CN111004087A - Post-treatment method of trifluorostyrene synthetic liquid - Google Patents
Post-treatment method of trifluorostyrene synthetic liquid Download PDFInfo
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Abstract
The invention discloses a post-treatment method of trifluorostyrene synthetic liquid, which comprises the steps of distilling the synthetic liquid and rectifying fractions to prepare trifluorostyrene.
Description
Technical Field
The present invention relates to a post-treatment method of trifluorostyrene, which is used for treating trifluorostyrene synthetic fluid after trifluorostyrene synthesis (a synthesis method of trifluorostyrene compound disclosed in patent document with an authorization publication number of CN 103708988B).
Background
Patent document No. CN103708988B discloses a method for synthesizing trifluorostyrene compounds, which comprises the following steps:
(i) subjecting a halobenzene to a grignard reaction with magnesium in an organic solvent to form a grignard reagent having the formula:
wherein X is a chlorine atom; r is selected from hydrogen, fluorine, C1-8 alkyl, C1-8 alkoxy; said C1-8 alkyl, C1-8 alkoxy may each be optionally substituted with a group selected from halogen, phenyl, benzyl, C1-4 alkyl; n is an integer of 0 to 5;
(ii) and (2) carrying out a trifluorostyrene synthesis reaction on the Grignard reagent and tetrafluoroethylene in an organic solvent to prepare trifluorostyrene or substituted trifluorostyrene, wherein the molar ratio of the tetrafluoroethylene to the Grignard reagent is not less than 1.2-5: 1.
the method greatly improves the yield of the trifluorostyrene by selecting a synthesis route and optimizing the process, and has the characteristics of short synthesis route, easily obtained and cheap raw materials, mild process conditions, good selectivity and high yield. However, the synthetic solution of trifluorostyrene contains many organic solvents, such as tetrahydrofuran, and the concentration of trifluorostyrene can be increased to more than 90% by post-treatment.
Disclosure of Invention
The invention aims to solve the technical problem of providing a post-treatment method of trifluorostyrene synthetic liquid, which is simple and convenient and has high yield.
In order to solve the above technical problems, the post-treatment method of the trifluorostyrene synthetic solution of the present invention comprises distilling the synthetic solution and rectifying the distillate to obtain trifluorostyrene, wherein the trifluorostyrene synthetic solution is obtained by the synthesis method of trifluorostyrene compound disclosed in the patent document with the publication number of CN 103708988B.
The distillate of the distillation is more than 85 percent of organic solvent, more than 90 percent of benzene and 92 to 95 percent of trifluorostyrene.
The distillation distilled off 80% liquid with 20% solids remaining.
The distillation temperature is less than 60 ℃, and overhigh temperature can cause the trifluorostyrene to self polymerize.
Collecting the fraction at 45 deg.C under vacuum degree of-0.068 MPa, and collecting the fraction at vacuum degree of-0.099 MPa and temperature of above 46 deg.C.
Specifically, the distillation adopts a rotary evaporator to distill out all liquid, and then the trifluorostyrene is obtained by rectification. Or distilling all the liquid by adopting a fractionating tower and rectifying to obtain the trifluorostyrene. The liquid distilled off comprises most of the organic solvent (such as tetrahydrofuran) and a small amount of benzene and the product trifluorostyrene. The remainder is magnesium chlorofluoride, byproduct 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane, a small amount of trifluorostyrene, and tetrahydrofuran complexed with the above-mentioned material at about 10%.
The yield from the beginning of the treatment of the trifluorostyrene synthetic fluid to the obtaining of the trifluorostyrene product is more than 84 percent. The post-treatment method of the trifluorostyrene synthetic liquid has higher yield than the post-treatment method (about 50-55 percent) reported in the prior literature.
The specific synthesis and post-treatment method comprises the following steps:
1. preparation of Grignard reagents
The process of the present invention comprises the step of subjecting chlorobenzene to a grignard reaction with magnesium in an organic solvent to form a grignard reagent having the following formula.
The synthesis of the grignard reagent of the invention is based on the following reaction:
wherein X is a chlorine atom.
The reaction reagent is not particularly limited as long as the purity thereof does not affect the stability and purity of the finally produced grignard reagent. For example, chlorobenzene is used as a commercially or experimentally pure reagent, whereas magnesium is generally a relatively thin roll of magnesium, which in a preferred embodiment of the invention has an impurity content of less than 2% by weight, preferably less than 0.5% by weight; the magnesium has an impurity content of less than 3% by weight, preferably less than 1% by weight.
The reaction is usually carried out in an organic solvent, and the organic solvent to be used is not particularly limited as long as it does not affect the above-mentioned chemical reaction as a carrier. In one embodiment of the invention, a mixture of two or more selected from tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether or mixtures thereof in any ratio is used. In a preferred embodiment of the present invention, tetrahydrofuran is used as the organic solvent.
The reaction also typically uses a catalyst, and suitable catalysts may be any conventional catalyst known in the art. In a preferred embodiment of the invention, the catalyst is a preformed qualified grignard reagent or iodine.
In the reaction, the reaction temperature is usually 45 to 80 ℃ and preferably 60 to 70 ℃. In a preferred embodiment of the present invention, the reaction is carried out under an inert atmosphere, for example, a reaction atmosphere formed by using neon, argon, nitrogen or a mixture of two or more thereof, preferably a reaction atmosphere using nitrogen, in order to prevent the introduction of moisture and oxygen.
If necessary, the magnesium metal and the organic solvent (for example, tetrahydrofuran solvent) may be dehydrated, because the effective content of the grignard reagent is high when the water content of the system is low or no water is obtained, and the grignard reagent reacts with water or oxygen first in the presence of water and oxygen, so that the effective content of the grignard reagent is reduced.
The reactions used to prepare grignard reagents of the present invention typically undergo the following side reactions:
in order to increase the yield of the normal phenylmagnesium chloride product during the reaction, it is necessary to reduce the generation probability of the by-product biphenyl, which is a product of the reaction of phenylmagnesium chloride with chlorobenzene, as described above. Various methods can be employed to reduce the chance of biphenyl by-product generation. In one embodiment of the present invention, chlorobenzene is added dropwise to reduce the local concentration of chlorobenzene in the reaction solution to achieve the above-mentioned object. In another embodiment of the present invention, chlorobenzene is first diluted with an organic solvent (e.g., tetrahydrofuran), and then the diluted chlorobenzene is added dropwise to a magnesium-containing organic solvent to reduce the local concentration of chlorobenzene in the reaction solution, and the concentration of the solution formed by diluting chlorobenzene with the organic solvent is not particularly limited, and a person of ordinary skill in the art can easily determine an appropriate chlorobenzene concentration in view of reducing the local concentration of chlorobenzene. In one embodiment of the present invention, a solution of 10 to 95 wt% of chlorobenzene in an organic solvent selected from tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether or a mixture of two or more thereof at any ratio is used, preferably a solution of 20 to 90 wt% of chlorobenzene in an organic solvent selected from tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether or a mixture of two or more thereof at any ratio is used, and more preferably a solution of 30 to 70 wt% of chlorobenzene in an organic solvent selected from tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether or a mixture of two or more thereof at any ratio is used.
In a preferred embodiment of the present invention, the grignard reagent is prepared by the following method: a reaction vessel which is dry and equipped with a reflux unit is charged with magnesium (e.g., magnesium coil or magnesium ribbon), is heated to about 90 to 120 ℃ under a condition of replacing with an inert gas (preferably anhydrous inert gas such as nitrogen) and continuing to introduce an inert gas (e.g., anhydrous nitrogen), is kept at about 95 to 115 ℃ and more preferably 100 ℃ and 110 ℃ for 1.5 to 4.5 hours (preferably 2 to 4 hours and more preferably 2.5 to 3.5 hours), and is then cooled to room temperature under a condition of keeping the inert gas (e.g., anhydrous nitrogen) introduced. To the reaction vessel are added an organic solvent (e.g., tetrahydrofuran, preferably an anhydrous organic solvent such as anhydrous tetrahydrofuran) as a reaction medium, chlorobenzene, and a preformed acceptable grignard reagent as a catalyst. The liquid in the reaction vessel is heated while stirring until reflux occurs (45-80 ℃, preferably 60-70 ℃). Keeping the reflux state for continuously reacting for 7-10 hours (preferably 7.5-9.5 hours, more preferably 8-9 hours), confirming initiation by analysis and test, dropwise adding chlorobenzene mixed liquor while stirring, completely refluxing for 6-8 hours, confirming no chlorobenzene by analysis, and stopping reaction to obtain the Grignard reagent.
In a preferred embodiment of the present invention, the grignard reagent is prepared by the following method: adding an organic solvent and a prefabricated qualified Grignard reagent serving as a catalyst into a reaction container provided with a reflux device, then adding magnesium (dried), replacing by inert gas, adding part of chlorobenzene serving as a reaction medium into the reaction container, stirring and refluxing (45-80 ℃, preferably 60-70 ℃), dropwise adding a chlorobenzene mixed solution while stirring after initiation, completely refluxing for 6-8 hours after dropwise addition, analyzing and confirming that no chlorobenzene exists, and stopping reaction to obtain the Grignard reagent. In another preferred embodiment of the invention, the chlorobenzene is a solution in 10 to 20% by weight of an organic solvent, such as tetrahydrofuran.
2. Preparation of trifluorostyrene
The method for preparing trifluorostyrene is based on the following reaction:
wherein X is a chlorine atom.
The synthesis reaction temperature of the trifluorostyrene is usually more than-30 ℃, preferably 0-50 ℃, and more preferably 15-45 ℃; the reaction pressure is generally greater than 1MPa, generally from 1.5 to 3 MPa.
In the above reaction of the present invention, the higher the molar ratio of tetrafluoroethylene to grignard reagent phenylmagnesium halide, the higher the selectivity of trifluorostyrene as a synthetic reaction product, and the larger the proportion of trifluorostyrene produced. However, in consideration of process conditions, cost performance and the like, the molar ratio of the grignard reagent to the tetrafluoroethylene in the method of the present invention is generally 1: 1.9 to 5.0, preferably 1: 2.0 to 4.0, preferably 1: 2.1-3.0, preferably 1: 2.2-2.5.
In order to reduce the impurity content of the product, in a preferred embodiment of the invention, the tetrafluoroethylene is used in a polymer grade purity.
The above reaction is usually carried out in an organic medium which may be the same as or different from that of the preceding Grignard reaction, and it is preferable to use the same organic medium. Suitable organic media are, for example, tetrahydrofuran, diethyl ether, dioxane, glycol dimethyl ether or mixtures of two or more thereof in any desired ratio. In a preferred embodiment of the present invention, tetrahydrofuran is used as the organic solvent.
The most important side reactions in the synthesis of trifluorostyrene are as follows:
a) production of 1, 2-stilbene:
b) production of 1, 2-diphenylhexafluorocyclobutane:
however, as demonstrated in the examples of the present invention, by controlling the ratio of tetrafluoroethylene to grignard reagent, the contents of the main by-products, 1, 2-diphenyldifluoroethylene and 1, 2-diphenylhexachlorocyclobutane, can be controlled to be lower than 10% by weight and in the vicinity of 0% by weight, respectively, for example, by using a grignard reagent containing chlorine.
3. Post-treatment of trifluorostyrene synthetic liquid
The post-treatment process of trifluorostyrene synthetic liquid includes the separation and rectification of synthetic liquid. The organic Jiang xi Kui and the like adopt trifluorostyrene synthetic liquid, and after washing, drying and desolventizing, the raw product is distilled to obtain a crude product with the boiling range of 60-68 ℃ per 70mm, and the crude product is rectified to obtain the trifluorostyrene, and the trifluorostyrene product is obtained by processing the trifluorostyrene synthetic liquid, wherein the yield is about 53 percent.
The second method for post-treatment of synthetic trifluorostyrene liquid is to evaporate most of organic solvent, such as tetrahydrofuran, to extract product trifluorostyrene with solvent compatible with the product, to pump filter, to extract filter residue with small amount of 60-90 deg.c petroleum ether for three times, and to obtain filter residue with trifluorostyrene content less than 3%. The yield of the trifluorostyrene product obtained by starting the treatment of the trifluorostyrene synthetic solution reaches more than 68 percent.
The third method for post-treating the trifluorostyrene synthetic solution is to evaporate about 88% of organic solvent such as tetrahydrofuran, about 90% of benzene and about 92% of trifluorostyrene by using a rotary evaporator; then rectifying to obtain the trifluorostyrene. The yield is more than 85 percent from the beginning of the treatment of the trifluorostyrene synthetic fluid to the obtaining of the trifluorostyrene product. (because the solvent petroleum ether extraction and suction filtration are not used, although the content of the product in the filter residue is relatively high, the yield is greatly improved on the contrary because the steps are simplified, the cost is reduced and the industrial production is facilitated)
The TFS obtained by adopting the second trifluorostyrene synthetic fluid post-treatment method (the yield is more than 68%) has higher yield than the post-treatment method (50-55%) reported in the prior literature. However, the third method (the method of the present invention) is relatively more efficient and simpler.
The method has the advantages of short post-treatment route, high yield and easy industrialization, and more importantly, the solvent THF is easy to recover, so that the manufacturing cost of the trifluorostyrene is favorably reduced, and the industrial production is convenient to realize.
Detailed Description
Test method
1. Testing the content of benzene ring-containing organic matters by using liquid chromatography (HPLC); the instrument model is as follows: waters 1525.
2. Testing the contents of all components of the reaction solution and the product by Gas Chromatography (GC); the instrument model is as follows: and a GC 920.
3. Monitoring the water content of the raw material by a micro water content analyzer (Karl Fischer moisture analyzer) in the organic matter; the instrument model is as follows: mettler Toledo C30.
Synthesis example 1
1. Synthesis of Grignard reagents
At 6.3m dry and equipped with a reflux device3110 kg of magnesium coil is added into a reaction kettle (200 kg of qualified Grignard reagent is reserved for initiation). After nitrogen substitution, under the condition of continuously introducing nitrogen, 1051 kg of tetrahydrofuran and 60.2 kg of chlorobenzene were added into the reaction kettle. The reaction kettle was heated while stirring to raise the temperature of the liquid in the reaction kettle to reflux (about 65 ℃). Steady state of waiting for reflux 3After 5 hours, the mixed solution of tetrahydrofuran (1499.1 kg) and chlorobenzene (449.7 kg) is dripped in 9 to 12 hours, the reflux state is kept after the dripping is finished, the reaction is continued for 6 to 8 hours, and then the heating and the stirring are stopped, and the nitrogen gas is kept introduced. The liquid in the reaction kettle is the synthesized Grignard reagent.
2. Synthesis of trifluorostyrene
4.5m3After the inside of the pressure resistant reaction vessel was replaced with nitrogen three times, 3137.7 kg (1.4mol/kg) of the Grignard reagent synthesized above was added thereto, and the mixture was cooled while stirring, and 1046.1 kg of tetrafluoroethylene was introduced while keeping stirring at-20 ℃. After the addition of the tetrafluoroethylene is finished, the reaction is slowly heated until the temperature in the container is not more than 45 ℃, and the reaction is kept for 6 hours. And (3) stopping heating and stirring after the reaction is finished, recovering the residual tetrafluoroethylene (532 kg), and discharging to obtain the trifluorostyrene synthetic liquid.
Measured by nuclear magnetic resonance, which19F NMRδ(ppm)22.70，37.28，100.31。
The composition of the product was measured by liquid chromatography, and the yield of trifluorostyrene was calculated according to the following formula based on the areas of 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene, and the results are shown in Table 1.
Trifluorostyrene yield (trifluorostyrene area)/(1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene area sum)
Synthesis example 2
1. Synthesis of Grignard reagents
At 6.3m dry and equipped with a reflux device3110 kg of magnesium coil is added into a reaction kettle (200 kg of qualified Grignard reagent is reserved for initiation). After nitrogen substitution, 1051 kg of tetrahydrofuran and 60.8 kg of chlorobenzene were added to the reactor under continued introduction of nitrogen. The reaction kettle was heated while stirring to raise the temperature of the liquid in the reaction kettle to reflux (about 65 ℃). After the reflux state is stable for 3-5 hours, dropwise adding a mixed solution of tetrahydrofuran (1499.1 kg) and chlorobenzene (449.7 kg) within 9-12 hours, keeping the reflux state after dropwise adding, continuously reacting for 6-8 hours, and then stopping heating and stirring, and keeping the nitrogen gas introducing state. Inverse directionThe liquid in the reaction kettle is the synthesized Grignard reagent.
2. Synthesis of trifluorostyrene
4.5m3After the inside of the pressure resistant reaction vessel was replaced with nitrogen three times, 3136 kg (1.4mol/kg) of the Grignard reagent synthesized above was added thereto, and the mixture was cooled while stirring, and 1053.5 kg of tetrafluoroethylene was introduced while keeping the stirring at-20 ℃. After the addition of the tetrafluoroethylene is finished, the reaction is slowly heated until the temperature in the container is not more than 45 ℃, and the reaction is kept for 6 hours. And (3) stopping heating and stirring after the reaction is finished, recovering the residual tetrafluoroethylene (570 kg), and discharging to obtain the trifluorostyrene synthetic liquid.
Measured by nuclear magnetic resonance, which19F NMRδ(ppm)22.70，37.28，100.31。
The composition of the product was measured by liquid chromatography, and the yield of trifluorostyrene was calculated according to the following formula based on the areas of 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene, and the results are shown in Table 1.
Trifluorostyrene yield (trifluorostyrene area)/(1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene area sum)
Synthesis example 3
1. Synthesis of Grignard reagents
At 6.3m dry and equipped with a reflux device3110 kg of magnesium coil is added into a reaction kettle (200 kg of qualified Grignard reagent is reserved for initiation). After nitrogen substitution, 1053.2 kg of tetrahydrofuran and 60.2 kg of chlorobenzene were added to the reactor under continued introduction of nitrogen. The reaction kettle was heated while stirring to raise the temperature of the liquid in the reaction kettle to reflux (about 65 ℃). After the reflux state is stable for 3-5 hours, dropwise adding a mixed solution of tetrahydrofuran (1499.1 kg) and chlorobenzene (449.7 kg) within 9-12 hours, keeping the reflux state after dropwise adding, continuously reacting for 6-8 hours, and then stopping heating and stirring, and keeping the nitrogen gas introducing state. The liquid in the reaction kettle is the synthesized Grignard reagent.
2. Synthesis of trifluorostyrene
4.5m3The pressure-resistant reaction kettle is internally replaced by nitrogen for three times, and then the nitrogen is added3148.1 kg (1.4mol/kg) of the Grignard reagent prepared in the above reaction mixture was cooled while stirring, and 1097.4 kg of tetrafluoroethylene was introduced while keeping stirring at-20 ℃. After the addition of the tetrafluoroethylene is finished, the reaction is slowly heated until the temperature in the container is not more than 45 ℃, and the reaction is kept for 6 hours. And (3) stopping heating and stirring after the reaction is finished, recovering and discharging residual tetrafluoroethylene (589 kg), and thus obtaining the trifluorostyrene synthetic solution.
Measured by nuclear magnetic resonance, which19F NMRδ(ppm)22.70，37.28，100.31。
The composition of the product was measured by liquid chromatography, and the yield of trifluorostyrene was calculated according to the following formula based on the areas of 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene, and the results are shown in Table 1.
Trifluorostyrene yield (trifluorostyrene area)/(1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene area sum)
Synthesis example 4
1. Synthesis of Grignard reagents
At 6.3m dry and equipped with a reflux device3110 kg of magnesium coil is added into a reaction kettle (200 kg of qualified Grignard reagent is reserved for initiation). After nitrogen replacement, 1050 kg of tetrahydrofuran and 60.0 kg of chlorobenzene were added to the reactor under the condition of continuing to introduce nitrogen. The reaction kettle was heated while stirring to raise the temperature of the liquid in the reaction kettle to reflux (about 65 ℃). After the reflux state is stable for 3-5 hours, dropwise adding a mixed solution of tetrahydrofuran (1508 kg) and chlorobenzene (447 kg) within 9-12 hours, keeping the reflux state after dropwise adding, continuing to react for 6-8 hours, and then stopping heating and stirring and keeping the nitrogen gas state. The liquid in the reaction kettle is the synthesized Grignard reagent.
2. Synthesis of trifluorostyrene
4.5m3After the inside of the pressure resistant reaction vessel was replaced with nitrogen three times, 3165.5 kg (1.4mol/kg) of the Grignard reagent synthesized above was added thereto, and the mixture was cooled while stirring, and 1053.5 kg of tetrafluoroethylene was introduced while keeping stirring at-20 ℃. After the tetrafluoroethylene is added, the container is slowly heated to ensure that the temperature in the container is not overThe reaction was maintained at 45 ℃ for 6 hours. And (3) stopping heating and stirring after the reaction is finished, recovering residual tetrafluoroethylene (623 kg), and discharging to obtain the trifluorostyrene synthetic liquid.
Measured by nuclear magnetic resonance, which19F NMRδ(ppm)22.70，37.28，100.31。
The composition of the product was measured by liquid chromatography, and the yield of trifluorostyrene was calculated according to the following formula based on the areas of 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene, and the results are shown in Table 1.
Trifluorostyrene yield (trifluorostyrene area)/(1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene area sum)
Synthesis example 5
1. Synthesis of Grignard reagents
At 6.3m dry and equipped with a reflux device3110 kg of magnesium coil is added into a reaction kettle (200 kg of qualified Grignard reagent is reserved for initiation). After nitrogen substitution, 1051 kg of tetrahydrofuran and 59.6 kg of chlorobenzene were added to the reactor under continued introduction of nitrogen. The reaction kettle was heated while stirring to raise the temperature of the liquid in the reaction kettle to reflux (about 65 ℃). After the reflux state is stable for 3-5 hours, dropwise adding a mixed solution of tetrahydrofuran (1500 kg) and chlorobenzene (448.8 kg) within 9-12 hours, keeping the reflux state after dropwise adding, continuously reacting for 6-8 hours, then stopping heating and stirring, and keeping the nitrogen gas state. The liquid in the reaction kettle is the synthesized Grignard reagent.
2. Synthesis of trifluorostyrene
4.5m3The inside of the pressure resistant reaction vessel was replaced with nitrogen three times, and 3137.8 kg (1.4mol/kg) of the Grignard reagent synthesized above was added thereto, followed by cooling with stirring to-20 ℃ and 1100.0 kg of tetrafluoroethylene was introduced while maintaining the stirring. After the addition of the tetrafluoroethylene is finished, the reaction is slowly heated until the temperature in the container is not more than 45 ℃, and the reaction is kept for 6 hours. And (3) stopping heating and stirring after the reaction is finished, recovering the residual tetrafluoroethylene (633 kg), and discharging to obtain the trifluorostyrene synthetic solution.
The measurement is carried out by a nuclear magnetic resonance method,it is composed of19F NMRδ(ppm)22.70，37.28，100.31。
The composition of the product was measured by liquid chromatography, and the yield of trifluorostyrene was calculated according to the following formula based on the areas of 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene, and the results are shown in Table 1.
Trifluorostyrene yield (trifluorostyrene area)/(1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene area sum)
Synthesis example 6
1. Synthesis of Grignard reagents
At 6.3m dry and equipped with a reflux device3110 kg of magnesium coil is added into a reaction kettle (200 kg of qualified Grignard reagent is reserved for initiation). After nitrogen substitution, 1053.3 kg of tetrahydrofuran and 60.2 kg of chlorobenzene were added to the reactor under continued introduction of nitrogen. The reaction kettle was heated while stirring to raise the temperature of the liquid in the reaction kettle to reflux (about 65 ℃). After the reflux state is stable for 3-5 hours, dropwise adding a mixed solution of tetrahydrofuran (1499.1 kg) and chlorobenzene (448.8 kg) within 9-12 hours, keeping the reflux state after dropwise adding, continuously reacting for 6-8 hours, and then stopping heating and stirring, and keeping the nitrogen gas introducing state. The liquid in the reaction kettle is the synthesized Grignard reagent.
2. Synthesis of trifluorostyrene
4.5m3After the inside of the pressure resistant reaction vessel was replaced with nitrogen three times, 3128.4 kg (1.4mol/kg) of the Grignard reagent synthesized above was added thereto, and the mixture was cooled while stirring, and 1022.1 kg of tetrafluoroethylene was introduced while keeping stirring at-20 ℃. After the addition of the tetrafluoroethylene is finished, the reaction is slowly heated until the temperature in the container is not more than 45 ℃, and the reaction is kept for 6 hours. And (3) stopping heating and stirring after the reaction is finished, recovering and discharging residual tetrafluoroethylene (583 kg), and thus obtaining the trifluorostyrene synthetic solution.
Measured by nuclear magnetic resonance, which19F NMRδ(ppm)22.70，37.28，100.31。
The composition of the product was measured by liquid chromatography, and the yield of trifluorostyrene was calculated according to the following formula based on the areas of 1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene, and the results are shown in Table 1.
Trifluorostyrene yield (trifluorostyrene area)/(1, 2-diphenyldifluoroethylene, dimer 1, 2-diphenylhexafluorocyclobutane and trifluorostyrene area sum)
TABLE 1 TFS Synthesis raw material ratio and yield (containing organic solvent)
Example 1
Putting 3500 kg of trifluorostyrene synthetic liquid into a fractionating tower, stirring and heating for reduced pressure distillation, collecting the fraction at about 45 ℃ under the condition of vacuum degree of-0.068 MPa, and collecting the fraction at vacuum degree of-0.099 MPa and temperature of more than 46 ℃. Collecting about 3000 kg of liquid, wherein about 88% of tetrahydrofuran as a solvent, about 90% of benzene and about 92% of trifluorostyrene as a product; about 500 kg of residue containing organic substances such as magnesium chlorofluoride, dimer and diphenyldifluoroethylene; and rectifying the fraction to obtain TFS, and treating from the beginning of the trifluorostyrene synthetic liquid to obtain the trifluorostyrene product, wherein the total yield is more than 84%.
1. The synthetic fluid of TFS synthetic example 1 was used as a raw material: theoretical yield of TFS: 1.4 × 3.5301 × 158 × 0.8856 ═ 691.53 kg; actual yield: 590.16 kg.
2. The synthetic fluid of TFS synthetic example 2 is used as raw material: theoretical yield of TFS: 1.4 × 3.5330 × 158 × 0.8938 ═ 698.51 kg; actual yield: 5585.51 kg.
3. The synthetic fluid of TFS synthetic example 3 was used as a raw material: theoretical yield of TFS: 1.4 × 3.5561 × 158 × 0.8838 ═ 695.19 kg; actual yield: 602.75 kg.
4. The synthetic fluid of TFS synthetic example 4 was used as a raw material: theoretical yield of TFS: 1.4 × 3.5561 × 158 × 0.9082 ═ 714.39 kg; actual yield: 601.66 kg.
5. The synthetic fluid of TFS synthetic example 5 was used as a raw material: theoretical yield of TFS: 1.4 × 3.5330 × 158 × 0.9105 ═ 711.56 kg; actual yield: 604.54 kg.
6. The synthetic fluid of TFS synthetic example 5 was used as a raw material: theoretical yield of TFS: 1.4 × 3.547.4 × 158 × 0.8954 ═ 702.61 kg; actual yield: 599.45 kg.
The process yields in examples 1-6 are shown in Table 2.
TABLE 2 TFS aftertreatment yield (Pilot rectification, removal of organic solvent)
| Batches of | Theoretical yield (gram) of TFS | Actual yield (g) of TFS | Yield of trifluorostyrene (%) |
| 1 | 691.53 | 590.16 | 85.34％ |
| 2 | 698.51 | 585.51 | 83.82％ |
| 3 | 695.19 | 602.75 | 86.70％ |
| 4 | 714.39 | 601.66 | 84.22％ |
| 5 | 711.56 | 604.54 | 84.96％ |
| 6 | 702.61 | 599.45 | 85.32％ |
Example 2
200 g of trifluorostyrene synthetic liquid is put into a 500ml eggplant-shaped bottle, then reduced pressure distillation is carried out by adopting a rotary evaporator, fractions at about 45 ℃ are collected under the condition that the vacuum degree is-0.068 MPa, and then fractions at the vacuum degree of-0.099 MPa and the temperature of more than 46 ℃ are collected. About 170 g of liquid is collected, wherein about 88 percent of tetrahydrofuran is used as a solvent, about 90 percent of benzene and about 92 percent of trifluorostyrene is used as a product; about 40 g of residue containing organic substances such as magnesium chlorofluoride, dimer and diphenyldifluoroethylene; and rectifying the fraction to obtain TFS, and treating from the beginning of the trifluorostyrene synthetic liquid to obtain the trifluorostyrene product, wherein the total yield is more than 85%.
1. The synthetic fluid of TFS synthetic example 1 was used as a raw material: theoretical yield of TFS: 1.4 × 0.2 × 158 × 0.8856 ═ 39.18 g; actual yield: 33.85 g
2. The synthetic fluid of TFS synthetic example 2 is used as raw material: theoretical yield of TFS: 1.4 × 0.2 × 158 × 0.8938 ═ 39.54 g; actual yield: 34.05 g
3. The synthetic fluid of TFS synthetic example 3 was used as a raw material: theoretical yield of TFS: 1.4 × 0.2 × 158 × 0.8838 ═ 39.10 g; actual yield: 35.15 g
4. The synthetic fluid of TFS synthetic example 4 was used as a raw material: theoretical yield of TFS: 1.4 × 0.2 × 158 × 0.9082 ═ 40.18 g; actual yield: 34.2 g
5. The synthetic fluid of TFS synthetic example 5 was used as a raw material: theoretical yield of TFS: 1.4 × 0.2 × 158 × 0.9105 ═ 40.28 g; actual yield: 34.60 g
6. The synthetic fluid of TFS synthetic example 5 was used as a raw material: theoretical yield of TFS: 39.61 g for 1.4 × 0.2 × 158 × 0.8954; actual yield: 35.10 g
The process yields in examples 1 to 6 are shown in Table 3.
TABLE 3 TFS work-up yield (rotary evaporation, removal of organic solvent)
Comparative example 1
Extracting petroleum ether: adding 500 g of trifluorostyrene synthetic solution into a 1000ml reduced pressure distillation device, collecting fractions at about 45 ℃ under the condition that the vacuum degree is-0.068 MPa, extracting the product trifluorostyrene by using solvent petroleum ether, performing suction filtration, and extracting the filter residue for three times by using a small amount of 60-90 ℃ petroleum ether, wherein the content of the trifluorostyrene in the filter residue is less than 3%. The yield of the trifluorostyrene product obtained by starting the treatment of the trifluorostyrene synthetic solution reaches more than 68 percent.
1. The synthetic fluid of TFS synthetic example 1 is used as raw material: theoretical yield of TFS: 1.4 × 0.5 × 158 × 0.8856 ═ 97.95 g; actual yield: 70.45 g
2. The synthetic fluid of TFS synthetic example 2 is used as raw material: theoretical yield of TFS: 98.85 g of 1.4 × 0.5 × 158 × 0.8938; actual yield: 70.16 g
3. The synthetic fluid of TFS synthetic example 3 is used as raw material: theoretical yield of TFS: 1.4 × 0.5 × 158 × 0.8838 ═ 97.75 g; actual yield: 72.53 g
4. TFS synthesis example 4 synthetic fluid is used as raw material: theoretical yield of TFS: 1.4 × 0.5 × 158 × 0.9082 ═ 100.45 g; actual yield: 71.51 g
5. TFS synthesis example 5 synthetic fluid is used as raw material: theoretical yield of TFS: 1.4 × 0.5 × 158 × 0.9105 ═ 100.70 g; actual yield: 70.55 g
6. TFS synthesis example 5 synthetic fluid is used as raw material: theoretical yield of TFS: 99.03 g for 1.4 × 0.5 × 158 × 0.8954; actual yield: 68.28 g
The process yields of 1-6 in this comparative example are shown in Table 4.
TABLE 4 TFS aftertreatment yield (Petroleum Ether extraction, removal of organic solvent)
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (8)
1. The post-treatment method of trifluorostyrene synthetic liquid is characterized by that it includes the distillation of synthetic liquid and distillation of fraction to obtain trifluorostyrene.
2. The post-treatment method of trifluorostyrene synthetic fluid according to claim 1, wherein the post-treatment method comprises the following steps: the distillate of the distillation is more than 85 percent of organic solvent, more than 90 percent of benzene and 92 to 95 percent of trifluorostyrene.
3. The post-treatment method of trifluorostyrene synthetic fluid according to claim 1, wherein the post-treatment method comprises the following steps: the distillation distilled off 80% liquid with 20% solids remaining.
4. The post-treatment method of trifluorostyrene synthetic fluid according to claim 1, wherein the post-treatment method comprises the following steps: the distillation temperature is less than 60 ℃.
5. The post-treatment method of trifluorostyrene synthetic fluid according to claim 1, wherein the post-treatment method comprises the following steps: collecting the fraction at 45 deg.C under vacuum degree of-0.068 MPa, and collecting the fraction at vacuum degree of-0.099 MPa and temperature of above 46 deg.C.
6. The post-treatment method of trifluorostyrene synthetic fluid according to claim 1, wherein the post-treatment method comprises the following steps: evaporating all liquid by adopting a rotary evaporator, and rectifying to obtain the trifluorostyrene.
7. The post-treatment method of trifluorostyrene synthetic fluid according to claim 1, wherein the post-treatment method comprises the following steps: distilling all the liquid in a fractionating tower and rectifying to obtain trifluorostyrene.
8. The post-treatment method of trifluorostyrene synthetic fluid according to claim 6 or 7, wherein the post-treatment method comprises the following steps: the liquid comprises most of the organic solvent and a small amount of benzene and the product trifluorostyrene.
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| CN114085125A (en) * | 2021-12-01 | 2022-02-25 | 常熟三爱富中昊化工新材料有限公司 | Method for preparing trifluorostyrene compound by continuous method |
| CN114105729A (en) * | 2021-12-01 | 2022-03-01 | 常熟三爱富中昊化工新材料有限公司 | Method for purifying trifluorostyrene synthetic liquid |
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