Perfluoroketone compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of fluorine-containing chemicals, and provides a perfluoroketone compound as well as a preparation method and application thereof, the structural formula of the perfluoroketone compound is as shown in # imgabs0 #, and Rf1, Rf2 and Rf3 are the same or different and are independently selected from C1-C8 straight-chain or branched-chain perfluoroalkyl groups. The perfluoroketone has the beneficial effects that the carbon number of the perfluoroketone is controllable, and perfluoroketones with different boiling points can be obtained according to requirements; according to the method for preparing the perfluoroketone compound, the adopted raw materials are low in cost, good in safety and stability, non-toxic, harmless and easy to store, the reaction process is controllable, the selectivity is high, products are easy to separate, aftertreatment is simple, and the method is suitable for actual technological production; the perfluoroketone provided by the invention has a relatively low dielectric constant and relatively good heat transfer performance, is non-combustible, and has a very good application prospect in the aspects of semiconductors, refrigeration systems and fire fighting.

Description

Technical Field

[0001] The present application belongs to the technical field of fluorine-containing chemicals, and in particular relates to a perfluoroketone compound and a preparation method and application thereof. Background Art

[0002] Perfluoroketone has a low dielectric constant and good heat transfer performance, is almost non-toxic, non-flammable, has no unstable double bonds and a perfect temperature range, and a greenhouse effect potential (GWP) value of 1. It can be widely used in computer rooms, data centers, 5G base stations, semiconductors, aviation, ships, vehicles, refrigeration systems, fire protection and other places.

[0003] In the prior art, there are three main routes for the synthesis of perfluoroketones: the first route is the addition reaction of perfluoroolefins and acyl fluorides, specifically, in anhydrous diethylene glycol dimethyl ether solvent, pentafluoropropionyl fluoride and hexafluoropropylene react to obtain pentafluoroethyl perfluoroisopropyl ketone, with a yield of 20-63.5%; the second route is the free radical reaction of perfluoroolefins, specifically, perfluoro 2,3-dimethyl-2-butene can quickly generate trifluoromethyl perfluoroisopropyl ketone through photochemical free radical reaction, with a yield of 48%. However, photochemical free radical reactions generally exist in the atmosphere, and the reaction products are extremely complex, so they do not have industrial value; the third route is a thermal decomposition reaction under reflux conditions, specifically, perfluoro 4-methyl-2,3-butanedione is heated under conditions, with cesium fluoride as a catalyst, and reacts for 1 hour to obtain trifluoromethyl perfluoroisopropyl ketone, with a yield of 76%. In this route, the starting materials are not easy to obtain, and the industrial value is not high.

[0004] In summary, the existing technologies have the following problems: (1) Although the raw materials of the first route are easy to obtain, the acyl fluoride used is explosive, highly toxic, and has high storage requirements; (2) The free radical reaction used in the second route is difficult to control the reaction process and difficult to operate; (3) The third route produces too many types of fragments by pyrolysis, which greatly reduces the selectivity of the target product. Summary of the invention

[0005] The purpose of the present application is to provide a perfluoroketone compound and a preparation method and application thereof, aiming to solve the problems of difficult acquisition of raw materials, safety issues and uncontrollable reactions in the preparation process of perfluoroketone.

[0006] In order to achieve the above application purpose, the technical solution adopted in this application is as follows:

[0007] In a first aspect of the present application, a perfluoroketone compound is provided, the structural formula of which is shown below:

[0008]

[0009] Wherein, Rf1, Rf2, and Rf3 are the same or different, and are independently selected from a C1-C8 straight chain or branched perfluoroalkyl group.

[0010] According to some embodiments of the perfluoroketone compound described in the present application, the compounds include the following structural formulas I-1 to I-6:

[0011]

[0012] In a second aspect of the present application, a method for preparing a perfluoroketone compound is provided, comprising the following steps:

[0013] Compound A and compound B are subjected to an aldol condensation reaction to obtain an intermediate product;

[0014] The intermediate product is subjected to a fluorination reaction to obtain a perfluoroketone;

[0015] The structural formula of the compound A is shown below:

[0016]

[0017] The structural formula of the compound B is shown below:

[0018]

[0019] Wherein: Rf1, Rf2, and Rf3 are the same or different, and are independently selected from a C1-C8 straight chain or branched perfluoroalkyl group.

[0020] According to some embodiments of the preparation method described in the present application, the compound A includes one or more of methyl perfluoroethyl ketone, methyl perfluoropropyl ketone, methyl perfluorobutyl ketone, methyl perfluoropentyl ketone, methyl perfluorohexyl ketone, and methyl perfluoroheptyl ketone.

[0021] According to some embodiments of the preparation method described in the present application, the compound B includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, perfluoroheptanone, perfluorooctanone, and perfluorononanone.

[0022] According to some embodiments of the preparation method described in the present application, the catalyst includes a basic catalyst or an acidic catalyst.

[0023] According to some embodiments of the preparation method described in the present application, the aldol condensation reaction is carried out in a non-protonic polar solvent.

[0024] According to some embodiments of the preparation method described in the present application, the alkaline catalyst includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, sodium acetonitrile, sodium acetate, triethylamine, triethylenediamine, aniline, and alkaline anion exchange resin.

[0025] According to some embodiments of the preparation method described in the present application, the acidic catalyst includes one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and acidic cation exchange resin.

[0026] According to some embodiments of the preparation method described in the present application, the aprotic polar solvent includes one or more of acetonitrile, dichloromethane, chloroform, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, NN dimethylformamide, dimethyl sulfoxide, cyclopentane, and tetrahydrofuran.

[0027] According to some embodiments of the preparation method described in the present application, the molar ratio of the compound A to the compound B is 1:(1-1.5).

[0028] According to some embodiments of the preparation method described in the present application, the molar ratio of the compound A to the catalyst is 1:(0.2-0.5).

[0029] According to some embodiments of the preparation method described in the present application, the temperature of the aldol condensation reaction is 30° C.-60° C., and the reaction time is 0.5 h-2 h.

[0030] According to some embodiments of the preparation method described in the present application, the preparation method also includes the step of purifying the reaction mixed solution containing the intermediate product: allowing the reaction mixed solution containing the intermediate product to stand for stratification, collecting the lower layer solution and washing it with water until the pH value is neutral, combining the water washings for distillation, and collecting fractions with boiling points higher than the boiling points of compound A and compound B.

[0031] According to some embodiments of the preparation method described in the present application, the fluorination includes fluorination using fluorine gas.

[0032] According to some embodiments of the preparation method described in the present application, the preparation method further comprises washing the fluorinated product with water to remove fluorine, drying and filtering to obtain perfluoroketone.

[0033] The third aspect of the present application provides an application of the perfluoroketone compound described in the first aspect of the present application or the perfluoroketone compound obtained by the preparation method described in the second aspect of the present application in semiconductors, refrigeration systems and fire protection.

[0034] Compared with the prior art, the beneficial effects of this application are:

[0035] 1. The perfluoroketone described in this application has a higher boiling point and higher industrial application value.

[0036] 2. The method for preparing perfluoroketone compounds of the present application selects C1-C8 straight-chain or branched perfluoroalkyl groups with relatively more fluorine atoms, and the prepared perfluoro compounds have a relatively high fluorine content, thereby further improving the boiling point and stability of the perfluoro compounds. The method for preparing perfluoroketone compounds of the present application has a controllable reaction process, high selectivity, easy separation of products, and the selected raw materials are safe and easy to obtain, and the post-processing is simple, which is suitable for actual process production.

[0037] 3. When the perfluoroketone described in this application is applied to semiconductors, refrigeration systems and fire protection, the corresponding products have better flame retardant properties and heat transfer properties because the perfluoroketone has a higher boiling point and stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is the infrared spectrum of perfluorocarbon undecone prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0039] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0040] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0041] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0042] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0043] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0044] The moles of the relevant components mentioned in the embodiments of the present application may not only refer to the specific content of each component, but also indicate the molar ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiments of the present application, it is within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the embodiments of the present application may be μg, mg, g, kg, or other mass units known in the chemical industry.

[0045] In a first aspect of the embodiments of the present application, a perfluoroketone compound is provided, the structural formula of which is shown below:

[0046]

[0047] Wherein, Rf1, Rf2, and Rf3 are the same or different and are independently selected from a C1-C8 straight chain or branched perfluoroalkyl group. The perfluoroketone described in the present application has a higher boiling point and a higher industrial application value.

[0048] In some embodiments of the present application, the structural formula of the perfluoroketone compound includes the compounds shown in the following structural formulas I-1 to I-3:

[0049]

[0050] The perfluoroketone compounds shown in these structural formulas have relatively high boiling points and good stability.

[0051] A second aspect of the embodiments of the present application provides a method for preparing a perfluoroketone compound, comprising the following steps:

[0052] S10: subjecting compound A to an aldol condensation reaction with compound B to obtain an intermediate product;

[0053] S20: The intermediate product is subjected to a fluorination reaction to obtain a perfluoroketone.

[0054] The structural formula of compound A in step S10 is as follows:

[0055]

[0056] The structural formula of compound B is shown below:

[0057]

[0058] Rf1 in the structural formula of compound A and Rf2 and Rf3 in the structural formula of compound B are the same or different, and are independently selected from C1-C8 straight chain or branched perfluoroalkyl groups. The C1-C8 straight chain or branched perfluoroalkyl groups contain more fluorine atoms, and the prepared perfluoro compound has a relatively high fluorine content, thereby further improving the boiling point and stability of the perfluoro compound.

[0059] When compound A reacts with compound B, the α-carbon atom provided by compound A loses a hydrogen atom to form a carbon anion resonance hybrid, which then undergoes nucleophilic addition with the carbonyl group of another ketone molecule to form a new carbon-carbon single bond to obtain β-hydroxy ketone, which is then dehydrated to form a double bond and then fluorinated to obtain a perfluoroketone.

[0060] Alternatively, when compound A and compound B react, the α-carbon atom provided by compound A loses a hydrogen atom to generate an enolate, which then undergoes nucleophilic addition with the carbonyl group of another ketone molecule to form a new carbon-carbon single bond to obtain a β-hydroxy ketone, which is then dehydrated to generate a double bond and then fluorinated to obtain a perfluoroketone.

[0061] In addition, the method for preparing perfluoroketone compounds of the present application has a controllable reaction process, high selectivity, easy separation of products, safe and readily available raw materials, simple post-processing, and is suitable for actual process production.

[0062] In some embodiments of the present application, compound A includes one or more of methyl perfluoroethyl ketone, methyl perfluoropropyl ketone, methyl perfluorobutyl ketone, methyl perfluoropentyl ketone, methyl perfluorohexyl ketone, and methyl perfluoroheptyl ketone. The above raw materials are easily available on the market and help to ensure the stability of the reaction process.

[0063] In some embodiments of the present application, compound B includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, perfluoroheptanone, perfluorooctanone, and perfluorononanone. The above raw materials are easily available on the market and are more conducive to the aldol condensation reaction.

[0064] In some embodiments of the present application, the catalyst includes a basic catalyst or an acidic catalyst.

[0065] In some embodiments of the present application, the alkaline catalyst includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, sodium acetonitrile, sodium acetate, triethylamine, triethylenediamine, aniline, and alkaline anion exchange resin; under alkaline conditions, the α-carbon atom loses a hydrogen atom to form a carbon anion resonance hybrid, which then undergoes nucleophilic addition with the carbonyl of another ketone molecule to form a new carbon-carbon single bond to obtain a β-hydroxy ketone, which is dehydrated to form a double bond. In some embodiments, the alkaline anion exchange resin can be selected from D201 anion exchange resin and / or D301 anion exchange resin. The selected raw materials are cheap and readily available, which can further promote the aldol condensation reaction and make the reaction more thorough.

[0066] In some embodiments of the present application, the acidic catalyst includes one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and acidic cation exchange resin. Under acidic conditions, the α-carbon atom loses a hydrogen atom to generate an enolate, which then undergoes nucleophilic addition with the carbonyl group of another ketone molecule to form a new carbon-carbon single bond to obtain a β-hydroxy ketone, which is dehydrated to generate a double bond. In some embodiments, the acidic cation exchange resin can be selected from D001 cation exchange resin and / or D111 cation exchange resin; the selected raw materials are cheap and readily available, which can further promote the aldol condensation reaction and make the reaction more thorough.

[0067] In some embodiments of the present application, the aldol condensation reaction is carried out in an aprotic polar solvent, and the aprotic polar solvent includes one or more of acetonitrile, dichloromethane, chloroform, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, NN dimethylformamide, dimethyl sulfoxide, cyclopentane, and tetrahydrofuran. The above-mentioned aprotic polar solvent has high polarity, good solubility, no proton effect, and low cost.

[0068] In some embodiments of the present application, the molar ratio of compound A to compound B is 1:(1-1.5), for example 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.; because compound A may undergo self-condensation, increasing the dosage of compound B can increase the yield.

[0069] In some embodiments of the present application, the molar ratio of compound A to the catalyst is 1:(0.2-0.5), optionally, for example, 1:0.2, 1:0.3, 1:0.4, 1:05, etc.; the catalyst in this ratio range can effectively improve the reaction efficiency of the aldol condensation reaction, reduce the formation of side reaction products, and increase the yield of the target product.

[0070] In some embodiments of the present application, the molar ratio of compound A to aprotic polar solvent is 1:(2-4), such as 1:2, 1:2.5, 1:3, 1:4. The solvent in this ratio range can effectively improve the dispersion uniformity of compound A and reactant B in the reaction system, assist the reaction efficiency between the reactants, reduce side reaction products, and improve the yield of the target product.

[0071] In some embodiments of the present application, the temperature of the aldol condensation reaction is 30°C-60°C, such as 30°C, 35°C, 38°C, 40°C, 45°C, 50°C, 56°C, 60°C, etc., and the reaction time is 0.5h-2h, such as 0.5h, 0.8h, 1.2h, 1.6h, 1.8h, 2h, etc. Within an appropriate range, increasing the temperature will increase the reaction rate, but the reaction is an exothermic reaction, and too high a temperature will reduce the reaction yield.

[0072] In some embodiments of the present application, the preparation method also includes the step of purifying the reaction mixed solution containing the intermediate product: allowing the reaction mixed solution containing the intermediate product to stand and separate into layers, collecting the lower layer solution and washing it with water until the pH value is neutral, combining the washing liquids for distillation, and collecting the fractions with a boiling point higher than the boiling point of compound A and the boiling point of compound B.

[0073] In some embodiments of the present application, the fluorination includes fluorination using fluorine gas.

[0074] In some embodiments of the present application, the preparation method further comprises collecting the fluorination product and washing it with water to remove fluorine, drying and filtering it to obtain perfluoroketone.

[0075] In some embodiments of the present application, the reaction equation for preparing the perfluoroketone compound is:

[0076]

[0077] Compound A and compound B dissolved in a non-protonic polar solvent are reacted under the action of a catalyst (the catalyst provides OH-), and the α-carbon atom provided by compound A loses a hydrogen atom to form a carbon anion resonance hybrid, which then undergoes nucleophilic addition with the carbonyl group of another ketone molecule to form a new carbon-carbon single bond to obtain β-hydroxy ketone, which is then dehydrated to form a double bond, and then fluorinated to obtain a perfluoroketone;

[0078] Alternatively, compound A and compound B dissolved in a non-protonic polar solvent are reacted under the action of a catalyst (the catalyst provides H+), and the α-carbon atom provided by compound A loses a hydrogen atom to form an enolate, which then undergoes nucleophilic addition with the carbonyl group of another ketone molecule to form a new carbon-carbon single bond to obtain a β-hydroxy ketone, which is then dehydrated to form a double bond and then fluorinated to obtain a perfluoroketone.

[0079] A third aspect of the embodiments of the present application provides an application of the perfluoroketone compound of the first aspect of the present application or the perfluoroketone compound obtained by the preparation method of the second aspect of the present application in semiconductors, refrigeration systems and fire protection.

[0080] Specific implementation cases:

[0081] Example 1

[0082] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0083]

[0084] The preparation method of the perfluoroketone compound comprises the following steps:

[0085] (1) Feeding reaction: Weigh 1 mol of methyl perfluoropropyl ketone (212.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0086] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and the washing liquid is distilled to remove the low boiling point raw materials (methyl perfluoropropyl ketone 63°C, perfluorohexanone 49°C), and the fraction with a boiling range of 140°C-155°C is collected to obtain the product 5H-perfluoro(6-isopropyl-5-octen-4-one);

[0087] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 357.71 g of the product perfluorocarbon undecone with a yield of 63.2%.

[0088] Example 2

[0089] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0090]

[0091] The preparation method of the perfluoroketone compound comprises the following steps:

[0092] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0093] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0094] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 380.07 g of the product perfluorocarbon dodecanone with a yield of 61.7%.

[0095] Example 3

[0096] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0097]

[0098] The preparation method of the perfluoroketone compound comprises the following steps:

[0099] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluoropentanone (319.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0100] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (it can be neutralized with hydrochloric acid), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluoropentanone 24° C.), and the fraction with a boiling range of 140° C.-155° C. is collected to obtain the product 4H-perfluoro(2,3-dimethyl-3-nonen-5-one);

[0101] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 364.50 g of the product perfluorocarbon undecone with a yield of 64.4%.

[0102] Example 4

[0103] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0104]

[0105] The preparation method of the perfluoroketone compound comprises the following steps:

[0106] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of triethylamine (40.48 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the triethylamine is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0107] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0108] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 312.93 g of the product perfluorocarbon dodecanone with a yield of 50.8%.

[0109] Example 5

[0110] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0111]

[0112] The preparation method of the perfluoroketone compound comprises the following steps:

[0113] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of hydrochloric acid (14.60 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the hydrochloric acid is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0114] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0115] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 275.97 g of the product perfluorocarbon dodecanone with a yield of 44.8%.

[0116] Example 6

[0117] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0118]

[0119] The preparation method of the perfluoroketone compound comprises the following steps:

[0120] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.2 mol of potassium hydroxide (11.22 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 2 h;

[0121] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0122] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 388.70 g of the product perfluorocarbon dodecanone with a yield of 63.1%.

[0123] Example 7

[0124] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0125]

[0126] The preparation method of the perfluoroketone compound comprises the following steps:

[0127] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.4 mol of perfluorohexanone (442.46 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0128] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0129] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 403.48 g of the product perfluorocarbon dodecanone with a yield of 65.5%.

[0130] Example 8

[0131] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0132]

[0133] The preparation method of the perfluoroketone compound comprises the following steps:

[0134] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 4 mol of acetonitrile (164.20 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 1 hour;

[0135] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0136] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 352.97 g of the product perfluorocarbon dodecanone with a yield of 57.3%.

[0137] Example 9

[0138] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0139]

[0140] The preparation method of the perfluoroketone compound comprises the following steps:

[0141] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 60°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 60°C, maintain a constant temperature of 60°C and stir to react for 1 hour;

[0142] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0143] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 298.76 g of the product perfluorocarbon dodecanone with a yield of 48.5%.

[0144] Example 10

[0145] A perfluoroketone compound and a preparation method thereof, wherein the perfluoroketone compound has a structural formula as shown in

[0146]

[0147] The preparation method of the perfluoroketone compound comprises the following steps:

[0148] (1) Feeding reaction: Weigh 1 mol of methyl perfluorobutyl ketone (262.07 g), 0.4 mol of potassium hydroxide (22.44 g) and 2.5 mol of acetonitrile (102.63 g) and add them to a reaction container, heat to a reaction temperature of 40°C, stir until the potassium hydroxide is completely dissolved, then add 1.2 mol of perfluorohexanone (379.25 g) preheated at 40°C, maintain a constant temperature of 40°C and stir to react for 2 hours;

[0149] (2) Purification by standing: the mixed solution obtained in step (1) is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral (hydrochloric acid can be used for neutralization), the washing liquid is combined and distilled to remove low-boiling point raw materials (methyl perfluorobutyl ketone 69° C., perfluorohexanone 49° C.), and the fraction with a boiling range of 160° C.-170° C. is collected to obtain the product 4H-perfluoro(3-isopropyl-4-nonen-5-one);

[0150] (3) Fluorination: The product obtained in (2) was fluorinated with fluorine gas, washed with water, dried over anhydrous magnesium sulfate, and filtered to finally obtain 356.66 g of the product perfluorocarbon dodecanone with a yield of 57.9%.

[0151] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A perfluoroketone compound, characterized in that Its structural formula is as follows: Wherein, Rf1, Rf2, and Rf3 are the same or different, and are independently selected from a C1-C8 straight chain or branched perfluoroalkyl group.

2. The perfluoroketone compound according to claim 1, characterized in that Including compounds represented by the following structural formula I-1 to structural formula I-6:

3. A method for preparing a perfluoroketone compound, characterized in that: The following steps are involved: Compound A and compound B are subjected to an aldol condensation reaction to obtain an intermediate product; The intermediate product is subjected to a fluorination reaction to obtain a perfluoroketone; The structural formula of the compound A is shown below: The structural formula of the compound B is shown below: Wherein: Rf1, Rf2, and Rf3 are the same or different, and are independently selected from a C1-C8 straight chain or branched perfluoroalkyl group.

4. The preparation method according to claim 3, characterized in that: The compound A includes one or more of methyl perfluoroethyl ketone, methyl perfluoropropyl ketone, methyl perfluorobutyl ketone, methyl perfluoropentyl ketone, methyl perfluorohexyl ketone, and methyl perfluoroheptyl ketone; And / or, the compound B includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, perfluoroheptanone, perfluorooctanone, and perfluorononanone; And / or, the aldol condensation reaction is carried out in the presence of a catalyst, wherein the catalyst comprises a basic catalyst or an acidic catalyst; And / or, the reactant of the aldol condensation reaction is a non-protonic polar solvent.

5. The preparation method according to claim 4, characterized in that: The alkaline catalyst includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, sodium acetonitrile, sodium acetate, triethylamine, triethylenediamine, aniline, and alkaline anion exchange resin; and / or, the acidic catalyst comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and acidic cation exchange resin; And / or, the aprotic polar solvent includes one or more of acetonitrile, dichloromethane, chloroform, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, NN dimethylformamide, dimethyl sulfoxide, cyclopentane, and tetrahydrofuran.

6. The preparation method according to any one of claims 3 to 5, characterized in that: The molar ratio of the compound A to the compound B is 1:(1-1.5); And / or, the molar ratio of the compound A to the catalyst is 1:(0.2-0.5).

7. The preparation method according to any one of claims 3 to 5, characterized in that: The temperature of the aldol condensation reaction is 30° C.-60° C., and the reaction time is 0.5 h-2 h.

8. The preparation method according to any one of claims 3 to 5, characterized in that: The preparation method further comprises the step of purifying the reaction mixture solution containing the intermediate product: The reaction mixture solution containing the intermediate product is allowed to stand for stratification, the lower layer solution is collected and washed with water until the pH value is neutral, the washing liquids are combined for distillation, and the fractions with boiling points higher than the boiling points of compound A and compound B are collected.

9. The preparation method according to any one of claims 3 to 5, characterized in that: The fluorination comprises fluorination using fluorine gas; And / or, the preparation method further comprises washing the fluorinated product with water to remove fluorine, drying and filtering to obtain perfluoroketone.

10. Use of the perfluoroketone compound according to any one of claims 1 to 2 or the perfluoroketone compound obtained by the preparation method according to any one of claims 3 to 9 in semiconductors, refrigeration systems and fire protection.

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