CN111470936A

CN111470936A - Equipment and process for directly producing di-o-xylyl hexafluoroacetone from HFPO

Info

Publication number: CN111470936A
Application number: CN202010512718.4A
Authority: CN
Inventors: 周济苍; 廖敏; 周遇吉; 喻鼎辉; 廖志辉; 沈莆原
Original assignee: Jiuding Fluorin Chemicals Co ltd Zhangping Fujian
Current assignee: Jiuding Fluorin Chemicals Co ltd Zhangping Fujian
Priority date: 2020-06-08
Filing date: 2020-06-08
Publication date: 2020-07-31

Abstract

The invention provides equipment and a process for directly producing di-o-xylyl hexafluoroacetone by HFPO (HFPO), wherein the equipment comprises an isomeric kettle, a gas-liquid separation kettle, a rectification column, a condenser, a HFA (high frequency solvent) storage tank and a condensation kettle, the bottom of the isomeric kettle is connected to the bottom of the gas-liquid separation kettle, the upper part of the gas-liquid separation kettle is connected with the upper part of the isomeric kettle, the top of the gas-liquid separation kettle is connected to the bottom of the rectification column through a pipeline, the upper end of the rectification column is respectively connected to an HFPO (HFPO feed inlet) and the HFA storage tank of the isomeric kettle, and the connecting pipeline between the rectification column and the HFA storage tank; the HFA storage tank is connected to the condensation kettle. The condensation reaction product does not contain Cl impurities and is easy to separate; the raw materials used have low toxicity, the reaction catalyst can be directly recycled, the cost is low, and the harm to the environment is avoided; the production and consumption of the HFA can be synchronously carried out, and the risks caused by transportation and storage of the HFA are avoided.

Description

Equipment and process for directly producing di-o-xylyl hexafluoroacetone from HFPO

[ technical field ] A method for producing a semiconductor device

The invention relates to equipment and a process for directly producing di-o-xylyl hexafluoroacetone by HFPO.

[ background of the invention ]

Polyimide (PI) is an important polymer material, and has excellent high temperature resistance, environmental stability, mechanical properties and the like due to a rigid imide structure in a molecular chain, so that the PI is widely applied to high-tech fields such as aerospace, machinery, electricians, electronics and the like. However, PI has the disadvantage of being difficult to dissolve and difficult to mold, which limits its application to some extent. The introduction of the fluorine-containing group into the PI can greatly improve the solubility of the PI and endow the PI with more excellent physicochemical, optical, electrical and gas separation and other functionalities, so that the fluorine-containing polyimide has unique advantages and wide development prospects.

The fluorine-containing polyimide synthesized by using 2, 2-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (hexafluoro dianhydride, 6FDA) monomer has the following advantages in performance: 1) the dielectric constant of the common polyimide is about 3.4, while the dielectric constant can be reduced to 2.5 after 6FDA is added. 2) The transparency and the controllable refractive index of the common polyimide are slightly yellowish or brown, the common polyimide can be changed into the transparency by adding 6FDA, and the refractive index of the common polyimide is changed along with the adding amount of the 6FDA, so that the common polyimide is adjustable. 3) Because of the strong electronegativity of fluorine atoms, the fluorine-containing polyimide has better chemical and thermal stability, and the product can be used under special chemical environment or temperature. 4) Because of the low polarity of fluorine atoms, the fluorine-containing polyimide has very low surface free energy, so that the polyimide has the characteristics of smooth surface and small friction force. Up to now, the fluorine-containing polyimide based on 6FDA has gained important application in high-tech fields including space film diffractive optical imaging systems, flexible circuit boards and flexible touch screens.

2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane (bis-o-xylylhexafluoropropane, 6FXY or BoxAF) is a raw material for synthesizing 6FDA, and a preparation method thereof has been reported in patent documents at home and abroad.

As early as 1967, U.S. Pat. No. 4, 3310573A disclosed a synthesis method of diarylhexafluoropropanes by condensing two moles of aromatic compounds (such as aniline, acetanilide, nitroaniline, bromoaniline, and toluene, xylene, etc.) with hexafluoroacetone in the presence of hydrogen fluoride, in 2003, Zhu Shi-just et al (Journal of fluorine chemistry 123(2003) 221-.

The following patent technical literature is mainly optimized for the technical solutions disclosed earlier. For example, chinese patent publication No. CN 106699504 a provides a method for preparing bis-o-xylyl hexafluoroacetone, which comprises the following steps: 1) the molar ratio of hexafluoroacetone trihydrate to o-xylene is 1: 2-1: 6, carrying out azeotropic dehydration at the heating temperature of 90-100 ℃ under the heating reflux condition to obtain hexafluoroacetone monohydrate; 2) the hexafluoroacetone monohydrate-containing reaction solution obtained after azeotropic dehydration reaction can be directly used as a raw material to be mixed with o-xylene in a molar ratio of 1: 0.4-2 ℃, the reaction temperature is preferably 90-130 ℃, and the 2, 2-bis (3, 4-xylyl) hexafluoropropane is obtained by liquid phase reaction under the action of hydrogen fluoride accounting for 45-80 wt% of the total weight of the two. The method provided by the invention has the advantages of low toxicity of raw materials, low reaction pressure, easiness in operation, high reaction selectivity and yield and suitability for industrial production.

For another example, chinese patent No. CN1049420C discloses a method for synthesizing bis-o-xylylhexafluoropropane by directly using a trifluoromethanesulfonic acid catalyst and performing a condensation reaction between benzene or a benzene derivative as a raw material and hexafluoroacetone. Similarly, chinese patent publication No. CN 108395363 a further provides a method for synthesizing bis-o-xylylhexafluoropropane using sulfonic acid as a catalyst, comprising the following steps: 1) mixing ortho-xylene, sulfonic acid and a solvent according to a proportion, wherein the molar ratio of the ortho-xylene to the sulfonic acid is 1.0: 0.1 to 1.0: 1.0 to obtain a mixture. 2) Introducing hexafluoroacetone gas into the mixture obtained in the step 1), reacting at the reaction temperature and the reaction pressure to obtain a crude product, carrying out alkali washing, water washing and concentration on the crude product, crystallizing by using a crystallization solvent, and carrying out vacuum drying to obtain the 2, 2-bis (3, 4-xylyl) hexafluoropropane. The sulfonic acid is at least one selected from the group consisting of methanesulfonic acid, trifluoromethanesulfonic acid, 1-trifluoroethylsulfonic acid, pentafluoroethylsulfonic acid, propylsulfonic acid, 1-trifluoropropylsulfonic acid, benzenesulfonic acid, 4-methylbenzenesulfonic acid and 4-trifluoromethylbenzenesulfonic acid.

The Chinese patent of the publication No. CN104496763B provides a method for synthesizing the BoxAF directly by using the HFPO/o-xylene one-pot method, which is characterized in that aromatic hydrocarbon and anhydrous hydrogen fluoride are mixed in a reactor, a catalyst is added, then hexafluoropropylene oxide is added, stirring and heating are carried out, after the reaction is finished, the hydrogen fluoride is removed, and the rest product is refined to obtain a diaryl hexafluoropropane compound product, wherein the catalyst is SbCl5, TiCl4 or a mixture of the SbCl5 and the TiCl4, the aromatic hydrocarbon, the hexafluoropropylene oxide and the anhydrous hydrogen fluoride are mixed according to the mass ratio of 1 (0.5-4) to (0.5-4), the reaction temperature is 50-200 ℃, and the reaction time is 1-12 hours.

Finally, chinese patent No. CN101696199B provides another method for preparing bis-o-xylylhexafluoroacetone, in which o-xylene and 2, 2-dichlorohexafluoropropane are alkylated under heating in ionic liquid (1-butyl-3-methylimidazoline tetrafluoroborate, 1-butyl-3-methylimidazoline hexafluorophosphate, etc.) under catalysis of L ewis acid (AlCl3, ZnCl2) to obtain 4, 4' - (hexafluoroisopropenylene) di-o-xylene.

In summary, there are three methods of preparation of BoxAF currently disclosed 1) HFA process, which is based on HFA as a raw material and is a product obtained by condensation reaction of HFA with ortho-xylene in the presence of a catalyst, because HFA is highly toxic, there is a great risk of transportation, storage and use, not only HFA raw material is not easily available and expensive, and thus the production cost is relatively high, 2) HFPO/ortho-xylene one-pot process, which is based on HFPO as a raw material and combines isomerization of HFPO (to produce HFA) and condensation reaction of HFA with aromatic hydrocarbons, although this process avoids the risks associated with transportation and storage of HFA, a problem inevitably involved in the production process of L ewis acid catalyst, which generates a large amount of chlorine-containing by-products, which is difficult to separate, and several reactions are simultaneously performed, the reaction complexity increases, which is more difficult to control, which increases the consumption of HFPO alone, increases the production cost, and the catalyst is not easily recycled, and the discharge of HFPO is easily environmentally polluting, 3) 2-dichloro-propane, which is an important industrial process, which is not easily studied, and is expensive, and is not expensive.

[ summary of the invention ]

The invention aims to solve the technical problems of providing equipment and a process for directly producing di-o-xylyl hexafluoroacetone by HFPO, wherein the used raw materials are low in toxicity, safe and environment-friendly, and lower in cost; the condensation reaction product does not contain Cl impurities and is easy to separate; the reaction catalyst can be directly recycled, so that the cost is saved and the harm to the environment is avoided; the production and consumption of the HFA can be synchronously carried out, and the risks caused by transportation and storage of the HFA are avoided.

The invention is realized by the following steps:

the equipment for directly producing the bis-o-xylyl hexafluoroacetone by the HFPO comprises an isomerization kettle, a gas-liquid separation kettle, a rectifying column, a condenser, an HFA storage tank and a condensation kettle, wherein the isomerization kettle is provided with an HFPO feed port and an isomerization reaction catalyst feed port, a first circulating pipeline at the bottom of the isomerization kettle is connected to the bottom of the gas-liquid separation kettle through a first circulating pump, the upper part of the gas-liquid separation kettle is connected with the upper part of the isomerization kettle through a second circulating pipeline, and the second circulating pipeline is provided with a second circulating pump;

the top of the gas-liquid separation kettle is connected to the bottom of a rectifying column through a pipeline, the upper end of the rectifying column is respectively connected to an HFPO feed port and an HFA storage tank of the isomerization kettle, and a condenser is further arranged on a connecting pipeline between the rectifying column and the HFA storage tank;

the HFA storage tank is connected to the condensation kettle, and a raw material feeding port and a condensation reaction catalyst feeding port are further formed in the condensation kettle; and stirrers are arranged in the isomerization kettle and the condensation kettle.

Further, the equipment also comprises an HF recovery tank, and the HF recovery tank is connected with a condensation reaction catalyst feed inlet of the condensation kettle.

The invention also relates to a process for directly producing di-o-xylyl hexafluoroacetone by HFPO, which comprises the following steps:

step 1, heating a reaction device, vacuumizing and dehydrating;

step 2, replacing air in the reaction system with high-purity nitrogen, and removing oxygen;

step 3, starting a stirrer stirring system, and metering an isomerization reaction catalyst L ewis acid into the isomerization kettle;

step 4, metering and rapidly introducing HFPO, and heating for reaction;

step 5, after HFPO in the isomerization kettle is completely converted into HFA, starting a first circulating pump, and enabling reaction materials in the isomerization kettle to enter a gas-liquid separation kettle for gas-liquid separation;

further separating HFA gasified from the gas-liquid separation kettle from a small amount of an isomerization reaction catalyst L ewis acid carried in the HFA in a rectifying column, cooling the HFA gas with qualified purity by a condenser and then collecting the HFA gas into a HFA storage tank, returning the HFA gas with unqualified purity to the isomerization kettle, returning the carried small amount of the isomerization catalyst L ewis acid to the gas-liquid separation kettle, conveying the HFA gas to the isomerization kettle by a second circulating pump and continuously using the HFPO isomerization reaction catalyst;

step 6, metering HFA in an HFA storage tank into a condensation kettle for HFA condensation reaction, metering a condensation reaction catalyst, and then metering o-xylene;

and 7, heating for reaction, and obtaining a crude product of bis-o-xylyl hexafluoroacetone after HFA completely reacts.

Further, the process steps further include:

step 8, after the condensation reaction is finished, cooling the crude product of the bis-o-xylyl hexafluoroacetone, distilling to remove the condensation reaction catalyst, and recycling the condensation reaction catalyst to a condensation reaction catalyst storage tank;

step 9, conveying the residue obtained in the step 8 to an ultracentrifugal extraction tower by using a pump, and extracting by using 10% of sodium hydroxide solution and deionized water in sequence to remove water-soluble impurities; then extracting by using an organic solvent, concentrating, drying and recrystallizing to obtain the final product of the bis-o-xylyl hexafluoroacetone.

Further, the isomerization catalyst L ewis acid is SbF₅、Al₂O₃、TiO₂、WO₂、AlCl₃、AlBr₃、SnCl₄、FeCl₃、CuCl₂Or ZrOCl₂；

The dosage of the isomerization catalyst L ewis acid is 5-20% of the addition of HFPO, and the temperature of the isomerization reaction is 30-150 ℃.

Further, the L ewis acid is SbF₅The dosage of the isomerization catalyst L ewis acid is 10% of the dosage of HFPO, and the temperature of the isomerization reaction is 90 ℃.

Further, the condensation reaction catalyst is sulfonic acid and HF;

the amount of the HF is 40-80 wt% of the total weight of the hexafluoroacetone HFA and the o-xylene;

the molar ratio of the HFA to the o-xylene is 1: 2-1: 6;

the HFA condensation reaction temperature is 60-180 ℃.

Further, the HFA condensation reaction solvent and the catalyst are HF;

the HFA condensation reaction temperature is 90-150 ℃.

Further, the pressure of the HFPO isomerization reaction is 1-20 atm; the isomerization reaction time of the HFPO is 1-24 hours;

the HFA condensation reaction pressure is 1-20 atm; the HFA condensation reaction time is 1-24 hours.

Further, in the step 8, after the HFA condensation reaction is completed, the recovery temperature of the condensation reaction catalyst HF is 60-180 ℃.

The invention has the following advantages:

the HFPO isomerization reaction process is carried out in an external circulation reactor and comprises an isomerization kettle with a stirrer and a gas-liquid separation kettle connected with the isomerization kettle. The HFPO isomerization reaction is carried out in an isomerization kettle, and the separation of the reaction product and the catalyst is completed in a gas-liquid separation kettle tank. The gas-liquid separation kettle is further connected with a rectifying column, the rectifying column is connected with a condenser, and the condenser is connected with an HFA storage tank. In the reaction process, materials circularly flow in the isomerization kettle and the gas-liquid separation kettle, and the reaction and the separation process are carried out simultaneously. By such a reaction separation system, the isomerization reaction of HFPO, the separation and purification of products, and the storage can be achieved; and the simultaneous production (HFPO isomerization) and consumption (HFA condensation) of HFA can be achieved, thus minimizing the risks associated with transportation and storage of HFA.

Compared with HFPO one-pot method, the condensation process of HFPO and ortho-xylene of the invention uses HF as solvent and catalyst, does not use L ewis acid, so the reaction product does not contain Cl impurity, and is easy to separate.

[ description of the drawings ]

The invention will be further described with reference to the following examples with reference to the accompanying drawings.

FIG. 1 is a schematic diagram of an apparatus for directly producing bis-o-xylylhexafluoroacetone from HFPO of the present invention.

[ detailed description ] embodiments

Referring to fig. 1, the invention relates to a device for directly producing di-o-xylyl hexafluoroacetone from HFPO, which comprises an isomerization kettle 1, a gas-liquid separation kettle 2, a rectification column 3, a condenser 4, a HFA storage tank 5 and a condensation kettle 6, wherein the isomerization kettle 1 is provided with a HFPO feed inlet 11 and an isomerization reaction catalyst feed inlet 12, a first circulation pipeline 13 at the bottom of the isomerization kettle 1 is connected to the bottom of the gas-liquid separation kettle 2 through a first circulation pump 14, the upper part of the gas-liquid separation kettle 2 is connected with the upper part of the isomerization kettle 1 through a second circulation pipeline 21, and the second circulation pipeline 21 is provided with a second circulation pump 22; one end of the second circulation pipe 21 located at the gas-liquid separation kettle 2 extends into the bottom of the gas-liquid separation kettle 2.

The top of the gas-liquid separation kettle 2 is connected to the bottom of a rectification column 3 through a pipeline, the upper end of the rectification column 3 is respectively connected to an HFPO feed inlet 11 of the isomerization kettle 1 and an HFA storage tank 5, and a condenser 4 is further arranged on a connecting pipeline between the rectification column 3 and the HFA storage tank 5;

the HFA storage tank 5 is connected to the condensation kettle 6, and the condensation kettle 6 is also provided with a raw material feeding port 61 and a condensation reaction catalyst feeding port 62; the isomerous kettle 1 and the condensation kettle 6 are both internally provided with a stirrer 7.

The apparatus further comprises an HF recovery tank connected to a condensation reaction catalyst feed port 62 of the condensation vessel 6.

The invention also relates to a process for directly producing di-o-xylyl hexafluoroacetone from HFPO in the reaction device, which comprises the following steps:

step 1, heating a reaction device, vacuumizing and dehydrating;

step 3, starting a stirrer stirring system, and metering an isomerization reaction catalyst L ewis acid into the isomerization kettle at room temperature, wherein the isomerization reaction catalyst L ewis acid is SbF₅、Al₂O₃、TiO₂、WO₂、AlCl₃、AlBr₃、SnCl₄、FeCl₃、CuCl₂Or ZrOCl₂Preferably, the L ewis acid is SbF₅；

The dosage of the isomerization catalyst L ewis acid is 5-20% of the dosage of HFPO, preferably, the dosage of the isomerization catalyst L ewis acid is 10% of the dosage of HFPO,

step 4, metering and rapidly introducing HFPO, and heating for reaction; the temperature of the isomerization reaction is 30-150 ℃; preferably, the temperature of the isomerization reaction is 90 ℃. When the temperature is too high, the isomerization reaction is easy to generate byproducts, and when the temperature is too low, the isomerization reaction speed is too slow.

step 6, metering HFA in an HFA storage tank into a condensation kettle for HFA condensation reaction at room temperature, metering a condensation reaction catalyst, and then metering o-xylene; the condensation reaction catalyst is sulfonic acid and HF; the amount of the HF is 40-80 wt% of the total weight of the hexafluoroacetone HFA and the o-xylene; the molar ratio of the HFA to the o-xylene is 1: 2-1: 6; preferably, the HFA condensation reaction solvent and catalyst is HF.

And 7, heating for reaction, and obtaining a crude product of bis-o-xylyl hexafluoroacetone after HFA completely reacts. The HFA condensation reaction temperature is 60-180 ℃; preferably, the HFA condensation reaction temperature is 90-150 ℃.

Step 8, after the condensation reaction is finished, cooling the crude product of the bis-o-xylyl hexafluoroacetone, distilling to remove the condensation reaction catalyst, and recycling the condensation reaction catalyst to a condensation reaction catalyst storage tank; the recovery temperature of the condensation reaction catalyst HF is 60-180 ℃.

The pressure of the HFPO isomerization reaction is 1-20 atm; the isomerization reaction time of the HFPO is 1-24 hours;

The present invention is further illustrated by the following examples. These examples should not be construed as limiting the scope of the invention. All the technical schemes which belong to the technical scheme equivalent to the invention belong to the protection scope of the invention.

Comparative example 1

The reaction was carried out in a 1000ml Monel reaction system. The reaction system is heated, vacuumized to remove water, and the whole system is purged with high-purity nitrogen to remove oxygen. HFPO (165.37g, 0.996mol) was fed into the reactor at room temperature, anhydrous HF (200g, 10mol) was metered in, and then o-xylene (212.2g, 2mol) was metered in. The temperature is raised to 130 ℃, and the pressure of the reaction kettle is 10 kilograms. After a reaction time of 16 h. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into a storage tank for recycling. Pumping the residue into an ultracentrifugal extraction tower, extracting with 10% sodium hydroxide (NaOH) solution and deionized water to neutrality, concentrating, and drying. The product yield was 0%.

Comparative example II

The reaction was carried out in a 1000ml Monel reaction system. The reaction system is heated, vacuumized to remove water, and the whole system is purged with high-purity nitrogen to remove oxygen. HFPO (165.37g, 0.996mol) was fed into the reactor at room temperature, anhydrous HF (200g, 10mol) and AlCl3(13.3g,0.1mol) as catalyst were metered in, and o-xylene (212.2g, 2mol) was then metered in. The temperature is raised to 130 ℃, and the pressure of the reaction kettle is 10 kilograms. After a reaction time of 16 h. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into a storage tank for recycling. The residue was pumped into an ultracentrifugal extraction column, extracted to neutrality with 10% sodium hydroxide (NaOH) solution followed by deionized water, concentrated, dried, recrystallized with ethanol, and vacuum dried at 40 ℃ for 12 hours to give product (107.67g, 0.299mol), with a total yield of 30% including chlorine-containing impurities.

Example one

Synthesis of 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane from hexafluoropropylene oxide by direct continuous method was simulated in a set of 2 Monel reaction systems each containing 1000ml of solvent. The reaction system is heated, vacuumized to remove water, and the whole system is purged with high-purity nitrogen to remove oxygen. Under the protection of nitrogen, introducing a catalyst SbF into an HFPO isomerization reaction kettle, namely an isomerization kettle₅(21.67g, 0.1mol) followed by the rapid metered addition of hexafluoropropylene oxide (166.02g, 1mol), warming to 90 ℃ and catalytic rearrangement to give Hexafluoroacetone (HFA) (165.37g, 0.996 mol). Cooling to rectify HFPO isomerization reaction product HFA, cooling HFA by a condenser, and then feeding the HFA into an HFA storage tank, wherein a catalyst SbF₅Refluxing into HFPO isomerization reaction kettle. After the rectification is finished, the HFPO isomerization reaction kettle continues to rapidly meter and introduce the HFPO at room temperature, and a small amount of catalyst SbF is added according to the requirement₅Ready to enter a second reaction.

HFA (165.37g, 0.996mol) was charged into an HFA storage tank into a 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane reaction synthesis reactor, i.e., a condensation reactor, at room temperature, and anhydrous HF (200g, 10mol) was metered in. O-xylene (212.2g, 2mol) was then metered in. The temperature is raised to 130 ℃, and the pressure of the condensation kettle is 10 kilograms. After 16h reaction time, the HFA was completely reacted. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into an HF recycling tank for recycling. The residue was pumped to an ultracentrifugal extraction column, extracted to neutrality with 10% sodium hydroxide (NaOH) solution followed by deionized water, concentrated, dried, recrystallized with ethanol, and vacuum dried wet at 40 ℃ for 12 hours to give the product (218g, 0.605mol) with a GC purity of 99.8% and a calculated yield of 60.5%.

Example two

Synthesis of 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane from hexafluoropropylene oxide by direct continuous method was simulated in a set of 2 Monel reaction systems each containing 1000ml of solvent. The reaction system is heated, vacuumized to remove water, and the whole system is purged with high-purity nitrogen to remove oxygen. Under the protection of nitrogen, hexafluoropropylene oxide (166.02g, 1mol) is rapidly metered into an HFPO isomerization reaction kettle (isomerization kettle) described in the first example, the temperature is raised to 90 ℃, and Hexafluoroacetone (HFA) (164.53g, 0.991mol) is obtained through catalytic rearrangement. Cooling to rectify HFPO isomerization reaction product HFA, cooling HFA by a condenser, and feeding the HFA into an HFA storage tank, wherein a catalyst is SbF₅Refluxing into HFPO isomerization reaction kettle. After the rectification is finished, continuously and quantitatively introducing HFPO into the HFPO isomerization reaction kettle, and adding a small amount of catalyst SbF5 as required to prepare for a second reaction.

164.53g (0.991mol) of HFA in an HFA storage tank is introduced into a 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane reaction synthesis kettle, i.e. a condensation kettle at room temperature, and anhydrous HF (200g, 10mol) is metered in. O-xylene (212.2g, 2mol) was then metered in. The temperature is raised to 130 ℃, and the pressure of the condensation kettle is 10 kilograms. After 16h reaction time, the HFA was completely reacted. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into an HF recycling tank for recycling. The residue was pumped to an ultracentrifugal extraction column, extracted to neutrality with 10% sodium hydroxide (NaOH) solution followed by deionized water, concentrated, dried, then recrystallized with ethanol, and the wet product was dried under vacuum at 40 ℃ for 12 hours to give the product (210.8g, 0..585mol) with a GC purity of 99.6% and a calculated yield of 58.5%.

EXAMPLE III

Synthesis of 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane from hexafluoropropylene oxide by direct continuous method was simulated in a set of 2 Monel reaction systems each containing 1000ml of solvent. Reaction system heatingVacuumizing to remove water, and purging the whole system with high-purity nitrogen to remove oxygen. Under the protection of nitrogen, introducing a catalyst SbF into an HFPO isomerization reaction kettle, namely an isomerization kettle₅(21.67g, 0.1mol) followed by the rapid metered addition of hexafluoropropylene oxide (166.02g, mol), warming to 90 ℃ and catalytic rearrangement to give Hexafluoroacetone (HFA) (165.37g, 0.996 mol). Cooling to rectify HFPO isomerization reaction product HFA, cooling HFA by a condenser, and then feeding the HFA into an HFA storage tank, wherein a catalyst SbF₅Refluxing into HFPO isomerization reaction kettle. After the rectification is finished, continuously and rapidly metering HFPO in the HFPO isomerization reaction kettle at room temperature, and adding a small amount of catalyst SbF according to the requirement₅Ready to enter a second reaction.

HFA (165.37g, 0.996mol) in an HFA storage tank was charged into a 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane reaction synthesis reactor, i.e., a condensation reactor, at room temperature, and anhydrous HF (200g, 10mol) was metered in. O-xylene (212.2g, 2mol) was then metered in. The temperature is raised to 150 ℃, and the pressure of the condensation kettle is 11 kilograms. After 16h reaction time, the HFA was completely reacted. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into an HF recycling tank for recycling. The residue was pumped to an ultracentrifugal extraction column, extracted to neutrality with 10% sodium hydroxide (NaOH) solution followed by deionized water, concentrated, dried, recrystallized with ethanol, and vacuum dried wet at 40 ℃ for 12 hours to give the product (246.8g, 0.685mol) with a GC purity of 99.8% and a calculated yield of 68.5%.

Example four

Synthesis of 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane from hexafluoropropylene oxide by direct continuous method was simulated in a set of 2 Monel reaction systems each containing 1000ml of solvent. The reaction system is heated, vacuumized to remove water, and the whole system is purged with high-purity nitrogen to remove oxygen. Under the protection of nitrogen, introducing a catalyst SbF into an HFPO isomerization reaction kettle, namely an isomerization kettle₅(21.67g, 0.1mol) followed by the rapid metered addition of hexafluoropropylene oxide (166.02g, mol), warming to 60 ℃ and catalytic rearrangement to give Hexafluoroacetone (HFA) (165.37g, 0.996 mol). Cooling to rectify HFPO isomerization reaction product HFA, cooling HFA by a condenser, and then feeding the HFA into an HFA storage tank, wherein a catalyst SbF₅Refluxing HFPO isomerizationIn a reaction kettle. After the rectification is finished, continuously and rapidly metering HFPO into the HFPO isomerization reaction kettle at room temperature, and adding a small amount of catalyst SbF according to the need₅Ready to enter a second reaction.

HFA (165.37g, 0.996mol) in an HFA storage tank was charged into a 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane reaction synthesis reactor, i.e., a condensation reactor, at room temperature, and anhydrous HF (200g, 10mol) was metered in. O-xylene (212.2g, 2mol) was then metered in. The temperature is raised to 130 ℃, and the pressure of the condensation kettle is 10 kilograms. After 16h reaction time, the HFA was completely reacted. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into an HF recycling tank for recycling. The residue was pumped to an ultracentrifugal extraction column, extracted to neutrality with 10% sodium hydroxide (NaOH) solution followed by deionized water, concentrated, dried, recrystallized with ethanol, and vacuum dried wet at 40 ℃ for 12 hours to give the product (241.4g, 0.67mol) with a GC purity of 99.8% and a calculated yield of 67.0%.

EXAMPLE five

Synthesis of 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane from hexafluoropropylene oxide by direct continuous method was simulated in a set of 2 Monel reaction systems each containing 1000ml of solvent. The reaction system is heated, vacuumized to remove water, and the whole system is purged with high-purity nitrogen to remove oxygen. Under the protection of nitrogen, introducing a catalyst SbF into an HFPO isomerization reaction kettle, namely an isomerization kettle₅(21.67g, 0.1mol) followed by the rapid metered addition of hexafluoropropylene oxide (166.02g, mol), warming to 60 ℃ and catalytic rearrangement to give Hexafluoroacetone (HFA) (165.37g, 0.996 mol). Cooling to rectify HFPO isomerization reaction product HFA, cooling HFA by a condenser, and then feeding the HFA into an HFA storage tank, wherein a catalyst SbF₅Refluxing into HFPO isomerization reaction kettle. After the rectification is finished, continuously and rapidly metering HFPO into the HFPO isomerization reaction kettle at room temperature, and adding a small amount of catalyst SbF according to the need₅Ready to enter a second reaction.

HFA (165.37g, 0.996mol) in an HFA storage tank was introduced into a 2, 2-bis (3, 4-dimethylphenyl) hexafluoropropane reaction synthesis reactor, i.e., a condensation reactor, at room temperature, and anhydrous HF (200g, 10mol) was metered in. O-xylene (212.2g, 2mol) was then metered in. The temperature is raised to 130 ℃, and the pressure of the condensation kettle is 10 kilograms. After 16h reaction time, the HFA was completely reacted. And (4) cooling, distilling to remove the solvent HF, and recycling the solvent HF into an HF recycling tank for recycling. The residue was pumped to an ultracentrifugal extraction column, extracted to neutrality with 10% sodium hydroxide (NaOH) solution followed by deionized water, concentrated, dried, recrystallized with ethanol, and vacuum dried wet at 40 ℃ for 12 hours to give the product (250.4g, 0.695mol) with a GC purity of 99.8% and a calculated yield of 69.5%.

Compared with the prior HFPO one-pot method, the HFPO isomerization reaction and the HFA condensation reaction are respectively carried out in two reaction kettles which are connected in series, the HFA is consumed immediately after being produced, the risk caused by transportation and storage of the HFA is reduced, and then, HF is used as a solvent and a catalyst in the HFA and o-xylene condensation process, L ewis acid is not used, Cl impurities are not generated in the condensation process, the side reaction in the HFA condensation process can be easily separated, the unit consumption of the HFPO is reduced, the solvent and the catalyst HF are easily recycled after the reaction is finished, and finally, the catalyst antimony pentafluoride (SbF) in the HFPO isomerization process is used (SbF F) after the reaction is finished)₅) Separating HFA in a gas-liquid separation tank to realize catalyst SbF₅The direct recycling not only reduces the discharge, but also reduces the cost.

Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.

Claims

1. The utility model provides a HFPO directly produces equipment of two o-xylyl hexafluoroacetone which characterized in that: the device comprises an isomerization kettle, a gas-liquid separation kettle, a rectifying column, a condenser, a HFA storage tank and a condensation kettle, wherein the isomerization kettle is provided with an HFPO feed port and an isomerization reaction catalyst feed port;

2. The apparatus for directly producing bis-o-xylylhexafluoroacetone from HFPO according to claim 1, wherein: the equipment also comprises an HF recovery tank, and the HF recovery tank is connected with a condensation reaction catalyst feed inlet of the condensation kettle.

3. A process for directly producing di-o-xylyl hexafluoroacetone from HFPO is characterized in that: the process comprises the following steps:

step 1, heating a reaction device, vacuumizing and dehydrating;

step 4, metering and rapidly introducing HFPO, and heating for reaction;

4. The process for directly producing bis-o-xylylhexafluoroacetone from HFPO according to claim 3, wherein: the process steps further include:

5. The process for directly producing di-o-xylylhexafluoroacetone from HFPO as claimed in claim 3 or 4, wherein the isomerization catalyst L ewis acid is SbF₅、Al₂O₃、TiO₂、WO₂、AlCl₃、AlBr₃、SnCl₄、FeCl₃、CuCl₂Or ZrOCl₂；

6. A process according to claim 5The process for directly producing the bis-o-xylyl hexafluoroacetone by HFPO is characterized in that the L ewis acid is SbF₅The dosage of the isomerization catalyst L ewis acid is 10% of the dosage of HFPO, and the temperature of the isomerization reaction is 90 ℃.

7. The process for directly producing bis-o-xylylhexafluoroacetone from HFPO according to claim 3 or 4, wherein: the condensation reaction catalyst is sulfonic acid and HF;

the molar ratio of the HFA to the o-xylene is 1: 2-1: 6;

the HFA condensation reaction temperature is 60-180 ℃.

8. The process for directly producing bis-o-xylylhexafluoroacetone from HFPO according to claim 7, wherein:

the HFA condensation reaction solvent and the catalyst are HF;

the HFA condensation reaction temperature is 90-150 ℃.

9. The process for directly producing bis-o-xylylhexafluoroacetone from HFPO according to claim 3 or 4, wherein: the pressure of the HFPO isomerization reaction is 1-20 atm; the isomerization reaction time of the HFPO is 1-24 hours;

10. The process for directly producing bis-o-xylylhexafluoroacetone from HFPO according to claim 8, wherein:

in the step 8, after the HFA condensation reaction is finished, the recovery temperature of the condensation reaction catalyst HF is 60-180 ℃.