of the catalyst is 2-3% of the molar quantity of methyl methacrylate.
The content of the byproduct chlorotrifluoroethane is more than or equal to 99.5wt%.
The rate of the byproduct chlorotrifluoroethane is 5.59cm 3/h, and the byproduct chlorotrifluoroethane is introduced for 4-6h.
Trifluoroethyl methacrylate is synthesized by the synthesis method of the trifluoroethyl methacrylate.
Specifically, the method for synthesizing trifluoroethyl methacrylate comprises the steps of adding 225g of solvent (one of water, methanol, ethyl acetate, diethyl ether, tetrahydrofuran and methylene dichloride), 25g (0.25 mol) of methyl methacrylate, 2-3 mol of polymerization inhibitor (2, 6-di-tert-butyl-p-cresol or p-methoxyphenol) and 2-3 mol of catalyst (one of triethylamine, trimethylamine and N, N-diethylaniline) into a four-necked flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 25-100 ℃, introducing byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 4-6h, and removing the solvent after the reaction is finished to obtain trifluoroethyl methacrylate.
According to the synthesis method of trifluoroethyl methacrylate, the adopted solvent is a polar solvent, so that the charge property is improved, a four-ring transition state is easier to generate, the yield is improved, and the optimal solvent is water. The invention uses triethylamine, trimethylamine and N, N-diethylaniline as catalysts, thereby effectively improving the utilization rate of the chlorotrifluoroethane. The reaction mechanism of the present invention is shown in FIG. 1.
The catalyst is used for polymerization of triethylamine and chlorotrifluoroethane, and the catalyst is used for reversible reaction at the temperature of 25-70 ℃, has good constraint effect on chlorotrifluoroethane gas, and effectively improves the utilization rate of chlorotrifluoroethane and the final yield. The mechanism is shown in figure 2.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the synthesis method of the trifluoroethyl methacrylate, the yield of the trifluoroethyl methacrylate is increased to 98%, and compared with the yield of 80% synthesized by the traditional method, the utilization rate of resources is greatly improved.
(2) Compared with the traditional synthesis method, the synthesis method of the trifluoroethyl methacrylate has the advantages that the steps are simplified, the reaction time is shortened by about 50% compared with 12 hours of the traditional method, and the production efficiency is obviously improved.
(3) Compared with the traditional synthesis method, the synthesis method of the trifluoroethyl methacrylate has the advantages that the generated waste is greatly reduced, and the pressure on the environment is obviously reduced.
(4) The trifluoroethyl methacrylate prepared by the synthesis method has the purity reaching more than 99 percent, and the reliability of the product is greatly improved.
Drawings
FIG. 1 is a reaction mechanism diagram of the present invention.
FIG. 2 is a diagram showing the reaction mechanism of the polymerization of chlorotrifluoroethane with triethylamine as catalyst.
FIG. 3 is a gas chromatogram of trifluoroethyl methacrylate synthesized in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The raw materials and reagents used in the following examples and comparative examples were commercially available products. The byproduct chlorotrifluoroethane gas adopted below is a byproduct of other production lines of enterprises, and the content of the byproduct chlorotrifluoroethane gas is more than or equal to 99.5wt%.
Example 1
The method for synthesizing the trifluoroethyl methacrylate comprises the steps of adding 225g of water, 25g of methyl methacrylate, 1.1g (0.005 mol) of 2, 6-di-tert-butyl-p-cresol and 0.51g of triethylamine into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 25 ℃, introducing a byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 4h, standing, separating liquid, filtering an organic phase to obtain 41.33g of trifluoroethyl methacrylate, detecting the content of the trifluoroethyl methacrylate by GC to be 99.854%, and calculating the yield of the trifluoroethyl methacrylate to be 98.33% as shown in a table 1.
Table 1 peak table
Example 2
The method for synthesizing the trifluoroethyl methacrylate comprises the following steps of adding 225g of methanol, 25g of methyl methacrylate, 0.62g (0.005 mol) of p-methoxyphenol and 0.3g of trimethylamine into a four-necked flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 50 ℃, introducing byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 6h, and distilling off the methanol at 75 ℃ after the reaction is finished to obtain 40.52g of trifluoroethyl methacrylate, wherein the content of the trifluoroethyl methacrylate is 99.72% by GC detection, and the yield is 96.41% by calculation.
Example 3
The method for synthesizing the trifluoroethyl methacrylate comprises the steps of adding 225g of ethyl acetate, 25g of methyl methacrylate, 0.93g (0.0075 mol) of methoxyphenol and 1.12g of N, N-diethylaniline into a four-necked flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 70 ℃, introducing a byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 6h, distilling at 80 ℃ to remove the ethyl acetate, and obtaining 39.52g of trifluoroethyl methacrylate, wherein the content of the trifluoroethyl methacrylate is detected to be 99.81% by GC, and the yield is calculated to be 94.03%.
Example 4
The method for synthesizing the trifluoroethyl methacrylate comprises the steps of adding 225g of diethyl ether, 25g of methyl methacrylate, 1.65g (0.0075 mol) of 2, 6-di-tert-butyl-p-cresol and 0.76 g g of triethylamine into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 25 ℃, introducing byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 5h, distilling and removing diethyl ether at 50 ℃ to obtain 38.77g of trifluoroethyl methacrylate, detecting the content of the trifluoroethyl methacrylate to be 99.66% by GC, and calculating the yield of the trifluoroethyl methacrylate to be 92.24%.
Example 5
The method for synthesizing the trifluoroethyl methacrylate comprises the following steps of adding 225g of tetrahydrofuran, 25g of methyl methacrylate, 1.65g (0.0075 mol) of 2, 6-di-tert-butyl-p-cresol and 0.44g of trimethylamine into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 25 ℃, introducing byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 5h, distilling at 80 ℃ to remove the tetrahydrofuran, and obtaining 39.18g of trifluoroethyl methacrylate, wherein the content of the trifluoroethyl methacrylate is 99.59% by GC detection, and the yield is 93.21% by calculation.
Example 6
The method for synthesizing the trifluoroethyl methacrylate comprises the steps of adding 225g of methylene dichloride, 25g of methyl methacrylate, 1.1g (0.005 mol) of 2, 6-di-tert-butyl-p-cresol and 0.3g of trimethylamine into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 25 ℃, introducing byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 4h, distilling and removing the methylene dichloride at 50 ℃ to obtain 38.99g of trifluoroethyl methacrylate, detecting the content of the trifluoroethyl methacrylate to be 99.58% by GC, and calculating the yield of the trifluoroethyl methacrylate to be 92.77%.
Example 7
The method for synthesizing the trifluoroethyl methacrylate comprises the following steps of adding 225g of water, 25g of methyl methacrylate, 0.62g (0.005 mol) of p-methoxyphenol, 1.12g of N, N-diethylaniline into a four-necked flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to 50 ℃, introducing a byproduct chlorotrifluoroethane gas at a rate of 5.59cm 3/h, reacting for 6h, standing, separating liquid, filtering an organic phase to obtain 40.82g of trifluoroethyl methacrylate, detecting the content of the trifluoroethyl methacrylate by GC to be 99.61%, and calculating the yield of the trifluoroethyl methacrylate to be 97.12%.
Comparative example 1
Otherwise, the catalyst was removed under the same conditions as in example 1, and after the completion of the reaction, the mixture was allowed to stand for separation, and the organic phase was collected by filtration to give 34.93g of trifluoroethyl methacrylate, the content of which was 99.43% by GC, and the yield was 83.11%.
Comparative example 2
Otherwise, the solvent was removed under the same conditions as in example 1, and after the completion of the reaction, the organic phase was collected to give 36.11g of trifluoroethyl methacrylate, the content of which was 99.52% by GC, and the yield thereof was calculated to be 85.91%.
Comparative example 3
Otherwise, the polymerization inhibitor was removed under the same conditions as in example 1, and after the completion of the reaction, the mixture was allowed to stand for separation, and the organic phase was collected by filtration to give 34.79g of trifluoroethyl methacrylate, the content of which was 99.56% by GC detection, and the yield thereof was calculated to be 82.78%.
Claims (5)
1. The method for synthesizing the trifluoroethyl methacrylate is characterized by comprising the following steps of firstly mixing a solvent, methyl methacrylate, a catalyst and a polymerization inhibitor, heating to 25-70 ℃, then introducing byproduct chlorotrifluoroethane, reacting for 4-6 hours after the addition, and finally carrying out aftertreatment on a reaction solution to obtain the trifluoroethyl methacrylate;
the solvent is one of water, methanol, ethyl acetate, diethyl ether, tetrahydrofuran and dichloromethane;
the catalyst is one of triethylamine, trimethylamine and N, N-diethylaniline;
The polymerization inhibitor is 2, 6-di-tert-butyl-p-cresol or p-methoxyphenol;
The molar quantity of the catalyst is 2-3% of the molar quantity of methyl methacrylate.
2. The method for synthesizing trifluoroethyl methacrylate according to claim 1, wherein the post-treatment of the reaction solution is a solvent removal by distillation.
3. The method for synthesizing trifluoroethyl methacrylate according to claim 1, wherein the molar amount of the polymerization inhibitor is 2 to 3 mol% based on the molar amount of methyl methacrylate.
4. The method for synthesizing trifluoroethyl methacrylate according to claim 1, wherein the content of the byproduct chlorotrifluoroethane is more than or equal to 99.5wt%.
5. The method for synthesizing trifluoroethyl methacrylate according to claim 1, wherein the rate of introducing the byproduct chlorotrifluoroethane is 5.59cm 3/h, and the reaction time is 4-6h.
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