Phosphate alkenyl ester compound and preparation method thereof

Abstract

The invention relates to an alkenyl phosphate compound and a preparation method thereof. The preparation method comprises the following steps: (1) adding a monohydric alcohol compound into phosphorus oxychloride for substitution reaction to obtain a monosubstituted phosphorus oxychloride compound; and (2) carrying out cyclization reaction on the monosubstituted phosphorus oxychloride compound obtained in the step (1) and a dihydric alcohol compound to obtain the phosphorene ester compound. The preparation method is simple in technological process and convenient to operate, and the obtained product is high in purity, high in yield and suitable for industrial large-scale production.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a phosphate ester compound and its preparation method. Background Technology

[0002] Industrially used electrolyte solvents, primarily carbon-based solvents such as straight-chain and cyclic carbonates, offer advantages including non-toxicity, small molecular weight, low viscosity, and high conductivity. However, electrolytes formulated with these solvents pose flammable and explosive risks during processing and use, with an explosive equivalent three times that of battery energy storage. Directly using flame-retardant straight-chain phosphates, such as trimethyl phosphate or triethyl phosphate, to partially replace carbonic acid has been proven to have incompatibility issues with the negative electrode and electrolytes such as lithium hexafluorophosphate, thus shortening battery life.

[0003] Zheng et al. (Zheng, Q., Yamada, Y., Shang, R. et al. A cyclic phosphate-based battery electrolyte for high voltage and safe operation. Nat Energy 5,291-298 (2020). https: / / doi.org / 10.1038 / s41560-020-0567-z.) designed and synthesized a cyclic fluoroethyl vinyl phosphate (TFEP) and applied it to lithium-ion batteries, developing a high-voltage and safe cyclic phosphate battery electrolyte. However, the synthesis cost of fluorinated fluoroethyl vinyl phosphate is high, and there is limited research on the production technology and performance systems of cyclic phosphates, resulting in difficulties in the industrial synthesis of cyclic phosphates and hindering their widespread application in secondary batteries.

[0004] Therefore, designing and providing a method for preparing phosphate olefin compounds suitable for industrial production is of great significance. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a phosphate olefin compound and its preparation method. The preparation method features a simple process flow, convenient operation, and yields a product with high purity and high yield, making it suitable for large-scale industrial production.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing a phosphate ester compound, the method comprising the following steps:

[0008] (1) Add monohydric alcohol compounds to phosphorus oxychloride to carry out a substitution reaction to obtain monosubstituted phosphorus oxychloride compounds;

[0009] (2) The monosubstituted phosphorus oxychloride compound described in step (1) is subjected to a cyclization reaction with a diol compound to obtain the phosphate ester compound.

[0010] This invention prepares a structurally stable phosphate olefin compound with excellent flame-retardant properties by first adding a monohydric alcohol compound to phosphorus oxychloride for monosubstitution, followed by a dihydric alcohol compound for disubstitution and cyclization. The preparation method is simple, easy to operate, and has a mild reaction, effectively reducing the formation of byproducts such as phosphate polymers. It offers advantages of high yield and high purity, making it suitable for large-scale industrial production.

[0011] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0012] As a preferred technical solution of the present invention, the molar ratio of phosphorus oxychloride to monohydric alcohol in step (1) is 1:(1.0-1.3), wherein (1.0-1.3) can be, for example, 1.0, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.15, 1.2, 1.25 or 1.3, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and is further preferably 1:(1.05-1.15).

[0013] This invention optimizes the molar ratio of phosphorus oxychloride to monohydric alcohols, thereby improving the yield and purity of the monosubstituted phosphorus oxychloride compounds and obtaining high-yield phosphate ester compounds. When the molar ratio is low, i.e. the content of monohydric alcohols is high, more phosphate diesters are obtained, the distillation yield decreases, and the synthesis cost increases.

[0014] Preferably, the monohydric alcohol compound in step (1) has the structural formula R1OH;

[0015] R1 is selected from substituted or unsubstituted C1-C6 alkyl groups. Substituted or unsubstituted C2-C6 alkenyl groups, substituted or unsubstituted C2-C6 alkynyl groups;

[0016] R ’ 1. R ’ 2. R ’ 3. They may be the same or different, and each is independently selected from halogenated, substituted or unsubstituted C1-C3 alkyl groups;

[0017] The substituted group is selected from halogens or C1-C3 alkyl groups.

[0018] In this invention, the C1-C6 alkyl group can be C1, C2, C3, C4, C5 or C6 alkyl, the C2-C6 alkenyl group can be C2, C3, C4, C5 or C6 alkenyl, the C2-C6 alkynyl group can be C2, C3, C4, C5 or C6 alkynyl, and the C1-C3 alkyl group can be C1, C2 or C3 alkyl.

[0019] As a preferred technical solution of the present invention, the monohydric alcohol compound in step (1) includes any one of CH3OH, CH3CH2OH, HOCH2CH2F, HOCH2CH2Cl, CF3CH2OH, (CH3)3SiOH, HOSiF3, (CF3)3SiOH, (C2H5)3SiOH or (CF3CH2)3SiOH.

[0020] Preferably, the temperature of the substitution reaction in step (1) is 30-60°C, for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0021] Preferably, the substitution reaction time in step (1) is 1-3 h, for example, it can be 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, 2.2 h, 2.5 h, 2.8 h or 3 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0022] Preferably, the substitution reaction in step (1) is carried out under a protective gas atmosphere.

[0023] Preferably, the protective gas includes any one or a combination of at least two of nitrogen, argon, or helium.

[0024] Preferably, the substitution reaction in step (1) is followed by a post-processing step.

[0025] Preferably, the post-processing method includes distillation and vacuum distillation.

[0026] It should be noted that the present invention does not have any special limitations on the temperature and time of distillation in the post-processing. In actual production, it is necessary to make adaptive selections and adjustments according to the raw materials used, including but not limited to 50-60℃ and 10-20min.

[0027] In this invention, the distillation step after the substitution reaction in step (1) is used to remove dissolved hydrogen chloride, which not only helps to improve the purity of the obtained product, but also can effectively recover hydrogen chloride, making it economical and safe.

[0028] Preferably, the method of vacuum distillation includes vacuum distillation using a distillation column.

[0029] Preferably, the vacuum degree of the distillation column is 10-20 mmHg, for example, it can be 10 mmHg, 11 mmHg, 12 mmHg, 13 mmHg, 14 mmHg, 15 mmHg, 16 mmHg, 17 mmHg, 18 mmHg, 19 mmHg or 20 mmHg, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0030] It should be noted that the present invention relates the top feed temperature of the distillation column to the vacuum degree, but does not impose a specific limitation. It can be adaptively adjusted according to the specific raw material selection, including but not limited to 60-100℃, such as 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃, as well as specific point values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0031] Preferably, the molar ratio of the monosubstituted phosphorus oxychloride compound to the diol compound in step (2) is 1:(1.0-1.3), wherein (1.0-1.3) can be, for example, 1.0, 1.05, 1.06, 1.07, 1.1, 1.12, 1.15, 1.18, 1.2, 1.25 or 1.3, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but preferably it is 1:(1.06-1.12).

[0032] This invention optimizes the molar ratio of monosubstituted phosphorus oxychloride compounds to diol compounds, thereby further improving the yield and purity of the obtained phosphate ester compounds. When the molar ratio is low, that is, the content of diol compounds is high, the distillation time for excess diols increases, the cost increases, and the production benefits of the obtained phosphate ester compounds are reduced.

[0033] Preferably, the diol compound in step (2) has the structure shown in Formula I:

[0034] Formula I;

[0035] n is selected from 1, 2 or 3; R2 is selected from H or C1-C3 alkyl.

[0036] As a preferred technical solution of the present invention, the diol compound in step (2) includes any one or at least two of ethylene glycol, 1,2-propanediol or 1,3-propanediol.

[0037] Preferably, the cyclization reaction in step (2) is carried out in an isolation diluent.

[0038] Preferably, the isolation diluent includes any one or a combination of at least two of chloroform, tetrachloroethylene, benzene, or chlorobenzene, and more preferably chlorobenzene.

[0039] The isolation diluent specifically used in this invention has good stability and is easy to separate, which can reduce the formation of phosphate polymers and thus improve the yield and purity of the obtained phosphate olefin compounds.

[0040] Preferably, the molar ratio of the isolating diluent to the monosubstituted phosphorus oxychloride compound is (0.6-1.5):1, wherein (0.6-1.5) can be, for example, 0.6, 0.7, 0.8, 0.9, 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.3, 1.4 or 1.5, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0041] Preferably, the cyclization reaction in step (2) is carried out under reflux.

[0042] Preferably, the cyclization reaction time in step (2) is 1-3 h, for example, it can be 1 h, 1.2 h, 1.4 h, 1.6 h, 1.8 h, 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h or 3 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0043] Preferably, the cyclization reaction in step (2) further includes a post-processing step.

[0044] Preferably, the post-processing method includes distillation and vacuum distillation.

[0045] It should be noted that the distillation step after the cyclization reaction in step (2) is used to remove the isolation diluent. The specific temperature used is adjusted adaptively according to the selection of the isolation diluent, and this invention does not impose any special limitations. At the same time, the vacuum distillation is divided into a first vacuum distillation and a second vacuum distillation. The purpose of the first vacuum distillation is to remove excess diol compounds, and the purpose of the second vacuum distillation is to obtain the target product, phosphate olefin compounds. Similarly, the specific temperature selection for the two vacuum distillations is adjusted adaptively according to the added raw materials and the target product, and no special limitations are imposed here. In addition, the material obtained in the final column of this invention is a high-boiling-point polymer, which can be used as a high-quality flame retardant for rubber and tires, improving the utilization rate of materials and being economical and practical.

[0046] Preferably, the preparation method of the phosphate ester compound specifically includes the following steps:

[0047] (1) Under a protective gas atmosphere, a monohydric alcohol compound is added to phosphorus oxychloride and a substitution reaction is carried out at 30-60℃ for 1-3 h. After distillation and vacuum distillation, a monosubstituted phosphorus oxychloride compound is obtained, wherein the molar ratio of phosphorus oxychloride to alcohol compound is 1:(1.0-1.3).

[0048] (2) A monosubstituted phosphorus oxychloride compound with a molar ratio of 1:(1.0-1.3) and a diol compound were refluxed in an isolation diluent for 1-3 h, and the phosphate ester compound was obtained by distillation and vacuum distillation.

[0049] The preparation process of this invention is simple and easy to operate. By selecting the molar ratio of the raw materials and controlling the process parameters, the occurrence of side reactions can be effectively reduced, thereby obtaining high-purity, high-yield, structurally stable phosphate ester compounds.

[0050] The synthetic route involved in the preparation method of the phosphate ester compound provided by this invention is as follows:

[0051] ;

[0052] ;

[0053] Wherein, R1 is selected from substituted or unsubstituted C1-C6 alkyl groups, Substituted or unsubstituted C2-C6 alkenyl groups, substituted or unsubstituted C2-C6 alkynyl groups;

[0054] R ’ 1. R ’ 2. R ’ 3. They may be the same or different, and each is independently selected from halogenated, substituted or unsubstituted C1-C3 alkyl groups;

[0055] The substituted substituents are selected from halogens or C1-C3 alkyl groups;

[0056] n is selected from 1, 2 or 3; R2 is selected from H or C1-C3 alkyl.

[0057] In a second aspect, the present invention provides a phosphate olefin compound, which is prepared by the preparation method described in the first aspect.

[0058] The phosphate olefin compounds prepared by the preparation method provided by this invention have few impurities and high purity (up to 99.9%). When applied to electrolytes, they can give them better electrochemical performance, especially cycle life and safety.

[0059] Compared with the prior art, the present invention has at least the following beneficial effects:

[0060] This invention prepares a structurally stable phosphate olefin compound with excellent flame-retardant properties by first monosubstituted with phosphorus oxychloride and then cyclizing it with a diol compound. The preparation method is simple, easy to operate, and has a mild reaction, effectively reducing the formation of byproducts such as phosphate polymers. It boasts advantages of high yield (≥82%) and high purity (>99.5%), making it suitable for large-scale industrial production. Detailed Implementation

[0061] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0062] Unless otherwise specified, all raw materials and reagents used in the following examples and comparative examples are commercially available.

[0063] Example 1

[0064] This embodiment provides a method for preparing phosphate ester compound 1 (trimethoxypropyl phosphate), the preparation method comprising the following steps:

[0065] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous trimethylsilyl alcohol (310 g, 3.44 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 110-120℃. 610 g of trimethylsiloxyphosphoryl dichloride was obtained from the top of the column.

[0066] (2) After adding the trimethylsiloxyphosphoryl dichloride (610 g, 2.95 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous 1,2-propanediol (240 g, 3.15 mol) was added dropwise under stirring, and the material temperature was controlled at 50-60℃. After the addition was completed, the temperature was gradually raised to the reflux temperature of chlorobenzene, 130℃, to remove hydrogen chloride. After maintaining this temperature for 2 h, chlorobenzene was distilled off at atmospheric pressure, 130-135℃. Excess 1,2-propanediol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 150-170℃ for distillation to obtain 588 g of the phosphate ester compound 1.

[0067] The structure of the phosphate ester compound 1 is shown in Formula II:

[0068] Formula II.

[0069] The 1H NMR characterization data of the phosphate olefin compound 1 are as follows:

[0070] 1 H NMR (500 MHz, CDCl3): δ4.61(dddt, J=9.2, 8.0, 5.9, 3.1 Hz, 1H), 4.22(ddd, J=10.8, 8.6, 3.3 Hz, 1H), 3.97(ddd, J=10.8, 8.5, 3.3 Hz, 1H), 1.31(s, 3H), 0.22(s,9H).

[0071] Example 2

[0072] This embodiment provides a method for preparing phosphate ester compound 2 (ethyl vinyl phosphate), the preparation method comprising the following steps:

[0073] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous ethanol (165 g, 3.58 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 70-80℃. 470 g of ethoxyphosphoric acid dichloride was obtained from the top of the column.

[0074] (2) After adding the ethylphosphoryl dichloride (470 g, 2.92 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous ethylene glycol (190 g, 3.06 mol) was added dropwise under stirring, and the material temperature was controlled at 30-60℃. After the addition was completed, the temperature was gradually raised to the reflux temperature of chlorobenzene (130℃) to remove hydrogen chloride. After maintaining this temperature for 1 h, chlorobenzene was distilled off at atmospheric pressure (130-135℃). Excess anhydrous ethanol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 120-140℃ for distillation to obtain 416 g of phosphate ester compound 2.

[0075] The structure of the phosphate ester compound 2 is shown in Formula III:

[0076] Formula III.

[0077] The 1H NMR characterization data of the phosphate ester compound 2 are as follows:

[0078] 1 H NMR (500 MHz, CDCl3): δ4.32(d, J=8.4 Hz, 4H), 4.10(dq, J=8.4, 6.9Hz, 2H), 1.57-1.01(m, 3H).

[0079] Example 3

[0080] This embodiment provides a method for preparing phosphate olefin compound 3, the preparation method comprising the following steps:

[0081] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous 2-fluoroethanol (221 g, 3.45 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 80-90℃. 526 g of intermediate was obtained from the top of the column.

[0082] (2) After adding the intermediate (526 g, 2.92 mol) and tetrachloroethylene (299 g, 1.80 mol) from step (1) to a four-necked flask, anhydrous ethylene glycol (198 g, 3.19 mol) was added dropwise under stirring, and the material temperature was controlled at 30-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of tetrachloroethylene 120℃ to remove hydrogen chloride. After maintaining this temperature for 3 h, tetrachloroethylene was distilled off at atmospheric pressure 120-125℃. Excess anhydrous ethylene glycol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 90-100℃ for distillation to obtain 470 g of phosphate ester compound 3.

[0083] The structure of the phosphate ester compound 3 is shown in Formula IV:

[0084] Formula IV.

[0085] The 1H NMR characterization data of the phosphate ester compound 3 are as follows:

[0086] 1 H NMR (500 MHz, CDCl3): δ4.67(t, J=4.2 Hz, 1H), 4.58(t, J=4.2 Hz, 1H), 4.32(d, J=8.4 Hz, 4H), 4.29-4.18(m, 2H).

[0087] Example 4

[0088] This embodiment provides a method for preparing phosphate olefin compound 4, the preparation method comprising the following steps:

[0089] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous CF3CH2OH (355 g, 3.55 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 95-105℃. 631 g of intermediate was obtained from the top of the column.

[0090] (2) After adding the intermediate (631 g, 2.92 mol) and benzene (240 g, 3.1 mol) from step (1) to a four-necked flask, anhydrous 1,2-propanediol (240 g, 3.15 mol) was added dropwise under stirring. The temperature of the material was controlled at 30-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of benzene (80℃) to remove hydrogen chloride. After maintaining this temperature for 1.5 h, benzene was distilled off at atmospheric pressure (80-85℃). Excess 1,3-propanediol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 150-155℃ for distillation to obtain 589 g of phosphate ester compound 4.

[0091] The structure of the phosphate ester compound 4 is shown in Formula V:

[0092] Formula V.

[0093] The 1H NMR characterization data of the phosphate ester compound 4 are as follows:

[0094] 1 H NMR (500 MHz, CDCl3): δ4.72-4.57(m, 3H), 4.30 (ddd, J=10.6, 8.5,3.3 Hz, 1H), 4.05 (ddd, J=10.8, 8.6, 3.3 Hz, 1H), 1.31(s, 3H).

[0095] Example 5

[0096] This embodiment provides a method for preparing phosphate olefin compound 5, the preparation method comprising the following steps:

[0097] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous trimethylsilyl alcohol (355 g, 3.72 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 90-100℃. 610 g of trimethylsiloxyphosphoryl dichloride was obtained from the top of the column.

[0098] (2) After adding the trimethylsiloxyphosphoryl dichloride (610 g, 2.94 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous ethylene glycol (204 g, 3.29 mol) was added dropwise under stirring. The temperature of the material was controlled at 50-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of chlorobenzene (130℃) to remove hydrogen chloride. After maintaining this temperature for 2 h, chlorobenzene was distilled off at atmospheric pressure (130-135℃). Excess anhydrous ethylene glycol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 150-160℃ for distillation to obtain 555 g of phosphate ester compound 5.

[0099] The structure of the phosphate ester compound 5 is shown in Formula VI:

[0100] Formula VI.

[0101] The 1H NMR characterization data of the phosphate ester compound 5 are as follows:

[0102] 1 H NMR (500 MHz, CDCl3): δ4.32(d, J=8.6 Hz, 4H), 0.22(s, 9H).

[0103] Example 6

[0104] This embodiment provides a method for preparing phosphate olefin compound 6, the method comprising the following steps:

[0105] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous methanol (115 g, 3.59 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 90-100℃. 438 g of methoxyphosphoric acid dichloride was obtained from the top of the column.

[0106] (2) After adding the methoxyphosphoryl dichloride (438 g, 2.94 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous 1,2-propanediol (241 g, 3.17 mol) was added dropwise under stirring. The material temperature was controlled at 50-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of chlorobenzene (130℃) to remove hydrogen chloride. After maintaining this temperature for 2 h, chlorobenzene was distilled off at atmospheric pressure (130-135℃). Excess anhydrous 1,2-propanediol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 150-160℃ for distillation to obtain 416 g of phosphate ester compound 6.

[0107] The structure of the phosphate ester compound 6 is shown in Formula VII:

[0108] Formula VII.

[0109] The 1H NMR characterization data of the phosphate ester compound 6 are as follows:

[0110] 1 H NMR (500 MHz, CDCl3): δ4.64(dddt, J=9.3, 8.2, 6.1, 3.0 Hz, 1H), 4.29 (ddd, J=10.8, 8.4, 3.3 Hz, 1H), 4.04(ddd, J=10.8, 8.4, 3.3 Hz, 1H), 3.75(d, J=11.0 Hz, 3H), 1.31(s, 3H).

[0111] Example 7

[0112] This embodiment provides a method for preparing phosphate olefin compound 7, the preparation method comprising the following steps:

[0113] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous trifluorosilanol (355 g, 3.48 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 90-100℃. 644 g of trifluorosiloxyphosphoryl dichloride was obtained from the top of the column.

[0114] (2) After adding the trifluorosiloxyphosphoryl dichloride (644 g, 2.93 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous 1,2-propanediol (241 g, 3.17 mol) was added dropwise under stirring. The material temperature was controlled at 50-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of chlorobenzene (130℃) to remove hydrogen chloride. After maintaining this temperature for 2 h, chlorobenzene was distilled off at atmospheric pressure (130-135℃). Excess anhydrous 1,2-propanediol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 170-180℃ for distillation to obtain 600 g of phosphate ester compound 7.

[0115] The structure of the phosphate ester compound 7 is shown in Formula VIII:

[0116] Formula VIII.

[0117] The 1H NMR characterization data of the phosphate ester compound 7 are as follows:

[0118] 1 H NMR (500 MHz, CDCl3): δ4.61(dddt, J=9.2, 8.0, 5.9, 3.1 Hz, 1H), 4.22(ddd, J=10.8, 8.6, 3.3 Hz, 1H), 3.97 (ddd, J=10.8, 8.5, 3.3 Hz, 1H), 1.31(s, 3H).

[0119] Example 8

[0120] This embodiment provides a method for preparing phosphate olefin compound 8, the preparation method comprising the following steps:

[0121] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous 2-chloroethanol (283 g, 3.52 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 90-100℃. 581 g of 2-chloroethoxyphosphoryl dichloride was obtained from the top of the column.

[0122] (2) After adding 2-chloroethoxyphosphoryl dichloride (581 g, 2.93 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous 1,2-propanediol (245 g, 3.22 mol) was added dropwise under stirring. The temperature of the material was controlled at 50-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of chlorobenzene (130℃) to remove hydrogen chloride. After maintaining this temperature for 2 h, chlorobenzene was distilled off at atmospheric pressure (130-135℃). Excess anhydrous 1,2-propanediol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 150-170℃ for distillation to obtain 542 g of phosphate olefin compound 8.

[0123] The structure of the phosphate ester compound 8 is shown in Formula IX:

[0124] Formula IX.

[0125] The 1H NMR characterization data of the phosphate olefin compound 8 are as follows:

[0126] 1H NMR (500 MHz, CDCl3): δ4.63 (dddt, J=9.3, 8.0, 6.1, 3.1 Hz, 1H), 4.34-4.25 (m, 3H), 4.04(ddd, J=10.8, 8.5, 3.3 Hz, 1H), 3.75(t, J=2.9 Hz, 2H),1.31(s, 3H).

[0127] Example 9

[0128] This embodiment provides a method for preparing phosphate olefin compound 9, the method comprising the following steps:

[0129] (1) Under a nitrogen atmosphere, anhydrous phosphorus oxychloride (500 g, 3.26 mol) was added to a 1000 mL reaction flask, and anhydrous 2-fluoroethanol (228 g, 3.56 mol) was added dropwise with stirring. The reaction temperature was controlled at 30-60℃. After the addition was completed, the mixture was distilled at 50-60℃ for 15 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the column was controlled at 90-100℃. 532 g of 2-fluoroethoxyphosphoryl dichloride was obtained from the top of the column.

[0130] (2) After adding 2-chloroethoxyphosphoryl dichloride (532 g, 2.93 mol) and chlorobenzene (310 g, 2.75 mol) from step (1) to a four-necked flask, anhydrous 1,2-propanediol (245 g, 3.22 mol) was added dropwise under stirring. The temperature of the material was controlled at 50-60℃. After the addition was completed, the temperature was gradually increased to the reflux temperature of chlorobenzene (130℃) to remove hydrogen chloride. After maintaining this temperature for 2 h, chlorobenzene was distilled off at atmospheric pressure (130-135℃). Excess anhydrous 1,2-propanediol was distilled off under a vacuum of 10-20 mmHg. Finally, the temperature was raised to 150-170℃ for distillation to obtain 516 g of phosphate olefin compound 9.

[0131] The structure of the phosphate ester compound 9 is shown in Formula X:

[0132] Formula X.

[0133] The 1H NMR characterization data of the phosphate olefin compound 9 are as follows:

[0134] 1 H NMR (500 MHz, CDCl3): δ4.70-4.55(m, 3H), 4.33-4.19(m, 3H), 4.04(ddd, J=10.8, 8.5, 3.3 Hz, 1H), 1.31(s, 3H).

[0135] Comparative Example 1

[0136] This comparative example provides a method for preparing phosphate olefin compound 2, the method comprising the following steps:

[0137] (1) Under a nitrogen atmosphere, phosphorus oxychloride (500 g, 3.26 mol) and chlorobenzene (346 g, 3.07 mol) were added to a 1000 mL reaction flask, and anhydrous ethylene glycol (196 g, 3.16 mol) was added dropwise. After the addition was completed, the reaction was carried out at 50 °C for 1 h. Chlorobenzene and excess phosphorus oxychloride were distilled off, and 269 g of cycloethylene phosphoric acid chloride intermediate was obtained by vacuum distillation.

[0138] (2) The intermediate (269 g, 1.89 mol) from step (1) was added to a 1000 mL reaction flask, followed by chlorobenzene (310 g, 2.75 mol). Anhydrous ethanol (106 g, 2.30 mol) was added with stirring. The reaction temperature was controlled at 110 °C. After reacting for 2 h, the mixture was distilled at 50-60 °C for 10 min to remove dissolved hydrogen chloride. Then, it was subjected to vacuum distillation in a distillation column with a vacuum degree of 10-20 mmHg. The top temperature of the feed was controlled at 90-110 °C. The unconverted feed was distilled off, and 224 g of phosphate ester compound 2 was obtained from the bottom of the column.

[0139] The yields and purities of the phosphate ester compounds obtained in Examples 1-9 and Comparative Example 1 are shown in Table 1.

[0140] Table 1

[0141]

[0142] The test results show that:

[0143] (1) As can be seen from Examples 1 to 9, the present invention obtains phosphate olefin compounds with high yield (82-86%) and high purity (99.7-99.9%) by first adding monohydric alcohol compounds to phosphorus oxychloride for monosubstitution and then cyclizing them with dihydric alcohol compounds. This is suitable for large-scale industrial production.

[0144] (2) By comparing Examples 1 to 9 with Comparative Example 1, it can be seen that Comparative Example 1 uses a synthesis method of first di-substituted cyclization and then mono-substituted, which will result in more phosphate polymers, making distillation difficult and significantly reducing the yield and product purity. The total yield of the obtained phosphate olefin compound is only 47% and the purity is only 95%. This shows that the present invention can obtain phosphate olefin compounds with better yield and purity by using a specific synthesis method.

[0145] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for producing a phosphonate compound, characterized by, The preparation method comprises the following steps: (1) adding a monohydric alcohol compound into phosphorus oxychloride to perform a substitution reaction, to obtain a monosubstituted phosphorus oxychloride compound; (2) performing a cyclization reaction of the monosubstituted phosphorus oxychloride compound in step (1) with a dihydric alcohol compound, to obtain the phosphonate compound.

2. The production method according to claim 1, characterized by, The molar ratio of the phosphorus oxychloride to the monohydric alcohol compound in step (1) is 1:(1.0-1.3), preferably 1:(1.05-1.15).

3. The production method according to claim 1 or 2, characterized by, The monohydric alcohol compound in step (1) has a structural formula of R1OH. R1is selected from substituted or unsubstituted C1-C6alkyl, substituted or unsubstituted C2-C6alkenyl, substituted or unsubstituted C2-C6alkynyl; R ’ 1. R ’ 2. R ’ 3identical or different, each independently selected from halogen, substituted or unsubstituted C1-C3alkyl; The substituent group is selected from halogen or C1-C3 alkyl.

4. The production method according to any one of claims 1 to 3, characterized by, The temperature of the substitution reaction in step (1) is 30-60°C. Preferably, the time of the substitution reaction in step (1) is 1-3 h. Preferably, the substitution reaction in step (1) is performed under a protective gas atmosphere. Preferably, the protective gas comprises any one or a combination of at least two of nitrogen, argon or helium.

5. The method of any one of claims 1-4, wherein, The substitution reaction in step (1) further comprises a post-treatment step. Preferably, the post-treatment method comprises distillation and vacuum rectification. Preferably, the vacuum rectification method comprises vacuum rectification using a rectification tower. Preferably, the vacuum degree of the rectification tower is 10-20 mmHg.

6. The method of any one of claims 1-5, wherein, The molar ratio of the monosubstituted phosphorus oxychloride compound to the dihydric alcohol compound in step (2) is 1:(1.0-1.3), preferably 1:(1.06-1.12).

7. The method of any one of claims 1-6, wherein, The dihydric alcohol compound in step (2) has a structure as shown in Formula I: Formula I; n is selected from 1, 2 or 3; and R2 is selected from H or C1-C3 alkyl.

8. The method of any one of claims 1-7, wherein, The cyclization reaction in step (2) is performed in an isolated diluent. Preferably, the isolated diluent comprises any one or a combination of at least two of chloroform, tetrachloroethylene, benzene or chlorobenzene. Preferably, the molar ratio of the isolated diluent to the monosubstituted phosphorus oxychloride compound is (0.6-1.5):

1. Preferably, the cyclization reaction in step (2) is performed under reflux. Preferably, the time of the cyclization reaction in step (2) is 1-3 h. Preferably, the cyclization reaction in step (2) further comprises a post-treatment step. Preferably, the post-treatment method comprises distillation and vacuum rectification.

9. The method of any one of claims 1-8, wherein, The preparation method specifically comprises the following steps: (1) under a protective gas atmosphere, adding a monohydric alcohol compound into phosphorus oxychloride to perform a substitution reaction at 30-60°C for 1-3 h, and after distillation and vacuum rectification, obtaining a monosubstituted phosphorus oxychloride compound, wherein the molar ratio of the phosphorus oxychloride to the alcohol compound is 1:(1.0-1.3); (2) performing a reflux reaction of the monosubstituted phosphorus oxychloride compound with a dihydric alcohol compound in an isolated diluent for 1-3 h, and after distillation and vacuum rectification, obtaining the phosphonate compound, wherein the molar ratio of the monosubstituted phosphorus oxychloride compound to the dihydric alcohol compound is 1:(1.0-1.3).

10. A phosphonate compound, characterized by, The phosphonate compound is prepared by the preparation method in any one of claims 1-9.

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