A catalytic process for the preparation of methyl perfluorobutyl ether from hexafluoropropylene trimer

Abstract

The application provides a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, and belongs to the technical field of hydrogen fluoride ether preparation. Seven-fluoro-isobutenyl methyl ether, perfluorocarbon and a solid catalyst are put into a fluorination reactor, fluorine-nitrogen mixed gas is introduced for fluorination reaction, the reaction is terminated when the molar ratio of the seven-fluoro-isobutenyl methyl ether to the introduced fluorine gas reaches a set ratio, tail gas is removed, and methyl perfluorobutyl ether is obtained through filtration and rectification. The method uses hexafluoropropylene trimer as a solvent which can be recycled and used, is green and environment-friendly, has high product purity, and the reaction yield can reach more than 75%.

Description

Technical Field

[0001] This invention relates to the field of hydrofluoroether preparation technology, and in particular to a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer. Background Technology

[0002] Methyl perfluorobutyl ether (MEPA), also known as methyl nonafluorobutyl ether or methyl perfluoroisobutyl ether, is a colorless, odorless, non-toxic, non-corrosive, and non-flammable liquid. It is a fluorinated ether solvent, miscible with many components, and considered to have good lubricity, making it suitable as a solvent for oil-based formulations. Perfluoroisobutyl methyl ether is used as a precision cleaning agent in the cleaning of printed circuit boards, metals and their components, liquid crystal displays, and precision cleaning (including electronic devices, optical components, aerospace equipment components, medical device components, plastic parts, etc.) to remove grease, wax, rosin flux, fingerprints, sweat stains, particles, etc. Because perfluoroisobutyl methyl ether's properties are closest to CFCs, with an ODP value of zero and a GWP value of 320, it is an ideal substitute for solvents containing ozone-depleting substances such as CFC-113, trichloroethane, and carbon tetrachloride. Therefore, the market demand for perfluorobutyl methyl ether is significant.

[0003] Patent No. CN201010607067.3 relates to a method for synthesizing hydrofluoroethers. The method involves using 20-100 parts by weight of an alcohol as a raw material, wherein the alcohol is one of methanol, ethanol, propanol, trifluoromethanol, tetrafluoropropanol, and octafluoropentanol. In the presence of 1-6 parts of a strong base catalyst, 34-108 parts of a fluorinated olefin are continuously added. The reaction is carried out at 110-180°C, with a reaction pressure of 0.6-1.2 MPa and a reaction time of 1-5 h. The target product is obtained after distillation separation.

[0004] Patent No. CN202010672282.5 relates to "a method for synthesizing perfluorobutyl methyl ether," belonging to the field of organic chemical synthesis. The method for synthesizing perfluorobutyl methyl ether is characterized by the following steps: Step 1: Carbon tetrachloride (molecular formula CCl4) and pentachloropropene (molecular formula CCl3CH=CCl2) react with a telomerization catalyst to generate nonachlorobutane (molecular formula CCl3CH(CCl3)CCl3). Step 2: Nonachlorobutane undergoes gas-phase catalytic dehydrochlorination under the action of a catalyst to generate perchlorobutene (CCl3C=(CCl2)CCl3). Step 3: Perchlorobutene reacts with anhydrous hydrogen fluoride (AHF) under the action of a catalyst to generate hexafluorodichlorobutene (CF3C=(CCl2)CF3). Step 4: Hexafluorodichlorobutene undergoes telomerization with methanol (CH3OH) and triethylamine to generate hexafluoromonochloroisopropene methyl ether (CH3O(Cl)C=C(CF3)2). Step 5: Hexafluorochloroisopropenyl methyl ether is catalytically synthesized in the gas phase with chlorine and anhydrous hydrogen fluoride in the presence of a catalyst to form perfluorobutyl methyl ether (CH3O(F2)CC(CF3)2).

[0005] However, most of the existing publicly available methods for preparing hydrofluoroethers involve long reaction times and high temperatures, resulting in high production costs, while the product yield and purity are also insufficient.

[0006] In view of this, the present invention proposes a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer. Summary of the Invention

[0007] This invention provides a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, thereby solving at least one of the technical problems mentioned in the background art, and belongs to the field of hydrofluoroether preparation technology.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0009] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0010] S1: By weight, add 100-300 parts of heptafluoroisobutylene methyl ether and 300-500 parts of perfluorocarbon, 30-50 parts of supported catalyst to the fluorination reactor, start stirring in the reactor, cool the reactor, and slowly introduce fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0011] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0012] In the above technical solution, the perfluorocarbon is further described as a hexafluoropropylene trimer.

[0013] In the above technical solution, the temperature of the reaction vessel is further -45 to 5°C.

[0014] In the above technical solution, the concentration of fluorine in the fluorine-nitrogen mixed gas is further 5-15 wt%.

[0015] In the above technical solution, the molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is further set to 1:0.6-0.9.

[0016] In the above technical solution, the reaction continues for 10-30 minutes after the fluorine-nitrogen mixed gas is stopped.

[0017] In the above technical solution, the further supported catalyst is a fluorinated catalyst of organometallic antimony supported on tourmaline ceramic spheres, and its preparation method is as follows:

[0018] S1: Dissolve 5-12 parts of antimony pentachloride in 100-150 parts of N-methyl-2-pyrrolidone (DMF) according to the mass fraction to prepare a metal ion solution;

[0019] S2: According to the mass percentage, 13-26 parts of 3-vinyl-2-methylpyridine, 120-200 parts of N-methyl-2-pyrrolidone, and 3-6 parts of hydrochloric acid with a mass percentage of 20-30% are added to a stirred tank and stirred at 70-80℃ for 50-100 min. Then, the metal ion solution prepared in S1 is poured into the ligand solution for mixing, and then added to a hydrothermal reactor and reacted at 70-85℃ for 1-4 hours to obtain a vinyl fluorine-containing organometallic intermediate.

[0020] S3: Under a nitrogen atmosphere, add 50-100 parts of tourmaline ceramic balls treated with mercaptosilane, 0.05-0.4 parts of 1-vinyl-3-ethylimidazolium hexafluorophosphate (1034364-43-6), 7-11 parts of triethylamine, and 600-800 parts of N-methyl-2-pyrrolidone to a reactor. Stir at 70-80°C for 40-70 minutes, then add the vinyl fluorinated organometallic intermediate prepared in S2. Stir at 70-80°C for 40-60 hours, filter, and then vacuum dry at 50-80°C for 12-36 hours to obtain a tourmaline ceramic ball-supported organometallic antimony fluorination catalyst.

[0021] In the above technical solution, the further preparation method of the tourmaline ceramic balls treated with mercaptosilane is as follows:

[0022] According to the mass fraction, take 150-240 parts of tourmaline ceramic balls and dissolve them in 1000-1500 parts of water, add 4-7 parts of mercaptosilane, react at 30-45℃ for 40-150 minutes, filter, dry, and obtain mercaptosilane-treated tourmaline ceramic balls.

[0023] In the above technical solution, the mercaptosilane is further selected from one or more of mercaptopropyltrimethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptomethyltrimethoxysilane, mercaptomethyldimethoxymethylsilane, and mercaptoethyldimethoxymethylsilane.

[0024] In the above technical solution, the supported catalyst can be reused.

[0025] The reaction mechanism for the preparation of the above-mentioned supported catalysts:

[0026] The catalyst used is a tourmaline ceramic ball treated with mercaptosilane. The mercapto group of the ball first undergoes an addition reaction with 1-vinyl-3-ethylimidazolium hexafluorophosphate, and then undergoes a mercapto-ethylene addition reaction with a vinyl fluorinated organometallic intermediate to obtain a tourmaline ceramic ball supported on organometallic antimony fluorination catalyst.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The process flow adopted in this method is simple, avoiding cumbersome operations, shortening the reaction time and reducing the reaction temperature, thereby improving production efficiency.

[0029] (2) This method uses hexafluoropropylene trimer as a solvent to prepare methyl perfluorobutyl ether with fluorine gas and heptafluoroisobutylene methyl ether. The hexafluoropropylene trimer can be recycled and reused, which is green and environmentally friendly.

[0030] (3) The methyl perfluorobutyl ether product prepared by this method has high purity and the reaction yield can reach more than 75%.

[0031] (4) The fluorination catalyst of organometallic antimony supported on tourmaline ceramic balls can be easily separated. At the same time, its tetrafluoroalkyl group has good compatibility with the reactants, and its structure is conducive to the enrichment of heptafluoroisobutylene methyl ether on the catalyst surface and micropores, which can effectively improve the catalytic effect and shorten the reaction time.

[0032] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined with each other to obtain various preferred embodiments of the present invention. Detailed Implementation

[0033] The present invention will be further described below with reference to specific embodiments, but the invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all alternatives, improvements, and equivalents that may be included within the scope of the claims.

[0034] <Example 1>

[0035] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0036] S1: Add 100g of heptafluoroisobutylene methyl ether, 30g of perfluorocarbon, and 30g of supported catalyst to the fluorination reactor. Turn on the reactor and stir. Cool the reactor and slowly introduce a fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0037] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0038] The perfluorocarbon described in this specific embodiment is a hexafluoropropylene trimer.

[0039] The temperature of the reactor in this specific embodiment is -45℃.

[0040] In this specific embodiment, the fluorine concentration in the fluorine-nitrogen mixed gas is 5 wt%.

[0041] In this specific embodiment, the set molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is 1:0.6.

[0042] In this specific embodiment, the reaction continues for 30 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.

[0043] The supported catalyst in this specific embodiment is a fluorinated catalyst of organometallic antimony supported on tourmaline ceramic spheres, and its preparation method is as follows:

[0044] S1: Dissolve 5g of antimony pentachloride in 100g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;

[0045] S2: 13g of 3-vinyl-2-methylpyridine, 120g of N-methyl-2-pyrrolidone, and 3g of 20% hydrochloric acid were added to a stirred tank and stirred at 70°C for 50 min. Then, the metal ion solution prepared in S1 was poured into the ligand solution and mixed. The mixture was then added to a hydrothermal reactor and reacted at 70°C for 1 hour to obtain a vinyl fluorine-containing organometallic intermediate.

[0046] S3: Under a nitrogen atmosphere, 50g of tourmaline ceramic balls treated with mercaptosilane, 0.1g of 1-vinyl-3-ethylimidazolium hexafluorophosphate (1034364-43-6), 7g of triethylamine, and 600g of N-methyl-2-pyrrolidone were added to a reactor. The mixture was stirred at 70°C for 40 minutes, and then the vinyl fluorinated organometallic intermediate prepared in S2 was added. The mixture was stirred at 70°C for 40 hours, filtered, and then vacuum dried at 50°C for 12 hours to obtain a tourmaline ceramic ball-supported organometallic antimony fluorination catalyst.

[0047] The method for preparing the mercaptosilane-treated tourmaline ceramic balls in this specific embodiment is as follows:

[0048] Dissolve 150g of tourmaline ceramic balls in 1000g of water, add 4g of mercaptosilane, react at 30℃ for 40 minutes, filter, and dry to obtain mercaptosilane-treated tourmaline ceramic balls.

[0049] The mercaptosilane described in this specific embodiment is selected from mercaptopropyltrimethoxysilane.

[0050] Analysis and calculation show that the yield of methyl perfluorobutyl ether prepared by this method is 83.8%, and the purity of the product is 99.94%.

[0051] <Example 2>

[0052] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0053] S1: Add 200g of heptafluoroisobutylene methyl ether, 400g of perfluorocarbon, and 40g of supported catalyst to the fluorination reactor. Turn on the reactor and stir. Cool the reactor and slowly introduce a fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0054] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0055] The perfluorocarbon described in this specific embodiment is a hexafluoropropylene trimer.

[0056] In this specific embodiment, the temperature of the reactor is -15℃.

[0057] In this specific embodiment, the fluorine concentration in the fluorine-nitrogen mixed gas is 10 wt%.

[0058] In this specific embodiment, the set molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is 1:0.8.

[0059] In this specific embodiment, the reaction continues for 20 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.

[0060] The supported catalyst in this specific embodiment is a fluorinated catalyst of organometallic antimony supported on tourmaline ceramic spheres, and its preparation method is as follows:

[0061] S1: Dissolve 9g of antimony pentachloride in 125g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;

[0062] S2: 19g of 3-vinyl-2-methylpyridine, 160g of N-methyl-2-pyrrolidone, and 4.5g of 25% hydrochloric acid were added to a stirred tank and stirred at 75°C for 75 min. Then, the metal ion solution prepared in S1 was poured into the ligand solution and mixed. The mixture was then added to a hydrothermal reactor and reacted at 78°C for 3 hours to obtain a vinyl fluorine-containing organometallic intermediate.

[0063] S3: Under a nitrogen atmosphere, 75g of tourmaline ceramic balls treated with mercaptosilane, 0.2g of 1-vinyl-3-ethylimidazolium hexafluorophosphate (1034364-43-6), 9g of triethylamine, and 700g of N-methyl-2-pyrrolidone were added to a reactor. The mixture was stirred at 75°C for 55 minutes, and then the vinyl fluorinated organometallic intermediate prepared in S2 was added. The mixture was stirred at 75°C for 50 hours, filtered, and then vacuum dried at 65°C for 24 hours to obtain a tourmaline ceramic ball-supported organometallic antimony fluorination catalyst.

[0064] The method for preparing the mercaptosilane-treated tourmaline ceramic balls in this specific embodiment is as follows:

[0065] Dissolve 195g of tourmaline ceramic balls in 1250g of water, add 6g of mercaptosilane, react at 35℃ for 90 minutes, filter, and dry to obtain mercaptosilane-treated tourmaline ceramic balls.

[0066] The mercaptosilane described in this specific embodiment is selected from mercaptopropyl dimethoxymethylsilane.

[0067] Analysis and calculation show that the yield of methyl perfluorobutyl ether prepared by this method is 87.5%, and the purity of the product is 99.97%.

[0068] <Example 3>

[0069] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0070] S1: Add 300g of heptafluoroisobutylene methyl ether, 500g of perfluorocarbon, and 50g of supported catalyst to the fluorination reactor. Start the reactor stirring, cool the reactor, and slowly introduce a fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0071] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0072] The perfluorocarbon described in this specific embodiment is a hexafluoropropylene trimer.

[0073] The temperature of the reactor in this specific embodiment is 5°C.

[0074] In this specific embodiment, the fluorine concentration in the fluorine-nitrogen mixed gas is 15 wt%.

[0075] In this specific embodiment, the set molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is 1:0.9.

[0076] In this specific embodiment, the reaction continues for 10 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.

[0077] The supported catalyst in this specific embodiment is a fluorinated catalyst of organometallic antimony supported on tourmaline ceramic spheres, and its preparation method is as follows:

[0078] S1: Dissolve 12g of antimony pentachloride in 150g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;

[0079] S2: 26g of 3-vinyl-2-methylpyridine, 200g of N-methyl-2-pyrrolidone, and 6g of 30% hydrochloric acid were added to a stirred tank and stirred at 80°C for 100 min. Then, the metal ion solution prepared in S1 was poured into the ligand solution and mixed. The mixture was then added to a hydrothermal reactor and reacted at 85°C for 4 hours to obtain a vinyl fluorine-containing organometallic intermediate.

[0080] S3: Under a nitrogen atmosphere, 100g of tourmaline ceramic balls treated with mercaptosilane, 0.4g of 1-vinyl-3-ethylimidazolium hexafluorophosphate (1034364-43-6), 11g of triethylamine, and 800g of N-methyl-2-pyrrolidone were added to a reactor. The mixture was stirred at 80°C for 70 minutes, and then the vinyl fluorinated organometallic intermediate prepared in S2 was added. The mixture was stirred at 80°C for 60 hours, filtered, and then vacuum dried at 80°C for 36 hours to obtain a tourmaline ceramic ball-supported organometallic antimony fluorination catalyst.

[0081] The method for preparing the mercaptosilane-treated tourmaline ceramic balls in this specific embodiment is as follows:

[0082] Dissolve 240g of tourmaline ceramic balls in 1500g of water, add 7g of mercaptosilane, react at 45℃ for 150 minutes, filter, and dry to obtain mercaptosilane-treated tourmaline ceramic balls.

[0083] The mercaptosilane described in this specific embodiment is selected from mercaptomethyldimethoxymethylsilane.

[0084] Analysis and calculation show that the yield of methyl perfluorobutyl ether prepared by this method is 88.0%, and the purity of the product is 99.98%.

[0085] <Comparative Example 1>

[0086] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0087] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0088] S1: Add 100g of heptafluoroisobutylene methyl ether, 30g of perfluorocarbon, and 30g of antimony fluoride to the fluorination reactor, start stirring in the reactor, cool the reactor, and slowly introduce a fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0089] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0090] The perfluorocarbon described in this specific embodiment is a hexafluoropropylene trimer.

[0091] The temperature of the reactor in this specific embodiment is -45℃.

[0092] In this specific embodiment, the fluorine concentration in the fluorine-nitrogen mixed gas is 5 wt%.

[0093] In this specific embodiment, the set molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is 1:0.6.

[0094] In this specific embodiment, the reaction continues for 30 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.

[0095] Analysis and calculation show that the yield of methyl perfluorobutyl ether prepared by this method is 69.1%, and the purity of the product is 99.88%.

[0096] <Comparative Example 2>

[0097] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0098] S1: Add 100g of heptafluoroisobutylene methyl ether, 30g of perfluorocarbon, and 30g of supported catalyst to the fluorination reactor. Turn on the reactor and stir. Cool the reactor and slowly introduce a fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0099] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0100] The perfluorocarbon described in this specific embodiment is a hexafluoropropylene trimer.

[0101] The temperature of the reactor in this specific embodiment is -45℃.

[0102] In this specific embodiment, the fluorine concentration in the fluorine-nitrogen mixed gas is 5 wt%.

[0103] In this specific embodiment, the set molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is 1:0.6.

[0104] In this specific embodiment, the reaction continues for 30 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.

[0105] The supported catalyst in this specific embodiment is a fluorinated catalyst of organometallic antimony supported on tourmaline ceramic spheres, and its preparation method is as follows:

[0106] S1: Dissolve 5g of antimony pentachloride in 100g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;

[0107] S2: 13g of 3-vinyl-2-methylpyridine, 120g of N-methyl-2-pyrrolidone, and 3g of 20% hydrochloric acid were added to a stirred tank and stirred at 70°C for 50 min. Then, the metal ion solution prepared in S1 was poured into the ligand solution and mixed. The mixture was then added to a hydrothermal reactor and reacted at 70°C for 1 hour to obtain a vinyl fluorine-containing organometallic intermediate.

[0108] S3: Under a nitrogen atmosphere, 50g of tourmaline ceramic balls treated with mercaptosilane, 7g of triethylamine, and 600g of N-methyl-2-pyrrolidone were added to a reactor and stirred at 70°C for 40 minutes. Then, the vinyl fluorinated organometallic intermediate prepared in S2 was added and stirred at 70°C for 40 hours. The mixture was filtered and then vacuum dried at 50°C for 12 hours to obtain a tourmaline ceramic ball-supported organometallic antimony fluorination catalyst.

[0109] The method for preparing the mercaptosilane-treated tourmaline ceramic balls in this specific embodiment is as follows:

[0110] Dissolve 150g of tourmaline ceramic balls in 1000g of water, add 4g of mercaptosilane, react at 30℃ for 40 minutes, filter, and dry to obtain mercaptosilane-treated tourmaline ceramic balls.

[0111] The mercaptosilane described in this specific embodiment is selected from mercaptopropyltrimethoxysilane.

[0112] Analysis and calculation show that the yield of methyl perfluorobutyl ether prepared by this method is 78.3%, and the purity of the product is 99.92%.

[0113] <Comparative Example 3>

[0114] A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized by comprising the following steps:

[0115] S1: Add 100g of heptafluoroisobutylene methyl ether, 30g of perfluorocarbon, and 30g of supported catalyst to the fluorination reactor. Turn on the reactor and stir. Cool the reactor and slowly introduce a fluorine-nitrogen mixed gas to carry out the fluorination reaction.

[0116] S2: When the molar ratio of heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches the set ratio, stop the introduction of the fluorine-nitrogen mixed gas, maintain the temperature and continue the reaction for a period of time, raise the temperature of the reactor to room temperature, remove the tail gas, filter the reaction liquid, and distill to obtain methyl perfluorobutyl ether.

[0117] The perfluorocarbon described in this specific embodiment is a hexafluoropropylene trimer.

[0118] The temperature of the reactor in this specific embodiment is -45℃.

[0119] In this specific embodiment, the fluorine concentration in the fluorine-nitrogen mixed gas is 5 wt%.

[0120] In this specific embodiment, the set molar ratio of heptafluoroisobutylene methyl ether to fluorine gas is 1:0.6.

[0121] In this specific embodiment, the reaction continues for 30 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.

[0122] The supported catalyst in this specific embodiment is a fluorinated catalyst of organometallic antimony supported on tourmaline ceramic spheres, and its preparation method is as follows:

[0123] S1: Dissolve 5g of antimony pentachloride in 100g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;

[0124] S2: 13g of 3-vinyl-2-methylpyridine, 120g of N-methyl-2-pyrrolidone, and 3g of 20% hydrochloric acid were added to a stirred tank and stirred at 70°C for 50 min. Then, the metal ion solution prepared in S1 was poured into the ligand solution and mixed. The mixture was then added to a hydrothermal reactor and reacted at 70°C for 1 hour to obtain a vinyl fluorine-containing organometallic intermediate.

[0125] S3: Under a nitrogen atmosphere, 50g of tourmaline ceramic balls treated with mercaptosilane, 0.1g of 1-vinyl-3-ethylimidazolium hexafluorophosphate (1034364-43-6), 7g of triethylamine, and 600g of N-methyl-2-pyrrolidone were added to a reactor. The mixture was stirred at 70°C for 40 minutes, and then the vinyl fluorinated organometallic intermediate prepared in S2 was added. The mixture was stirred at 70°C for 40 hours, filtered, and then vacuum dried at 50°C for 12 hours to obtain a tourmaline ceramic ball-supported organometallic antimony fluorination catalyst.

[0126] The method for preparing the mercaptosilane-treated tourmaline ceramic balls in this specific embodiment is as follows:

[0127] Dissolve 150g of tourmaline ceramic balls in 1000g of water, add 4g of mercaptosilane, react at 30℃ for 40 minutes, filter, and dry to obtain mercaptosilane-treated tourmaline ceramic balls.

[0128] The mercaptosilane described in this specific embodiment is selected from mercaptopropyltrimethoxysilane.

[0129] Analysis and calculation show that the yield of methyl perfluorobutyl ether prepared by this method is 77.9%, and the purity of the product is 99.91%.

[0130] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A catalytic process for the preparation of methyl perfluorobutyl ether from hexafluoropropylene trimer, characterized in that: The method comprises the following steps: S1: according to weight parts, 100-300 parts of heptafluoroisobutenyl methyl ether and 300-500 parts of hexafluoropropylene trimer are put into a fluorination reactor, 30-50 parts of a supported catalyst is put in, the reactor is started to stir, the reactor is cooled, and fluorine-nitrogen mixed gas is slowly introduced for fluorination reaction; S2: when the molar ratio of heptafluoroisobutenyl methyl ether to the introduced fluorine gas reaches a set ratio, the fluorine-nitrogen mixed gas is stopped, the temperature is kept to continue the reaction for a period of time, the reactor is warmed to room temperature, the tail gas is removed, the reaction liquid is filtered, and methyl perfluorobutyl ether is obtained by rectification; The supported catalyst is a fluorination catalyst of tourmaline ceramic ball loaded with organic metal antimony, and a preparation method thereof is as follows: A1: according to mass parts, 5-12 parts of antimony pentachloride is dissolved in 100-150 parts of N-methyl-2-pyrrolidone to prepare a metal ion solution; A2: according to mass parts, 13-26 parts of 3-vinyl-2-methylpyridine, 120-200 parts of N-methyl-2-pyrrolidone and 3-6 parts of 20-30% mass percentage hydrochloric acid are added into a stirring kettle, stirred at 70-80 DEG C for 50-100 min, then the metal ion solution prepared in A1 is poured into the ligand solution, and then added into a hydrothermal reaction kettle, and reacted at 70-85 DEG C for 1-4 hours to obtain a vinyl organic metal intermediate; A3: under a nitrogen atmosphere, 50-100 parts of tourmaline ceramic balls treated by mercapto silane, 0.05-0.4 parts of 1-vinyl-3-ethyl imidazole hexafluorophosphate (1034364-43-6), 7-11 parts of triethylamine, 600-800 parts of N-methyl-2-pyrrolidone are added into a reaction kettle, stirred at 70-80 DEG C for 40-70 min, then the vinyl organic metal intermediate prepared in A2 is added, stirred at 70-80 DEG C for 40-60 hours, filtered, and then vacuum dried at 50-80 DEG C for 12-36 hours to obtain the fluorination catalyst of tourmaline ceramic ball loaded with organic metal antimony.

2. A process according to claim 1 for the preparation of methyl perfluorobutyl ether by the catalytic trimerization of hexafluoropropene, characterized in that, The temperature of the reactor is -45-5 DEG C.

3. A process for the preparation of methyl perfluorobutyl ether from hexafluoropropene trimer according to claim 1, characterized in that: The fluorine concentration in the fluorine-nitrogen mixed gas is 5-15 wt%.

4. A process for the preparation of methyl perfluorobutyl ether from hexafluoropropene trimer according to claim 1, characterized in that: The set molar ratio of heptafluoroisobutenyl methyl ether to fluorine gas is 1:0.6-0.

9.

5. A process for the preparation of methyl perfluorobutyl ether from hexafluoropropene trimer according to claim 1, characterized in that: The reaction continues for 10-30 min after the fluorine-nitrogen mixed gas is stopped.

6. A process for the preparation of methyl perfluorobutyl ether from hexafluoropropene trimer according to claim 1, characterized in that: The preparation method of the tourmaline ceramic balls treated by mercapto silane is as follows: According to mass parts, 150-240 parts of tourmaline ceramic balls are dissolved in 1000-1500 parts of water, 4-7 parts of mercapto silane is added, reacted at 30-45 DEG C for 40-150 min, filtered, dried, and tourmaline ceramic balls treated by mercapto silane are prepared.

7. A process according to claim 1 for the preparation of methyl perfluorobutyl ether by the catalytic trimerization of hexafluoropropene, characterized in that: The mercapto silane is one or more of mercaptopropyl trimethoxysilane, mercaptopropyl dimethoxymethyl silane, mercaptomethyl trimethoxysilane, mercaptomethyl dimethoxymethyl silane and mercaptoethyl dimethoxymethyl silane.

8. A process according to claim 1 for the preparation of methyl perfluorobutyl ether by the catalytic trimerization of hexafluoropropene, characterized in that: The supported catalyst can be repeatedly used.