Perfluorophosphate allyl monomer as well as preparation method and application thereof

Abstract

The invention belongs to the field of chemical synthesis, relates to fluorine chemistry, phosphorus chemistry and photochemistry, and particularly relates to a perfluorophosphate allyl monomer as well as a preparation method and application thereof. According to the invention, commercial perfluoropropene is used as a raw material, a key intermediate iodide is synthesized by activating a C-F bond, and synthesis of the perfluoroallyl phosphate monomer containing phosphonate and double bonds is realized through a conversion reaction of the iodide. The monomer shows better prospect and potential in polymerization reaction, and provides a material basis for the development of novel perfluorosulfonic acid resin and perfluorophosphoric acid resin.

Description

Technical Field

[0001] The invention belongs to the field of chemical synthesis, relates to fluorine chemistry, phosphorus chemistry and photochemistry, and particularly refers to a novel resin monomer and a preparation method and application thereof. Background Art

[0002] As the world pays more attention to environmental protection and sustainable development, the pollution problems caused by the use of traditional fossil energy are becoming increasingly prominent, prompting people to actively seek efficient and clean new energy solutions. Among many new energy technologies, fuel cells, as an important energy conversion technology, have received widespread attention due to their high efficiency, environmental friendliness and sustainability. In particular, proton exchange membrane fuel cells (PEMFCs) have become an ideal choice for electric vehicles and other power source equipment due to their advantages such as rapid start-up, high specific energy and compact structure, showing broad application prospects.

[0003] The proton exchange membrane is the core component of PEMFC, and its performance directly affects the overall efficiency and stability of the fuel cell. High-quality proton exchange membranes not only need to have good proton conductivity and chemical stability, but also should maintain excellent performance under high temperature and low humidity conditions. However, traditional perfluorosulfonic acid resin membranes (such as DuPont's Nafion series) show defects such as rapid reduction of moisture and decreased conductivity under high temperature conditions, resulting in a reduction in the contact area between the membrane and the catalytic layer, thereby limiting the high-temperature application of proton exchange membrane fuel cells. In order to solve this problem, Chinese patent CN202211272307.8 discloses a perfluorosulfonic acid resin containing a phosphonic acid structural unit, which has low resistivity and excellent thermal stability under high temperature and low humidity. In this context, the synthesis of perfluoroolefin compounds with phosphorus-containing structural units has important scientific significance and application value. These compounds can be further used to construct new perfluorosulfonic acid resins through polymerization reactions, and even extended to the development of perfluorophosphoric acid resins. Summary of the invention

[0004] The invention provides a perfluoro phosphate ester allyl monomer and a preparation method and application thereof. A new synthesis method is proposed using perfluoropropylene as a raw material to synthesize a perfluoro allyl phosphate ester monomer containing a phosphonate and a double bond, which is used for preparing a novel perfluorosulfonic acid resin and a perfluorophosphoric acid resin.

[0005] The technical solution of the present invention is achieved in this way: The present application provides a perfluorophosphate allyl monomer having the following structural formula: .

[0006] Also provided is a method for preparing the above-mentioned perfluorophosphate allyl monomer, the technical route of which is: The synthesis principle is as follows: first, boron trichloride 1 and trifluoromethanesulfonic acid 2 are used to generate the corresponding boronic ester intermediate 3; intermediate 3 is subjected to a substitution reaction with hexafluoropropylene 4 to synthesize intermediate 5; intermediate 5 is subjected to an iodination substitution reaction to synthesize a key intermediate 6; a nucleophilic substitution reaction driven by ultraviolet light is used to allow perfluoroallyl iodide 6 to undergo a free radical substitution reaction with tetraethyl pyrophosphite 7 to prepare perfluoroallyl diethyl phosphite intermediate 8; subsequently, intermediate 8 is oxidized to synthesize the target compound 9.

[0007] The preparation steps are: (1) Adding boron trichloride to trifluoromethanesulfonic acid under vacuum and low temperature Ⅰ, and heating to react Ⅰ to obtain compound 3; (2) Compound 3 is added to hexafluoropropylene after cooling, and then added with ice water after heating to react II. The obtained reactant is separated from the organic phase and distilled under reduced pressure to obtain compound 5; (3) adding a sodium iodide solution in ethylene glycol dimethyl ether dropwise to compound 5, and reacting in the dark. The resulting reactant is washed with water, the organic phase is separated, and the resulting fraction is distilled under reduced pressure to obtain compound 6; (4) Compound 6 is added to tetraethyl pyrophosphite in a nitrogen atmosphere, and the nitrogen is removed under negative pressure. The temperature is then raised to react under light. The reaction solution is then cooled and tert-butyl peroxide is added. The reactants are reacted at room temperature, washed with water, separated, and passed through a silica gel column to obtain a perfluorophosphate allyl monomer.

[0008] Furthermore, in the above step (1), the mass ratio of boron trichloride to trifluoromethanesulfonic acid is 25:8-50.

[0009] Furthermore, the above low temperature I refers to -60°C--80°C, and the temperature of the temperature-raising reaction is 30°C and the time is 5-10 h.

[0010] Furthermore, in the above step (2), the mass ratio of compound 3 to hexafluoropropylene is 1:1-3.

[0011] Furthermore, the temperature after the above-mentioned cooling treatment is -80°C; the temperature rising reaction II is a staged temperature rising, the first stage is heated to 0°C, the reaction time is 4-10h, the second stage is heated to 10°C, the reaction time is 4-10h; the temperature of the ice water reaction is ≤25°C, and the reaction time is 30-60 min.

[0012] Furthermore, in the above step (3), the mass ratio of sodium iodide to compound 5 is 4-10:5-10; the mass concentration of sodium iodide in the ethylene glycol dimethyl ether solution of sodium iodide is 11.4%-60.6%; and the reaction time in the dark is 12-30°C.

[0013] Furthermore, in the above step (4), the mass ratio of tetraethyl pyrophosphite, compound 6 and tert-butyl peroxide is 10-20:5-10:1.7-6.8; the temperature after cooling is -78°C; the temperature of the light irradiation reaction is room temperature, the light is 254 nm wavelength, and the reaction time is 10-24h; the temperature after cooling is -20°C.

[0014] Preferably, the reaction steps in the above preparation method are all carried out under stirring conditions.

[0015] The present application also provides the use of the above-mentioned perfluorophosphate allyl monomer in the preparation of perfluorosulfonic acid resin.

[0016] The application steps are as follows: taking perfluorophosphate ester allyl monomer and pentafluorostyrene monomer as raw materials, a polymerization reaction is carried out in a trifluorotoluene solvent in the presence of an initiator to prepare a perfluorophosphate resin.

[0017] The present invention has the following beneficial effects: This application uses commercial perfluoropropylene as raw material, synthesizes the key intermediate iodide by activating the CF bond, and realizes the synthesis of a perfluoroallyl phosphate monomer containing phosphonate and double bonds through the conversion reaction of the iodide. The monomer shows good prospects and potential in the polymerization reaction, providing a material basis for the development of new perfluorosulfonic acid resins and perfluorophosphoric acid resins. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0019] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0020] Figure 2 This is the NMR fluorine spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0021] Figure 3 This is the nuclear magnetic resonance phosphorus spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0022] Figure 4 This is the carbon NMR spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0023] Figure 5 High resolution mass spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0024] Figure 6 This is the GC purity of the perfluorophosphate allyl monomer prepared in Example.

[0025] Figure 7 The following are photos and nuclear magnetic resonance phosphorus spectra of copolymer products prepared using the perfluorophosphate allyl monomer prepared in Example 1 of the present application.

[0026] Figure 8 This is the GPC spectrum of the copolymer used in the application example. DETAILED DESCRIPTION

[0027] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Unless otherwise specified, the experimental methods used in the following experimental examples are all conventional methods; the materials and reagents used are reagents and materials that can be obtained from commercial channels unless otherwise specified.

[0029] Example 1 The preparation method of the perfluorophosphate allyl monomer of this embodiment comprises the following steps: (1) CF3SO3H (50 g) was added to the autoclave, and the autoclave was evacuated. BCl3 gas (about 16 g, weighed after cooling) (purity 99.9%) was pressed into the autoclave at -80 °C, and the temperature was slowly raised to 30 °C. The pressure was controlled not to exceed 2 MPa, and the autoclave was stirred for 5 h. The pressure was slowly released, and the pressure was reduced to 1 atmosphere. The remaining gas was extracted by vacuum to obtain compound 3 as a white powdery solid, about 50 g.

[0030] (2) Compound 3 (50 g) and the autoclave were cooled to -80 °C, hexafluoropropylene 4 (about 50 g) was pressed into the autoclave, and the temperature was slowly raised to 0 °C. The mixture was stirred for 4 h, and the temperature was further raised to 10 °C for reaction for 4 h. The gas was slowly vented to release the boron trifluoride gas. When the pressure dropped to atmospheric pressure, ice water (150 mL) was slowly added and stirred for 30 min. The temperature was controlled not to exceed 25 °C. The organic phase was separated and dried to obtain a colorless transparent liquid compound 5. The mixture was distilled under reduced pressure and the 64-70 °C fraction was collected.

[0031] (3) Sodium iodide (22 g, about 2.2 eq) was dissolved in ethylene glycol dimethyl ether (50 g), and compound 5 (20 g) was slowly added dropwise. The mixture was stirred in the dark for 12 h. After the reaction was completed, the mixture was washed with water, the organic phase was separated, and vacuum distillation was performed at room temperature. The fractions were collected by low-temperature cooling to obtain compound 6.

[0032] (4) Take 10 g of tetraethyl pyrophosphite 7 and add it to a quartz bottle. Replace the atmosphere with nitrogen three times, quickly add compound 6 (5 g), quickly cool to -78 °C, remove nitrogen under negative pressure, and close the valve. Transfer the quartz bottle to a photoreactor, slowly warm it to room temperature, irradiate and stir at 254 nm for 10 h, and proceed to the next step without further treatment. Cool the reaction solution to -20 °C, slowly add 1 eq of tert-butyl peroxide (in terms of iodide), warm to room temperature, stir for 1 h, pour the reaction solution into ice water (50 mL), wash three times with water, separate the organic phase and dry it, and pass the organic phase through a silica gel column (petroleum ether: ethyl acetate = 5:1) to obtain about 4 g of compound 9 (yield 82%), which is a colorless or light yellow liquid, i.e., perfluorophosphate allylic monomer.

[0033] The obtained product was characterized and the results were as follows Figure 1-Figure 6 ; Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0034] Figure 2 This is the NMR fluorine spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0035] Figure 3 This is the nuclear magnetic resonance phosphorus spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0036] Figure 4 This is the carbon NMR spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0037] Figure 5 High resolution mass spectrum of the perfluorophosphate allyl monomer prepared in Example.

[0038] Figure 6 The GC purity of the perfluorophosphate allyl monomer prepared in the example was shown to be >99%.

[0039] Example 2 The preparation method of the perfluorophosphate allyl monomer of this embodiment comprises the following steps: CF3SO3H (50 g) was added to the autoclave, and the autoclave was evacuated. BCl3 gas (50 g) (purity 99.9%) was pressed into the autoclave at -60°C, and the temperature was slowly raised to 30°C. After stirring for 6 h, the pressure was slowly released and the remaining gas was removed by vacuum to obtain compound 3 as a white powdery solid, about 50 g.

[0040] Compound 3 (50 g) was cooled to -80 °C, hexafluoropropylene 4 (70 g) was pressed into it, and the temperature was slowly raised to 0 °C, stirred for 6 h, and then the temperature was continued to rise to 10 °C for 6 h, and the gas was slowly released to release the pressure. Subsequently, ice water (200 mL) was added and stirred for 40 minutes. The temperature was controlled not to exceed 25 °C, and the organic phase was separated and dried to obtain a colorless transparent liquid compound 5, which was distilled under reduced pressure, and the 64-70 °C fraction was collected.

[0041] Sodium iodide (30 g) was dissolved in ethylene glycol dimethyl ether (60 g), and compound 5 (25 g) was slowly added dropwise. The mixture was stirred in the dark for 20 h. After the reaction was completed, the mixture was washed with water, the organic phase was separated, and the mixture was distilled under reduced pressure at room temperature. The fractions were collected by low-temperature cooling to obtain compound 6.

[0042] Take 15 g of tetraethyl pyrophosphite 7 and add it to a quartz bottle. Replace the nitrogen three times, quickly add compound 6 (7 g), quickly cool to -78 ° C, extract the nitrogen under negative pressure, and close the valve. Transfer the quartz bottle to a photoreactor, slowly warm up to room temperature, irradiate and stir at 254 nm for 12 h, and proceed directly to the subsequent reaction without further treatment. Cool the reaction solution to -20 ° C, slowly add 1.1 equivalents of tert-butyl peroxide (in terms of iodide), warm to room temperature, stir for 1.5 h, pour the reaction solution into ice water (60 mL), wash three times with water, separate the organic phase and dry it, pass the organic phase through a silica gel column (petroleum ether / ethyl acetate), and obtain about 4 g of perfluoroallyl phosphonate compound 9, which is a light yellow liquid. The structure of the product was characterized by nuclear magnetic resonance hydrogen spectrum, fluorine spectrum, phosphorus spectrum, carbon spectrum, and high-resolution mass spectrum, confirming that it is the same substance as Example 1, that is, perfluorophosphate ester allyl monomer.

[0043] Example 3 The preparation method of the perfluorophosphate allyl monomer of this embodiment comprises the following steps: CF3SO3H (50 g) was added to the autoclave, and the autoclave was evacuated. BCl3 gas (30 g) (purity 99.9%) was pressed into the autoclave at -65 °C, and the temperature was slowly raised to 30 °C. After stirring for 7 h, the pressure was slowly released and the remaining gas was removed by vacuum to obtain compound 3 as a white powdery solid, about 50 g.

[0044] Compound 3 (50 g) was cooled to -80 °C, hexafluoropropylene 4 (80 g) was pressed into it, and the temperature was slowly raised to 0 °C, stirred for 7 h, and then the temperature was continued to rise to 10 °C for reaction for 6 h. The gas was slowly released to release the pressure, and then ice water (250 mL) was added and stirred for 45 minutes. The temperature was controlled not to exceed 25 °C. The organic phase was separated and dried to obtain a colorless transparent liquid compound 5, which was distilled under reduced pressure and the 64-70 °C fraction was collected.

[0045] Sodium iodide (25 g) was dissolved in ethylene glycol dimethyl ether (70 g), and compound 5 (30 g) was slowly added dropwise. The mixture was stirred in the dark for 22 h. After the reaction was completed, the mixture was washed with water, the organic phase was separated, and the mixture was distilled under reduced pressure at room temperature. The fractions were collected by low-temperature cooling to obtain compound 6.

[0046] Take 18 g of tetraethyl pyrophosphite 7 and add it to a quartz bottle. Replace the nitrogen three times, quickly add compound 6 (8 g), quickly cool to -78 ° C, extract the nitrogen under negative pressure, and close the valve. Transfer the quartz bottle to a photoreactor, slowly warm up to room temperature, irradiate and stir at 254 nm for 15 h, and proceed directly to the subsequent reaction without further treatment. Cool the reaction solution to -20 ° C, slowly add 1.3 equivalents of tert-butyl peroxide (in terms of iodide), warm to room temperature, stir for 1.8 h, pour the reaction solution into ice water (70 mL), wash three times with water, separate the organic phase and dry it, pass the organic phase through a silica gel column (petroleum ether / ethyl acetate), and obtain about 6 g of perfluoroallyl phosphonate compound 9, which is a light yellow liquid. The structure of the product was characterized by nuclear magnetic resonance hydrogen spectrum, fluorine spectrum, phosphorus spectrum, carbon spectrum, and high-resolution mass spectrum, confirming that it is the same substance as Example 1, that is, perfluorophosphate ester allyl monomer.

[0047] Example 4 The preparation method of the perfluorophosphate allyl monomer of this embodiment comprises the following steps: CF3SO3H (50 g) was added to the autoclave, and the autoclave was evacuated. BCl3 gas (60 g) (purity 99.9%) was pressed into the autoclave at -70 °C, and the temperature was slowly raised to 30 °C. After stirring for 8 h, the pressure was slowly released and the remaining gas was removed by vacuum to obtain compound 3 as a white powdery solid, about 50 g.

[0048] Compound 3 (50 g) was cooled to -80 °C, hexafluoropropylene 4 (120 g) was pressed into it, and the temperature was slowly raised to 0 °C, stirred for 9 h, and then the temperature was continued to rise to 10 °C for reaction for 8 h. The gas was slowly released to release the pressure, and then ice water (350 mL) was added and stirred for 60 minutes. The temperature was controlled not to exceed 25 °C, and the organic phase was separated and dried to obtain a colorless transparent liquid compound 5. It was distilled under reduced pressure and the 64-70 °C fraction was collected.

[0049] Sodium iodide (40 g) was dissolved in ethylene glycol dimethyl ether (90 g), and compound 5 (30 g) was slowly added dropwise. The mixture was stirred in the dark for 28 h. After the reaction was completed, the mixture was washed with water, the organic phase was separated, and the mixture was distilled under reduced pressure at room temperature. The fractions were collected by low-temperature cooling to obtain compound 6.

[0050] Take 18 g of tetraethyl pyrophosphite 7 and add it to a quartz bottle. Replace the nitrogen three times, quickly add compound 6 (8 g), quickly cool to -78 °C, extract the nitrogen under negative pressure, and close the valve. Transfer the quartz bottle to a photoreactor, slowly warm up to room temperature, irradiate and stir at 254 nm for 24 h, and proceed directly to the subsequent reaction without further treatment. Cool the reaction solution to -20 °C, slowly add 2 equivalents of tert-butyl peroxide (in terms of iodide), warm to room temperature, stir for 2.8 h, pour the reaction solution into ice water (90 mL), wash three times with water, separate the organic phase and dry it, pass the organic phase through a silica gel column (petroleum ether / ethyl acetate), and obtain about 8 g of perfluoroallyl phosphonate compound 9, which is a colorless liquid. The structure of the product was characterized by nuclear magnetic resonance hydrogen spectrum, fluorine spectrum, phosphorus spectrum, carbon spectrum, and high-resolution mass spectrum, confirming that it is the same substance as Example 1, that is, perfluorophosphate ester allyl monomer.

[0051] Example 5 The preparation method of the perfluorophosphate allyl monomer of this embodiment comprises the following steps: CF3SO3H (50 g) was added to the autoclave, and the autoclave was evacuated. BCl3 gas (100 g) (purity 99.9%) was pressed into the autoclave at -80 °C, and the temperature was slowly raised to 30 °C. After stirring for 10 h, the pressure was slowly released and the remaining gas was removed by vacuum to obtain compound 3 as a white powdery solid, about 50 g.

[0052] Compound 3 (50 g) was cooled to -80 °C, hexafluoropropylene 4 (150 g) was pressed into it, the temperature was slowly raised to 0 °C, stirred for 10 h, and the temperature was continued to rise to 10 °C for reaction for 10 h. The gas was slowly released to release the pressure, and then ice water (500 mL) was added and stirred for 55 minutes. The temperature was controlled not to exceed 25 °C. The organic phase was separated and dried to obtain a colorless transparent liquid compound 5, which was distilled under reduced pressure and the 64-70 °C fraction was collected.

[0053] Sodium iodide (35 g) was dissolved in ethylene glycol dimethyl ether (100 g), and compound 5 (40 g) was slowly added dropwise. The mixture was stirred in the dark for 30 h. After the reaction was completed, the mixture was washed with water, the organic phase was separated, and the mixture was distilled under reduced pressure at room temperature. The fractions were collected by low-temperature cooling to obtain compound 6.

[0054] Take 20 g of tetraethyl pyrophosphite 7 and add it to a quartz bottle, replace it with nitrogen three times, quickly add compound 6 (10 g), quickly cool it to -78 ° C, extract nitrogen under negative pressure, and close the valve. Transfer the quartz bottle to a photoreactor, slowly warm it to room temperature, and stir it under 254 nm for 23 h. Without further treatment, proceed directly to the subsequent reaction. Cool the reaction solution to -20 ° C, slowly add 1.8 equivalents of tert-butyl peroxide (in terms of iodide), warm it to room temperature, stir it for 2.8 h, pour the reaction solution into ice water (90 mL), wash it with water three times, separate the organic phase and dry it, and pass the organic phase through a silica gel column (petroleum ether / ethyl acetate) to obtain about 15 g of perfluoroallyl phosphonate compound 9, which is a light yellow liquid. The structure of the product was characterized by nuclear magnetic resonance hydrogen spectrum, fluorine spectrum, phosphorus spectrum, carbon spectrum, and high-resolution mass spectrum, confirming that it is the same substance as Example 1, that is, perfluorophosphate ester allyl monomer.

[0055] Example 6 The preparation method of the perfluorophosphate allyl monomer of this embodiment comprises the following steps: (1) CF3SO3H (50 g) was added to the autoclave, and the autoclave was evacuated. BCl3 gas (75 g) (purity 99.9%) was introduced at -68°C, and the temperature was slowly raised to 30°C. After stirring for 8 h, the pressure was slowly released and the remaining gas was removed by vacuum to obtain compound 3 as a white powdery solid, about 50 g.

[0056] (2) Compound 3 (50 g) was cooled to -80 °C, hexafluoropropylene 4 (110 g) was added, and the temperature was slowly raised to 0 °C and stirred for 9 h. The temperature was further raised to 10 °C and the reaction was continued for 8 h. The gas was slowly released to release the pressure. Ice water (450 mL) was then added and stirred for 55 min. The temperature was controlled not to exceed 25 °C. The organic phase was separated and dried to obtain a colorless transparent liquid compound 5. The mixture was distilled under reduced pressure and the 64-70 °C fraction was collected.

[0057] (3) Sodium iodide (38 g) was dissolved in ethylene glycol dimethyl ether (80 g), and compound 5 (30 g) was slowly added dropwise. The mixture was stirred in the dark for 27 h. After the reaction was completed, the mixture was washed with water, the organic phase was separated, and the mixture was distilled under reduced pressure at room temperature. The fractions were collected by low-temperature cooling to obtain compound 6.

[0058] (4) Take 11 g of tetraethyl pyrophosphite 7 and add it to a quartz bottle. Replace the atmosphere with nitrogen three times, quickly add compound 6 (6 g), quickly cool to -78 °C, remove nitrogen under negative pressure, and close the valve. Transfer the quartz bottle to a photoreactor, slowly warm it to room temperature, irradiate and stir at 254 nm for 12 h, and proceed directly to the subsequent reaction without further treatment. Cool the reaction solution to -20 °C, slowly add 1.4 equivalents of tert-butyl peroxide (in terms of iodide), warm it to room temperature, stir for 2 h, pour the reaction solution into ice water (80 mL), wash it with water three times, separate the organic phase and dry it, pass the organic phase through a silica gel column (petroleum ether / ethyl acetate), and obtain about 5 g of perfluoroallyl phosphonate compound 9, which is a light yellow liquid. The structure of the product was characterized by nuclear magnetic resonance hydrogen spectrum, fluorine spectrum, phosphorus spectrum, carbon spectrum, and high-resolution mass spectrum, confirming that it is the same substance as Example 1, namely, perfluorophosphate ester allyl monomer.

[0059] Application Examples The copolymerization reaction was carried out using the perfluorophosphate allyl monomer prepared in Example 1 as a raw material, and the steps are as follows: Perfluorophosphate allyl monomer (1.072 g, 4 mmol) and pentafluorostyrene monomer (0.2607 g, 1.3 mmol) were dissolved in trifluorotoluene (1.2 mL) solution, and then initiator AIBN (1 wt.%) was added, and the temperature was raised to 120 ° C under nitrogen protection for 24 h. After the reaction, the product was added dropwise to petroleum ether, the precipitate was collected by centrifugation, and the solid product was obtained after drying in an oven at 60 ° C for 24 h.

[0060] The obtained product is a yellow solid. Figure 7 The nuclear magnetic resonance phosphorus spectrum shown shows that it contains phosphorus element.

[0061] The elution curve of the GPC test of the obtained polymer is shown in Figure 8 The weight average molecular weight Mw of the polymer is calculated to be 1.09×10 4 .

[0062] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A perfluorophosphate allyl monomer having the following structural formula: 。 2. The method for preparing the perfluorophosphate allyl monomer according to claim 1, characterized in that: The steps are: (1) Adding boron trichloride to trifluoromethanesulfonic acid under vacuum and low temperature Ⅰ, and heating to react Ⅰ to obtain compound 3; (2) Compound 3 is added to hexafluoropropylene after cooling, and then added with ice water after heating to react II. The obtained reactant is separated from the organic phase and distilled under reduced pressure to obtain compound 5; (3) adding a sodium iodide solution in ethylene glycol dimethyl ether dropwise to compound 5, and reacting in the dark. The resulting reactant is washed with water, the organic phase is separated, and the resulting fraction is distilled under reduced pressure to obtain compound 6; (4) Compound 6 is added to tetraethyl pyrophosphite in a nitrogen atmosphere, and the mixture is cooled, the nitrogen is removed under negative pressure, and the temperature is raised to react under light. The reaction solution is then cooled and tert-butyl peroxide is added. The reaction mixture is reacted at room temperature, and the resulting reactant is washed with water, separated, and passed through a silica gel column to obtain a perfluorophosphate allyl monomer.

3. The method for preparing a perfluorophosphate allyl monomer according to claim 2, characterized in that: In the step (1), the mass ratio of boron trichloride to trifluoromethanesulfonic acid is 25:8-50; the structural formula of compound 3 is: .

4. The method for preparing a perfluorophosphate allyl monomer according to claim 3, characterized in that: The low temperature I refers to -60°C--80°C, and the temperature of the temperature-raising reaction is 30°C and the time is 5-10 h.

5. The method for preparing a perfluorophosphate allyl monomer according to claim 2, characterized in that: In the step (2), the mass ratio of compound 3 to hexafluoropropylene is 1:1-3; the structural formula of compound 5 is: .

6. The method for preparing a perfluorophosphate allyl monomer according to claim 5, characterized in that: The temperature after the cooling treatment is -80°C; the temperature rising reaction II is a staged temperature rising, the first stage is heated to 0°C, the reaction time is 4-10h, the second stage is heated to 10°C, the reaction time is 4-10h; the temperature of the ice water reaction is ≤25°C, and the reaction time is 30-60 min.

7. The method for preparing a perfluorophosphate allyl monomer according to claim 2, characterized in that: In step (3), the mass ratio of sodium iodide to compound 5 is 4-10:5-10; the mass concentration of sodium iodide in the ethylene glycol dimethyl ether solution of sodium iodide is 11.4%-60.6%; the structural formula of compound 6 is: ; The reaction time is 12-30℃ away from light.

8. The method for preparing a perfluorophosphate allyl monomer according to claim 2, characterized in that: In the step (4), the mass ratio of tetraethyl pyrophosphite, compound 6 and tert-butyl peroxide is 10-20:5-10:1.7-6.8; the temperature after cooling is -78°C; the temperature of the cooling and illumination reaction is room temperature, the illumination is light with a wavelength of 254 nm, and the reaction time is 10-24h; the temperature after cooling is -20°C.

9. Use of the perfluorophosphate allyl monomer according to claim 1 in the preparation of perfluorosulfonic acid resin.

10. The use according to claim 9, characterized in that: The steps are as follows: taking perfluorophosphate ester allyl monomer and pentafluorostyrene monomer as raw materials, a polymerization reaction is carried out in a trifluorotoluene solvent in the presence of an initiator to prepare a perfluorophosphate resin.

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