Low-energy-consumption electrosynthesis method of phosphotriester compound

Abstract

The invention discloses a low-energy-consumption electrosynthesis method of phosphotriester compounds, and belongs to the technical field of electrolysis processes for producing compounds. In the electrolysis process, the catalyst loses electrons on the surface of the anode, an oxidation-state catalyst with oxidability is formed, and then the oxidation-state catalyst flows into the reaction device along with oxidation-state catalytic liquid. The oxidation-state catalyst reacts with white phosphorus to oxidize the white phosphorus and reduce the white phosphorus into a normal-state catalyst, and the oxidation-state white phosphorus has good reactivity and can further react with a monohydric hydroxyl compound to form a target phosphotriester compound. According to the method, the catalytic liquid is used as a medium participating in circular reaction, the synthesis route overcomes production interruption caused by reaction and product separation of white phosphorus and the unitary hydroxyl compound in an electrolytic tank under the action of current in an existing electrolytic synthesis system, and the method has the advantages of being simple, efficient, green, environmentally friendly and capable of achieving full-continuous flow production; the method is suitable for industrial production and has a good application prospect.

Description

Technical Field

[0001] This invention relates to the field of electrolytic process technology for producing compounds, and more particularly to a low-energy electrosynthesis method for phosphate triester compounds. Background Technology

[0002] Triphosphate esters are a class of organic compounds containing phosphate ester groups, exhibiting high reactivity and stability. Industrially, they are primarily used as phosphorus-containing pesticides, nerve agents, flame-retardant hydraulic fluids, and lubricants. In the pharmaceutical field, some triphosphate esters possess insecticidal and bactericidal properties and can be used as pesticides. Furthermore, they are widely used as plastic additives to improve the flame retardancy, thermal stability, and mechanical properties of plastics. Therefore, triphosphate esters are a class of multifunctional organic compounds playing a vital role in multiple industrial sectors, and their synthesis and application research constitutes an important branch of chemical engineering and materials science.

[0003] Currently, the main industrial methods for synthesizing phosphate triesters are the sodium alkoxide method and electrochemically promoted synthesis. The sodium alkoxide method involves reacting an alcohol with sodium hydroxide to produce the corresponding sodium alkoxide, which is then esterified with phosphorus oxychloride to synthesize the phosphate ester product. This method has the advantage of high reactivity, but it suffers from drawbacks such as severe equipment corrosion, cumbersome procedures, and significant environmental pollution.

[0004] Electrochemically promoted synthesis of phosphate triesters is a novel synthetic method that utilizes electrochemical reactions to convert white phosphorus and alcohols into phosphate triesters under an inert atmosphere. This method avoids the high pollution and corrosiveness problems of traditional methods, achieves high white phosphorus conversion rates throughout the process, and ensures safe post-reaction handling.

[0005] For example, Chinese invention patent CN114752953A discloses an electrochemically promoted method for preparing trialkyl phosphates from white phosphorus. Under an inert atmosphere, a halogen-containing salt as an electrolyte, ROH (R representing alkyl), and a white phosphorus solution are added to a reaction vessel. The mixture is then placed in a mixed solvent (the solvent dissolving the white phosphorus) and a reactant alcohol, and an electric current is passed through the mixture for a certain period to obtain trialkyl phosphate derivatives. This method uses white phosphorus and alcohol as raw materials, and utilizes an electrochemical reaction catalyzed by halogen-containing alkali metal and alkaline earth metal salts to rapidly prepare trialkyl phosphates. Another example is Chinese invention patent CN115323406A, which provides an electrochemical preparation method for triphosphate compounds. An organic solvent, white phosphorus, alcohol or phenol, and electrolyte are mixed, and an electrolytic reaction is carried out in a constant current mode to obtain triphosphate compounds. However, the mainstream method for synthesizing triphosphate compounds in industry is still the sodium alkoxide method, because the production scale of electrochemical synthesis is limited by the electrolytic process. In electrolytic reactions, raw materials are added to the electrolytic cell in a "one-pot" manner, and the feeding, reaction, and product recovery steps are carried out in the same solution environment, making it difficult to form a continuous flow process. This makes it difficult to achieve continuous production of phosphate triester compounds, limiting the large-scale industrial application of electrochemical synthesis methods.

[0006] In summary, this invention provides a low-energy-consumption electrosynthesis method for the industrial production of phosphate triesters, achieving uninterrupted production of these compounds. This method is of great significance for promoting their application and has positive environmental benefits. Summary of the Invention

[0007] In view of the above-mentioned deficiencies of the prior art, the first aspect of the present invention provides a simple, efficient, green and environmentally friendly method for the low-energy electrosynthesis of phosphate triester compounds that can achieve fully continuous flow production, comprising the following steps: Step (1): The catalytic solution is fed into the electrolysis device, and electrolysis causes the catalyst in it to lose electrons on the anode surface to obtain an oxidized catalytic solution; the components of the catalytic solution include solvent, electrolyte and catalyst; Step (2): The oxidized catalyst solution is fed into the reaction device, and white phosphorus and excess monohydroxy compound are added to the reaction device in a continuous feeding manner; the white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with the monohydroxy compound to obtain a crude reaction solution; the monohydroxy compound is an alcohol or phenolic compound. Step (3): The target product, phosphate triester compounds, residual catalyst and unreacted monohydroxy compounds are separated from the crude reaction solution. The residual catalyst is recycled back to the electrolysis device for recycling. The unreacted monohydroxy compounds are recovered and added to the reaction device as raw materials to continuously synthesize phosphate triester compounds.

[0008] Preferably, in step (1), the solvent includes at least one of acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane, dichloroethane, water, methanol, ethanol, ethylene glycol dimethyl ether, trifluoroethanol, and nitromethane.

[0009] In this art, solvents are used to promote the dispersion of substances and create a suitable environment for the reaction. They are chemically inert relative to the raw materials, intermediates, or products used in the synthesis and do not react with them. Furthermore, based on the physical properties of white phosphorus in the reaction substrate of this invention, the solvent is preferably of a type that is insoluble or has low solubility for white phosphorus. Thus, in the reaction, white phosphorus, insoluble in the solvent in the oxidized catalytic solution, reacts directly with the monohydroxy compound, which helps to reduce the difficulty of subsequent separation and recovery of the product and the catalytic solution.

[0010] Preferably, in step (1), the electrolyte includes at least one of tetrabutylammonium iodide, tetraethylammonium bromide, potassium iodide, sodium iodide, ammonium iodide, lithium iodide, tetrabutylammonium bromide, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, potassium chloride, sodium chloride, ammonium chloride, lithium chloride, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, sodium sulfate, potassium sulfate, potassium nitrate, and potassium hydrosulfide.

[0011] Electrolytes enhance the conductivity of the solution system, which helps promote the normal progress of electrolysis and reduce energy consumption.

[0012] Preferably, in step (1), the catalyst is at least one of tetrabutylammonium iodide, tetraethylammonium bromide, potassium iodide, sodium iodide, ammonium iodide, lithium iodide, tetrabutylammonium bromide, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, potassium chloride, sodium chloride, ammonium chloride, lithium chloride, ferric chloride, ferric sulfate, ferric acetate, cobalt acetate, cobalt chloride, vanadium sulfate, 2,2,6,6-tetramethylpiperidine oxide, potassium iodide, sodium iodide, ammonium iodide, lithium iodide, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, tetraethylammonium bromide, tetraethylammonium chloride, potassium chloride, sodium chloride, ammonium chloride, lithium chloride, and tetrabutylammonium perchlorate.

[0013] The catalyst of this invention is converted into an oxidized state under the action of an electric current, serving as a medium for the synthesis of phosphate triester compounds in a cyclic reaction. It should be noted that some types of catalysts can also simultaneously function as electrolytes. For the same type of substance, the whole can be considered as the sum of the electrolyte and catalyst components.

[0014] Preferably, the concentration of the electrolyte in the catalytic solution is 0.01-10 mol / L, and the concentration of the catalyst is 0.01-10 mol / L.

[0015] Preferably, in step (1), an additive is added to the catalyst solution, and the additive includes one or two of sulfuric acid, hydrochloric acid, lithium perchlorate, lithium chloride, and trifluoroacetic acid.

[0016] More preferably, the molar ratio of white phosphorus to the additive is 0.01-10:1.

[0017] Preferably, in step (1), the electrolytic cell of the electrolytic device is a filter press type electrolytic cell; the anode is selected from one of graphite electrode, graphite felt electrode, and dimensionally stable anode (DSA); the cathode is selected from one of platinum electrode, stainless steel electrode, iron electrode, nickel electrode, nickel-plated platinum electrode, and nickel-plated ruthenium electrode.

[0018] More preferably, the area of ​​a single electrode in the filter press type electrolytic cell is 0.001-5 m². 2 The number of electrolysis units ranges from 1 to 150.

[0019] Preferably, in step (1), the electrolysis current density is 200-6000 A / m. 2 The electrolysis temperature is 0-100℃; the amount of electricity passed is 0.1-8 F / mol.

[0020] This process has good industrial applicability and requires no specialized equipment or special treatment. Within the above-defined parameter range, it facilitates the efficient conversion of raw materials and ensures the complete completion of the reaction.

[0021] Preferably, in step (2), the monohydroxy compounds include alcohols comprising C1-C9 saturated monohydric alcohols and their substitutes, wherein the number of substituents in the saturated monohydric alcohol substitutes is 1 or 2, and the substituent types include halogens; the phenolic compounds include phenols and their substitutes; the number of substituents in the phenol substitutes is 1-3, and the substituent types include at least one of halogens, C1-C9 alkyl groups, nitro groups, trifluoromethyl groups, and methoxy groups.

[0022] More preferably, the alcohol compound is methanol, ethanol, n-butanol, 2-chloroethanol, chloropropanol, dichloropropanol, 2-ethylhexanol, or isobutanol; and the phenol compound is phenol, 4-methylphenol, or 4-chlorophenol.

[0023] The crude reaction solution mainly contains phosphate triesters, unreacted alcohols or phenols, and a catalyst. These components can be processed using industrially common separation methods, such as column chromatography and distillation. The remaining alcohols or phenols can be recycled back to the reaction unit as raw materials, reducing production costs and waste.

[0024] In a second aspect of the invention, an application of a low-energy-consumption electrosynthesis method for phosphate triester compounds according to the first aspect of the invention is provided, specifically as an electrolytic process for the production of phosphate triester compounds.

[0025] Based on the above technical solutions, the inventive concept of this invention lies in adopting a synthesis strategy that separates the electro-oxidation process and the chemical reaction process, thereby achieving a fully continuous flow process based on the simplicity of the electrolysis system. A catalytic liquid is used as the electrolyte, which does not contain complex solutes with poor conductivity, thus reducing the cell voltage and lowering energy consumption and cost. During electrolysis, the catalyst loses electrons at the anode surface, forming an oxidizing catalyst, which then flows into the reaction device along with the oxidizing catalytic liquid. At this point, the oxidizing catalyst reacts with white phosphorus, oxidizing it and then reducing it back to its normal state. The oxidizing white phosphorus has good reactivity, reacting with a chemically reactant amount of a monohydroxy compound to form the target triphosphate ester compound. Thus, the product and catalytic liquid can be continuously separated from the crude reaction solution. After the catalytic liquid is returned to the electrolysis device, the above steps can be repeated to continuously and uninterruptedly synthesize the triphosphate ester compound. This invention uses the catalytic liquid as the medium participating in the cyclic reaction. This synthesis pathway overcomes the production interruptions caused by the reaction of white phosphorus and the monohydroxy compound in the electrolytic cell under the action of current and the product separation in existing electrolytic synthesis systems.

[0026] The following reaction formulas describe the reaction principles of each step in this invention: The electrolysis reaction formula in step (1) is as follows: ; In the formula, Cat. represents catalyst; The reaction formula in step (2) is as follows: ; In the formula, ROH represents a monohydroxy compound; R represents the functional group corresponding to an alcohol or phenol compound.

[0027] Compared with the prior art, the present invention has the following advantages and beneficial effects: This invention provides a low-energy-consumption electrosynthesis method for phosphate triester compounds, which has the advantages of being simple, efficient, green and environmentally friendly, and capable of fully continuous production. It is suitable for industrial production and improves the production capacity of phosphate triester compounds.

[0028] This invention provides an application of a low-energy electrosynthesis method for phosphate triester compounds, which has good application prospects as an electrolytic process in the production of phosphate triester compounds. Attached Figure Description

[0029] Figure 1 A process flow diagram for the fully continuous production of low-energy electrosynthesis of phosphate triesters. Detailed Implementation

[0030] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0031] In the following embodiments: Nafion TM 117 is a commercially available perfluorosulfonic acid ion exchange membrane with a high-performance perfluorosulfonic acid resin matrix and unique ion exchange function. In the examples, it is used as an electrolytic ion exchange membrane in an electrolyzer. It is commercially available from Chemours and is model N117. The commercial source of the dimensionally stable anode is Suzhou Shuertai Industrial Technology Co., Ltd., and the model is a ruthenium-iridium titanium plate with a specification of 100 mm × 100 mm.

[0032] Example 1 Low-energy electrosynthesis methods for phosphate triesters, such as... Figure 1 As shown, the steps are as follows:

[0033] Step (1): The catalytic solution is fed into a filter press electrolytic cell and electrolyzed at room temperature. The color of the catalytic solution gradually darkens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is acetonitrile, the electrolyte and catalyst are both tetrabutylammonium bromide with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode of the electrolysis is a graphite felt electrode, and the cathode is a stainless steel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol, and the cell voltage is approximately 4.7 V; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus (P4) and 100 mL of ethanol (EtOH) are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with ethanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, ethanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell, and the unreacted ethanol is recycled back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0034] In this embodiment, 51.6 g of product was collected, with a Faraday current efficiency of 95%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 4.18 – 4.06 (m, 6H), 1.41 – 1.31 (m, 9H). 13 C NMR (101 MHz, Chloroform- d ) δ 63.5 (d, J = 5.8 Hz), 16.0 (d, J = 6.6Hz). 31 P NMR (162 MHz, Chloroform- d ) δ -0.99. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0035] Example 2 The low-energy electrosynthesis method for the phosphate triester compounds in this embodiment is basically the same as that in Example 1, the only difference being that the solvent in this embodiment is dimethyl sulfoxide. This embodiment synthesizes the target product as in Example 1, with a Faraday current efficiency of 85%.

[0036] Example 3 The low-energy electrosynthesis method for the phosphate triester compounds in this embodiment is basically the same as that in Example 1, the only difference being that the solvent in this embodiment is N,N-dimethylformamide. This embodiment synthesizes the target product as in Example 1, with a Faraday current efficiency of 75%.

[0037] Example 4 The low-energy electrosynthesis method for the phosphate triester compounds in this embodiment is basically the same as that in Example 1, the only difference being that the solvent in this embodiment is N,N-dimethylacetamide. This embodiment synthesizes the target product as in Example 1, with a Faraday current efficiency of 78%.

[0038] Example 5 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 1, the only difference being that the solvent used in this embodiment is dichloromethane. This embodiment synthesizes the target product as in Example 1, with a Faraday current efficiency of 70%.

[0039] Example 6 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 1, the only difference being that the solvent in this embodiment is nitromethane. This embodiment synthesizes the target product as in Example 1, with a Faraday current efficiency of 87%.

[0040] Example 7 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 1, the only difference being that the solvent in this embodiment is water, and the electrolyte and catalyst are both tetrabutylammonium chloride; using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolyzer, which is then converted into a separation cell. In this embodiment, the target product as described in Example 1 is synthesized, with a Faraday current efficiency of 93%.

[0041] Example 8 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 1, except that the electrolyte in this embodiment is tetrabutylammonium tetrafluoroborate with a concentration of 1 mol / L; and the catalyst is ferric sulfate with a concentration of 1 mol / L. This embodiment synthesizes the target product as in Example 1 with a Faraday current efficiency of 82%.

[0042] Example 9 The low-energy electrosynthesis method for the phosphate triester compounds in this embodiment is basically the same as that in Example 1, except that the electrolyte in this embodiment is tetrabutylammonium tetrafluoroborate with a concentration of 1 mol / L; and the catalyst is 2,2,6,6-tetramethylpiperidine oxide with a concentration of 1 mol / L. This embodiment synthesizes the target product as in Example 1 with a Faraday current efficiency of 82%.

[0043] Example 10 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 3, the only difference being that the anode in this embodiment is a size-stable anode, and the cathode is a nickel electrode. This embodiment synthesizes the target product as in Example 3, with a Faraday current efficiency of 96%.

[0044] Example 11 The low-energy electrosynthesis method for phosphate triesters in this embodiment is basically the same as that in Example 6, except that the electrolysis current density in this embodiment is 5000 A / m. 2 In this embodiment, the target product as described in Example 6 was synthesized, with a Faraday current efficiency of 89%.

[0045] Example 12 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 6, except that the electrolysis temperature in this embodiment is 70 °C. This embodiment synthesizes the target product as in Example 6, with a Faraday current efficiency of 92%.

[0046] Example 13 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0047] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at room temperature. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 100 mL of methanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with methanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, methanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell for recycling, and the unreacted methanol is recycled back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0048] The Faraday current efficiency in this embodiment is 96%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 3.78 (d, J = 11.1 Hz, 9H). 13 C NMR (101 MHz, Chloroform- d ) δ 54.2 (d, J = 6.0 Hz). 31P NMR (162 MHz, Chloroform- d ) δ 2.34. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0049] Example 14 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0050] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalytic liquid is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 200 mL of n-butanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalytic liquid and reacts with n-butanol to obtain a crude reaction liquid. Step (3): The phosphate triester compounds, n-butanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled to the filter press electrolytic cell, and the unreacted n-butanol is recycled to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0051] The Faraday current efficiency in this embodiment is 94%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 4.04 (q, J = 6.7 Hz, 6H), 1.72 – 1.61(m, 6H), 1.49 – 1.35 (m, 6H), 0.94 (t, J = 7.4 Hz, 9H). 13 C NMR (101 MHz, Chloroform-d ) δ 67.2 (d, J = 6.1 Hz), 32.2 (d, J = 6.8Hz), 18.5, 13.4. 31 P NMR (162 MHz, Chloroform- d ) δ -0.68. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0052] Example 15 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0053] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 100 mL of 2-chloroethanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with 2-chloroethanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, 2-chloroethanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell, and the unreacted 2-chloroethanol is recycled back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0054] The Faraday current efficiency in this embodiment is 94%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 4.45 – 4.28 (m, 6H), 3.80 – 3.71 (m, 6H). 13 C NMR (101 MHz, Chloroform- d ) δ 67.3 (d, J = 5.5 Hz), 42.3 (d, J = 7.7Hz). 31 P NMR (162 MHz, Chloroform- d ) δ -2.21. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0055] Example 16 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0056] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 200 mL of chloropropanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with chloropropanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, chloropropanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled to the filter press electrolytic cell, and the unreacted chloropropanol is recycled to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0057] The Faraday current efficiency in this embodiment is 87%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 4.55 – 4.31 (m, 3H), 3.88 – 3.79 (m,6H) 1.18 (d, J = 5.5 Hz, 9 H). 13 C NMR (101 MHz, Chloroform- d ) δ 68.5 (d, J = 6.4 Hz), 43.5 (d, J = 7.4Hz), 13.9. 31 P NMR (162 MHz, Chloroform- d ) δ -1.82. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0058] Example 17 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0059] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 300 mL of dichloropropanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with dichloropropanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, dichloropropanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell, and the unreacted dichloropropanol is recycled back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0060] The Faraday current efficiency in this embodiment is 84%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 4.51 – 4.47 (m, 6H), 4.15 – 4.07 (m, 3H), 3.95 – 3.83 (m, 6H). 13 C NMR (101 MHz, Chloroform- d ) δ 68.5 (d, J = 6.4 Hz), 45.1 (d, J = 6.7Hz), 43.5 (d, J = 7.4 Hz). 31 P NMR (162 MHz, Chloroform- d ) δ -1.33. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0061] Example 18 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0062] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 300 mL of 2-ethylhexanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with 2-ethylhexanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, 2-ethylhexanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled to the filter press electrolytic cell, and the unreacted 2-ethylhexanol is recycled to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0063] The Faraday current efficiency in this embodiment is 91%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 3.94 (td, J = 5.5, 1.9 Hz, 6H), 1.57(p, J = 5.8 Hz, 3H), 1.49 – 1.35 (m, 9H), 1.32 – 1.22 (m, 16H), 0.90 (t, J = 7.5Hz, 18H). 13 C NMR (101 MHz, Chloroform- d ) δ 69.5 (d, J = 6.4 Hz), 40.0 (d, J = 7.4Hz), 29.8, 28.8, 23.6, 22.9, 13.9, 10.8. 31 P NMR (162 MHz, Chloroform- d ) δ -0.38. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0064] Example 19 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0065] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 100 mL of isobutanol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with isobutanol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, isobutanol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell, and the unreacted isobutanol is recycled back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0066] The Faraday current efficiency in this embodiment is 90%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 3.87 – 3.77 (m, 6H), 2.04 – 1.91 (m,3H), 1.02 – 0.93 (m, 18H). 13 C NMR (101 MHz, Chloroform- d ) δ 73.2 (d, J = 6.2 Hz), 28.7 (d, J = 7.1Hz), 18.3. 31 P NMR (162 MHz, Chloroform- d ) δ -0.99. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0067] Example 20 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0068] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 500 g of phenol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with phenol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, phenol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell. The unreacted phenol is added back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0069] The Faraday current efficiency in this embodiment is 91%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 6.73 (d, 6H), 7.09 – 7.11 (m, 6H)6.82 – 6.93 (m, 3H). 13 C NMR (101 MHz, Chloroform- d ) δ 150.5 (d, J = 7.6 Hz), 129.9, 125.6,120.1 (d, J = 4.9 Hz). 31 P NMR (162 MHz, Chloroform- d -17.70. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0070] Example 21 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0071] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 500 g of 4-methylphenol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with 4-methylphenol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, 4-methylphenol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell. The unreacted 4-methylphenol is added back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0072] The Faraday current efficiency in this embodiment is 88%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.19- 7.12 (m, 12H), 2.35 (s, 9H). 13 C NMR (101 MHz, Chloroform- d ) δ 148.4 (d, J = 7.6 Hz), 135.1, 130.3,119.9 (d, J = 4.9 Hz), 20.8. 31 P NMR (162 MHz, Chloroform- d ) δ-22.07. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0073] Example 22 The low-energy electrosynthesis method for phosphate triesters comprises the following steps:

[0074] Step (1): The catalyst solution is fed into a filter press electrolyzer, using Nafion... TM 117 is used as the electrolytic ion exchange membrane in the electrolytic cell. The electrolytic cell is changed to a separation cell. Electrolysis is carried out at 70 °C. The color of the catalytic solution gradually deepens, and hydrogen gas is released at the same time, resulting in an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and the catalyst are both tetrabutylammonium chloride with a concentration of 1 mol / L, and the additive is sulfuric acid with a concentration of 0.5 mol / L. The anode in the electrolysis is a size-stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m². 2 The current density is 1000 A / m 2 The applied charge is 5 F / mol; Step (2): The oxidized catalyst solution is introduced into the white phosphorus reactor, and the reaction substrate is added in a continuous feeding manner. In this embodiment, 9.25 g of white phosphorus and 500 g of 4-chlorophenol are added to the white phosphorus reactor. The white phosphorus is oxidized under the action of the oxidized catalyst solution and reacts with 4-chlorophenol to obtain a crude reaction solution. Step (3): The phosphate triester compounds, 4-chlorophenol and catalyst solution generated from the crude reaction solution are separated. The catalyst solution is recycled back to the filter press electrolytic cell. The unreacted 4-chlorophenol is added back to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0075] The Faraday current efficiency in this embodiment is 85%; the nuclear magnetic resonance spectral data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.24- 7.17 (m, 6H), 7.09- 7.04 (m, 6H). 13 C NMR (101 MHz, Chloroform- d ) δ 160.1 (dd, J = 245.2 Hz, J = 1.3 Hz), 146.1 (dd, J = 7.2 Hz, J = 2.7 Hz), 121.5 (dd, J = 8.4 Hz, J = 4.7 Hz), 116.6 (d, J =23.8 Hz). 31P NMR (162 MHz, Chloroform- d ) δ-17.1. The above results demonstrate that the product with the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0076] Example 23 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 1, except that the electrolyte in this embodiment is tetrabutylammonium tetrafluoroborate with a concentration of 1 mol / L; and the catalyst is potassium bromide with a concentration of 1 mol / L. This embodiment synthesizes the target product as in Example 1 with a Faraday current efficiency of 72%.

[0077] Example 24 The low-energy electrosynthesis method for phosphate triester compounds in this embodiment is basically the same as that in Example 1, except that the electrolyte in this embodiment is tetrabutylammonium tetrafluoroborate with a concentration of 1 mol / L, and the catalyst is ammonium chloride with a concentration of 1 mol / L. This embodiment synthesizes the target product as in Example 1 with a Faraday current efficiency of 69%.

[0078] Comparative Example 1 This comparative example is basically the same as Example 1, except that the solvent used in this example is trifluorotoluene. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 8%. To improve the yield, the solvent type selected in this invention is suitable for use in the process.

[0079] Comparative Example 2 This comparative example is basically the same as Example 1, except that the catalyst used in this example is chromium sulfate. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 15%. Similarly, to improve the yield, the catalyst type selected in this invention is suitable for the process.

[0080] Comparative Example 3 This comparative example is basically the same as Example 1, except that no additives are added in this example. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 10%. Similarly, to improve the yield, the additives required by this invention are suitable for use in the process.

[0081] Comparative Example 4 This comparative example is essentially the same as Example 1, except that the electrolyte and catalyst in this example are both tetrabutylammonium tetrafluoroborate. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 13%. Similarly, to improve the yield, the catalyst type selected in this invention is suitable for the process.

[0082] Comparative Example 5 This comparative example is basically the same as Example 1, except that the electrolyte and catalyst in this example are both tetrabutylammonium hexafluorophosphate. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 12%. Similarly, to improve the yield, the catalyst type selected in this invention is suitable for the process.

[0083] Comparative Example 5 This comparative example is essentially the same as Example 1, except that the electrolyte and catalyst in this example are both sodium sulfate. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 16%. Similarly, to improve the yield, the catalyst type selected in this invention is suitable for the process.

[0084] Comparative Example 6 This comparative example is basically the same as Example 1, except that the electrolyte and catalyst in this example are both potassium nitrate. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 12%. Similarly, to improve the yield, the catalyst type selected in this invention is suitable for the process.

[0085] Comparative Example 7 This comparative example is essentially the same as Example 1, except that the electrolyte and catalyst in this example are both potassium hydrosulfide. This example synthesizes the target product as in Example 1, but the Faraday current efficiency of the product is only 17%. Similarly, to improve the yield, the catalyst type selected in this invention is suitable for the process.

[0086] In summary, this invention employs a synthesis strategy that separates the electro-oxidation process from the chemical reaction process, successfully achieving a fully continuous flow synthesis of phosphate triester compounds under different parameters and selected raw materials. This process leverages the simplicity of the electrolysis system, using a catalytic solution as the electrolyte, resulting in a lower reaction tank voltage and thus reasonably reducing energy consumption and cost. During electrolysis, the catalyst first loses electrons at the anode surface, forming an oxidizing catalyst, which then flows into the reaction apparatus along with the oxidized catalytic solution. Subsequently, the oxidized catalyst reacts with white phosphorus, oxidizing it and then reducing it back to its normal state. The oxidized white phosphorus exhibits good reactivity, reacting with a stoichiometric amount of monohydroxy compound to form the target phosphate triester compound, which can be considered as continuously generated with the addition of substrate in actual industrial production. Thus, the product, catalytic solution, and unreacted alcohols or phenols can be continuously separated from the crude reaction solution. After recirculating the catalytic solution back to the electrolysis apparatus, the above steps can be repeated for the continuous synthesis of phosphate triester compounds. This invention uses a catalytic liquid as the medium for participating in the cyclic reaction. This synthetic route overcomes the production interruptions caused by the reaction of white phosphorus and monohydric hydroxyl compounds in an electrolytic cell under the action of current and product separation in existing electrolytic synthesis systems. It is particularly suitable for industrial production, improves the production capacity of phosphate triester compounds, and has good application prospects.

[0087] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A low-energy-consumption electrosynthesis method for phosphate triester compounds, characterized in that, Includes the following steps: Step (1): The catalytic solution is fed into the electrolysis device, and electrolysis causes the catalyst in it to lose electrons on the anode surface to obtain an oxidized catalytic solution; the components of the catalytic solution include solvent, electrolyte and catalyst; Step (2): The oxidized catalyst solution is fed into the reaction device, and white phosphorus and excess monohydroxy compound are added to the reaction device in a continuous feeding manner. White phosphorus is oxidized in the presence of an oxidizing catalyst and reacts with a monohydric hydroxyl compound to obtain a crude reaction solution; the monohydric hydroxyl compound is an alcohol or a phenolic compound. Step (3): The target product, phosphate triester compounds, residual catalyst and unreacted monohydroxy compounds are separated from the crude reaction solution. The residual catalyst is recycled to the electrolysis device and the unreacted monohydroxy compounds are recovered and added to the reaction device as raw materials to continuously synthesize phosphate triester compounds. In step (1), the solvent includes at least one of acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane, dichloroethane, water, methanol, ethanol, ethylene glycol dimethyl ether, and nitromethane; The electrolyte includes at least one of the following: tetrabutylammonium iodide, tetraethylammonium bromide, potassium iodide, sodium iodide, ammonium iodide, lithium iodide, tetrabutylammonium bromide, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, potassium chloride, sodium chloride, ammonium chloride, lithium chloride, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, sodium sulfate, potassium sulfate, potassium nitrate, and potassium hydrosulfide; The catalyst is at least one of the following: tetrabutylammonium bromide, tetrabutylammonium chloride, ferric sulfate, 2,2,6,6-tetramethylpiperidine oxide, potassium iodide, sodium iodide, ammonium iodide, lithium iodide, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, tetraethylammonium bromide, tetraethylammonium chloride, potassium chloride, sodium chloride, ammonium chloride, lithium chloride, and tetrabutylammonium perchlorate. Additives are added to the catalyst solution. The additives include one or two of sulfuric acid, hydrochloric acid, lithium perchlorate, lithium chloride, and trifluoroacetic acid. The molar ratio of white phosphorus to the additives is 0.01-10:

1.

2. The low-energy electrosynthesis method for phosphate triester compounds according to claim 1, characterized in that: The concentration of the electrolyte in the catalytic solution is 0.01-10 mol / L; the concentration of the catalyst is 0.01-10 mol / L.

3. The low-energy electrosynthesis method for phosphate triester compounds according to claim 1, characterized in that: In step (1), the electrolytic cell of the electrolysis device is a filter press type electrolytic cell; the anode is selected from one of graphite electrode, graphite felt electrode, and dimensionally stable anode; the cathode is selected from one of platinum electrode, stainless steel electrode, iron electrode, nickel electrode, nickel-plated platinum electrode, and nickel-plated ruthenium electrode; the area of ​​a single electrode in the filter press type electrolytic cell is 0.001-5 m². 2 ; The number of electrolysis units ranges from 1 to 150.

4. The low-energy electrosynthesis method for phosphate triester compounds according to claim 3, characterized in that: In step (1), the current density for electrolysis is 200-6000 A / m. 2 The electrolysis temperature is 0-100 ℃; the amount of electricity passed is 0.1-8 F / mol.

5. The low-energy electrosynthesis method for phosphate triester compounds according to claim 1, characterized in that: In step (2), among the monohydroxy compounds, alcohols include C1-C9 saturated monohydric alcohols and their substitutes, the number of substituents in the saturated monohydric alcohol substitutes is 1 or 2, and the substituent types include halogens; phenols include phenols and their substitutes; the number of substituents in the phenol substitutes is 1-3, and the substituent types include at least one of halogens, C1-C9 alkyl groups, nitro groups, trifluoromethyl groups, and methoxy groups.

6. The application of a low-energy electrosynthesis method for phosphate triester compounds as described in any one of claims 1-5, characterized in that: It is used as an electrolytic process to produce triphosphate compounds.

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