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] The invention relates to the technical field of electrolytic process for producing compounds, and in particular to a low-energy consumption electric synthesis method for phosphate triester compounds. Background Art

[0002] Trisphosphate compounds are a class of organic compounds containing phosphate groups, which have high reactivity and stability. Trisphosphate compounds are mainly used in industry as phosphorus-containing pesticides, nerve gases, flame-retardant hydraulic oils, lubricating oils, etc. In the medical field, some trisphosphate compounds have insecticidal and bactericidal effects and can be used as pesticides. In addition, they are also used in large quantities as plastic additives to improve the flame retardancy, thermal stability and mechanical properties of plastics. Therefore, trisphosphate compounds are a class of multifunctional organic compounds that play an important role in multiple industrial fields, and their synthesis and application research are important branches in the fields of chemical engineering and materials science.

[0003] At present, the methods for synthesizing triester phosphate compounds in industry are mainly sodium alcoholate method and electrochemically promoted synthesis of triester phosphate compounds. Among them, the sodium alcoholate method reacts alcohol with sodium hydroxide to generate the corresponding sodium alcoholate, which is then esterified with phosphorus oxychloride to synthesize phosphate products. The advantage of this method is high reaction activity, but there are disadvantages such as severe corrosion to the equipment, cumbersome steps and high environmental pollution.

[0004] Electrochemically promoted synthesis of triester phosphate compounds is a new synthesis method that uses electrochemical reactions to convert white phosphorus and alcohol into triester phosphate compounds under an inert atmosphere. This method avoids the problems of high pollution and high corrosion in traditional methods. The whole process has a high conversion rate of white phosphorus and a safe post-reaction treatment process.

[0005] For example, the Chinese invention patent with publication number CN114752953A discloses a method for preparing trialkyl phosphate from white phosphorus by electrochemical promotion. In an inert atmosphere, a halogen-containing salt as an electrolyte, ROH (R represents an alkyl group), and a white phosphorus solution are added to a reaction vessel. The mixture is placed in a mixed solvent of a solvent (a solvent for dissolving white phosphorus) and a reaction raw material alcohol, and an electric current is passed through the mixture for a certain period of time to react, thereby obtaining a trialkyl phosphate derivative. This scheme uses white phosphorus and alcohol as raw materials, and uses an electrochemical reaction under the catalytic action of halogen-containing alkali metal and alkaline earth metal salts to quickly prepare trialkyl phosphate. For another example, the Chinese invention patent with publication number CN115323406A provides an electrochemical preparation method for triester phosphate compounds, wherein an organic solvent, white phosphorus, alcohol or phenol and an electrolyte are mixed, and an electrolysis reaction is carried out in a constant current mode to obtain triester phosphate compounds. However, the mainstream method for synthesizing triester phosphate compounds in industry is still the sodium alcohol method, because the production scale of electrochemical synthesis is limited by the electrolysis process. In the electrolytic reaction, the raw materials are added in a "one-pot" manner and reacted in the electrolytic cell. The steps of feeding, reaction, and product recovery are carried out in the same solution environment, which makes it difficult to form a continuous flow process. This makes it difficult to achieve continuous production of triester phosphate compounds, limiting the large-scale application of electrochemical synthesis methods in industry.

[0006] In summary, a low-energy consumption electric synthesis method for phosphate triester compounds suitable for industrial production is provided to achieve the purpose of uninterrupted production of phosphate triester compounds, which is of great significance for promoting their application and has a positive environmental protection effect. Summary of the invention

[0007] In view of the above-mentioned defects of the prior art, the first aspect of the present invention provides a simple, efficient, green and environmentally friendly low-energy consumption electric synthesis method for phosphate triester compounds that can achieve full continuous flow production, comprising the following steps: Step (1), flowing the catalytic liquid into an electrolysis device, causing the catalyst therein to lose electrons on the anode surface through electrolysis, thereby obtaining an oxidized catalytic liquid; the components of the catalytic liquid include a solvent, an electrolyte, and a catalyst; Step (2), the oxidized catalyst liquid is flowed into the reaction device, and white phosphorus and an excess of 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 liquid and reacts with the monohydroxy compound to obtain a crude reaction liquid; the monohydroxy compound is an alcohol or a phenol compound; Step (3), separating the target product triester phosphate compound, residual catalyst liquid and unreacted monohydroxy compound from the crude reaction liquid, returning the residual catalyst liquid to the electrolysis device for recycling, recovering the unreacted monohydroxy compound as a reaction raw material and adding it to the reaction device to continuously synthesize triester phosphate 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 the art, solvents are used to promote the dispersion of substances and to create a suitable environment for reactions. Solvents are chemically inert relative to the raw materials, intermediates or products used in the synthesis and do not react with them. In addition, based on the physical properties of white phosphorus in the reaction substrate of the present invention, the solvent is preferably a type that is insoluble or has low solubility in white phosphorus. Thus, in the reaction, white phosphorus is insoluble in the solvent in the oxidized catalyst solution and directly reacts with the monovalent hydroxyl compound, which helps to reduce the difficulty of subsequent separation and recovery of the product and the catalyst 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] The electrolyte improves 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 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, ferric chloride, ferric sulfate, ferric acetate, cobalt acetate, cobalt chloride, vanadium sulfate, and 2,2,6,6-tetramethylpiperidinyl oxide.

[0013] The catalyst of the present invention is converted into an oxidized catalyst under the action of electric current and is used as a medium for cyclic reaction in the synthesis of phosphate triester compounds. It should be particularly noted that some types of catalysts can also simultaneously play the role of electrolytes. For such identical substances, the whole can be regarded as the sum of the electrolyte part and the catalyst part.

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

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

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

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

[0018] Further preferably, the area of ​​a single electrode in the filter press electrolytic cell is 0.001-5 m 2 ; The number of electrolytic units is 1-150.

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

[0020] The process has good industrial applicability and does not require specialized equipment or special treatment. Within the above-defined parameter range, it is conducive to the efficient conversion of raw materials and completes the reaction.

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

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

[0023] The crude reaction liquid obtained by the reaction mainly contains triester phosphate compounds, unreacted alcohol or phenol compounds and catalyst liquid, and the above components can be treated by common industrial separation means, such as column chromatography, distillation, etc. The remaining alcohol or phenol compounds can be recycled as raw materials to the reaction device, reducing production costs and waste.

[0024] In the second aspect of the present invention, there is provided an application of the low-energy consumption electric synthesis method of phosphate triester compounds according to the first aspect of the present invention, specifically as an electrolytic process for producing phosphate triester compounds.

[0025] Based on the above technical scheme, the inventive concept of the present invention is to adopt a synthesis strategy that separates the electro-oxidation process and the chemical reaction process, and realize a full continuous flow process based on the simplicity of the electrolysis process system. The catalytic liquid is used as the electrolyte, which does not contain complex, poorly conductive solutes, which is conducive to reducing the cell voltage of the reaction, so as to reduce energy consumption and cost. During the electrolysis process, the catalyst loses electrons on the anode surface to form an oxidized catalyst with oxidizing properties, and then flows into the reaction device with the oxidized catalytic liquid. At this time, the oxidized catalyst reacts with white phosphorus to oxidize it and reduce itself to a normal catalyst. The oxidized white phosphorus has good reactivity and reacts with a chemical reaction amount of a monohydroxy compound to form a target phosphate triester compound. In this way, the product and the catalytic liquid can be continuously separated from the crude reaction liquid. After the catalytic liquid is refluxed to the electrolysis device, the above steps can be circulated to continuously and uninterruptedly synthesize the phosphate triester compound. The present invention uses the catalytic liquid as a medium participating in the cyclic reaction. The synthesis path overcomes the production interruption caused by the reaction and product separation of white phosphorus and a monohydroxy compound in an electrolytic cell under the action of an electric current in the existing electrolysis synthesis system.

[0026] The following reaction formula describes the reaction principle of each step in the present invention: The electrolysis reaction in step (1) is: ; In the formula, Cat. represents catalyst; The reaction formula in step (2) is: ; In the formula, ROH represents a monohydroxy compound; R represents a 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: The present invention provides a low-energy consumption electric synthesis method for phosphate triester compounds, which has the advantages of being simple, efficient, green and environmentally friendly, and capable of realizing full continuous flow production, is suitable for industrial production, and improves the production capacity of phosphate triester compounds.

[0028] The present invention provides an application of a low-energy consumption electric synthesis method for phosphate triester compounds, which has good application prospects in the production of phosphate triester compounds as an electrolysis process. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The process flow chart of the low-energy consumption electrical synthesis method for the full continuous flow production of phosphate triester compounds. DETAILED DESCRIPTION

[0030] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0031] In the following embodiments: Nafion TM 117 is a commercially available perfluorosulfonic acid ion exchange membrane, which has an excellent perfluorosulfonic acid resin matrix and a unique ion exchange function. It is used as an electrolytic ion exchange membrane in the electrolytic cell in the embodiment. The commercial source is Chemours Company, and the model is N117; The commercial source of dimensionally stable anodes is Suzhou Shuertai Industrial Technology Co., Ltd., and the model specifications are ruthenium iridium titanium plates with a size of 100 mm × 100 mm.

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

[0033] Step (1), the catalyst liquid is flowed into the filter press electrolytic cell and electrolyzed at room temperature, the color of the catalyst liquid gradually deepens, and hydrogen is released, thereby obtaining an oxidized catalyst liquid; The solvent in the catalytic solution is acetonitrile, the electrolyte and catalyst are both tetrabutylammonium bromide, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis was a graphite felt electrode, the cathode was a stainless steel electrode, and the electrode area was 0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol, and the cell voltage is about 4.7 V; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the ethanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, ethanol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted ethanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0034] In this example, 51.6 g of product was collected, and the Faraday current efficiency was 95%; the nuclear magnetic resonance spectrum data of the product were 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0035] Example 2 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 1, except that the type of solvent in this embodiment is dimethyl sulfoxide. The target product synthesized in this embodiment is as in Example 1, and the Faraday current efficiency is 85%.

[0036] Example 3 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 1, except that the type of solvent in this embodiment is N,N-dimethylformamide. The target product synthesized in this embodiment is as in Example 1, and the Faraday current efficiency is 75%.

[0037] Example 4 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 1, except that the type of solvent in this embodiment is N,N-dimethylacetamide. The target product synthesized in this embodiment is as in Example 1, and the Faraday current efficiency is 78%.

[0038] Example 5 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 1, except that the type of solvent in this embodiment is dichloromethane. The target product synthesized in this embodiment is as in Example 1, and the Faraday current efficiency is 70%.

[0039] Example 6 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in embodiment 1, except that the type of solvent in this embodiment is nitromethane. The target product synthesized in this embodiment is as in embodiment 1, and the Faraday current efficiency is 87%.

[0040] Example 7 The low-energy consumption electrosynthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 1, except that the solvent in this embodiment is water, the electrolyte and the catalyst are both tetrabutylammonium chloride; Nafion TM 117 is used as the electrolytic ion exchange membrane of the electrolytic cell, and the electrolytic cell is changed into a separation cell. The target product as in Example 1 is synthesized in this embodiment, and the Faraday current efficiency is 93%.

[0041] Example 8 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 1, except that the type of electrolyte in this embodiment is tetrabutylammonium tetrafluoroborate, and its concentration is 1 mol / L; the type of catalyst is ferric sulfate, and its concentration is 1 mol / L. The target product synthesized in this embodiment is as in Example 1, and the Faraday current efficiency is 82%.

[0042] Example 9 The low-energy consumption electric synthesis method of the phosphate triester compound of this embodiment is basically the same as that of embodiment 1, except that the type of electrolyte in this embodiment is tetrabutylammonium tetrafluoroborate, and its concentration is 1 mol / L; the type of catalyst is 2,2,6,6-tetramethylpiperidinyl oxide, and its concentration is 1 mol / L. The target product synthesized in this embodiment is as in embodiment 1, and the Faraday current efficiency is 82%.

[0043] Example 10 The low-energy consumption electric synthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 3, except that the type of the anode in this embodiment is a dimensionally stable anode and the type of the cathode is a nickel electrode. The target product synthesized in this embodiment is as in Example 3, and the Faraday current efficiency is 96%.

[0044] Embodiment 11 The low-energy consumption electrosynthesis method of the phosphate triester compound in this embodiment is basically the same as that in Example 6, except that the current density of the electrolysis in this embodiment is 5000 A / m 2 The target product synthesized in this example is as shown in Example 6, and the Faradaic current efficiency is 89%.

[0045] Example 12 The low-energy consumption electrosynthesis method of the phosphate triester compound in this embodiment is basically the same as that in embodiment 6, except that the electrolysis temperature in this embodiment is 70° C. The target product synthesized in this embodiment is as in embodiment 6, and the Faraday current efficiency is 92%.

[0046] Embodiment 13 The low energy consumption electrosynthesis method of phosphate triester compounds comprises the following steps:

[0047] Step (1), the catalytic solution flows into the filter press electrolytic cell, and the Nafion TM 117 is used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell is changed into a separation cell. Electrolysis is carried out at room temperature. The color of the catalyst liquid gradually deepens, and hydrogen is released at the same time to obtain an oxidized catalyst liquid. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the methanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, methanol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted methanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0048] The Faraday current efficiency of this embodiment is 96%; the nuclear magnetic resonance spectrum 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0049] Embodiment 14 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0050] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 catalyst liquid and reacts with n-butanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, n-butanol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted n-butanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0051] The Faraday current efficiency of this embodiment is 94%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0052] Embodiment 15 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0053] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the 2-chloroethanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, 2-chloroethanol and the catalyst solution are separated from the crude reaction solution, the catalyst solution is refluxed to the filter press electrolytic cell for recycling, and the unreacted 2-chloroethanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0054] The Faraday current efficiency of this embodiment is 94%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0055] Example 16 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0056] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the chloropropanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, chloropropanol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted chloropropanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0057] The Faraday current efficiency of this embodiment is 87%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0058] Embodiment 17 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0059] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the dichloropropanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, dichloropropanol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted dichloropropanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0060] The Faraday current efficiency of this embodiment is 84%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0061] Embodiment 18 The low energy consumption electrosynthesis method of phosphate triester compounds comprises the following steps:

[0062] Step (1), the catalytic solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the 2-ethylhexanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, 2-ethylhexanol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted 2-ethylhexanol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0063] The Faraday current efficiency of this embodiment is 91%; the nuclear magnetic resonance spectrum 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0064] Embodiment 19 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0065] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the isobutanol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, isobutyl alcohol and catalyst liquid are separated from the crude reaction liquid, the catalyst liquid is refluxed to the filter press electrolytic cell for recycling, and the unreacted isobutyl alcohol is refluxed to the white phosphorus reactor as a reaction raw material to continuously synthesize the phosphate triester compounds.

[0066] The Faraday current efficiency of this embodiment is 90%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0067] Embodiment 20 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0068] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with the phenol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, phenol and catalyst solution are separated from the crude reaction solution, the catalyst solution is returned to the filter press electrolytic cell for recycling, and 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 of this embodiment is 91%; the nuclear magnetic resonance spectrum 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0070] Embodiment 21 The low energy consumption electric synthesis method of phosphate triester compounds comprises the following steps:

[0071] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with 4-methylphenol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, 4-methylphenol and catalyst solution are separated from the crude reaction solution, the catalyst solution is refluxed to the filter press electrolytic cell for recycling, and 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 of this embodiment is 88%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0073] Embodiment 22 The low energy consumption electrosynthesis method of phosphate triester compounds comprises the following steps:

[0074] Step (1), the catalyst solution flows into the filter press electrolytic cell, and the Nafion TM 117 was used as the electrolytic ion exchange membrane of the electrolytic cell. The electrolytic cell was changed into a separation cell. The electrolysis was carried out at 70 °C. The color of the catalytic solution gradually deepened, and hydrogen was released at the same time to obtain an oxidized catalytic solution. The solvent in the catalytic solution is water, the electrolyte and catalyst are both tetrabutylammonium chloride, the concentration of which is 1 mol / L, and the additive is sulfuric acid, the concentration of which is 0.5 mol / L; The anode of the electrolysis is a dimensionally stable anode, and the cathode is a nickel electrode with an electrode area of ​​0.01 m 2 , current density is 1000 A / m 2 , the charge input is 5 F / mol; Step (2), introducing the oxidized catalyst liquid into the white phosphorus reactor, adding the reaction substrate 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 liquid and reacts with 4-chlorophenol to obtain a crude reaction liquid; In step (3), the phosphate triester compounds, 4-chlorophenol and the catalyst solution are separated from the crude reaction solution, the catalyst solution is refluxed to the filter press electrolytic cell for recycling, and 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 of this embodiment is 85%; the product nuclear magnetic resonance spectrum data 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 show that the product of the target structure was synthesized with high Faraday current efficiency in this embodiment.

[0076] Comparative Example 1 This comparative example is basically the same as Example 1, except that the type of solvent 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%. For the purpose of improving the yield, the type of solvent selected by the present invention is preferably used in the process.

[0077] Comparative Example 2 This comparative example is basically the same as Example 1, except that the type of catalyst 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, based on the purpose of improving the yield, the catalyst type selected by the present invention is preferably used in the process.

[0078] Comparative Example 3 This comparative example is basically the same as Example 1, except that no additive is added in this example. The target product synthesized in this example is as in Example 1, but the Faraday current efficiency of the product is only 10%. Similarly, for the purpose of improving the yield, the additive required by the present invention is appropriately used in the process.

[0079] In summary, the present invention adopts a synthesis strategy that separates the electro-oxidation process and the chemical reaction process, and successfully realizes the full continuous flow synthesis of phosphate triester compounds under different parameters and selected raw materials. This process is based on the simplicity of the electrolysis process system, uses a catalytic liquid as an electrolyte, has a lower reaction tank voltage, and can reasonably reduce energy consumption and cost. During the electrolysis process, the catalyst first loses electrons on the anode surface to form an oxidized catalyst with oxidizing properties, and then flows into the reaction device with the oxidized catalytic liquid. Subsequently, the oxidized catalyst reacts with white phosphorus to oxidize it and reduce itself to a normal catalyst. The oxidized white phosphorus has good reactivity and reacts with a chemical reaction amount of a monohydroxy compound to form a target phosphate triester compound, which can be regarded as being continuously generated with the addition of a substrate in actual industrial production. Thus, the product, the catalytic liquid, and the unreacted alcohol or phenol compound can be continuously separated from the crude reaction liquid. After the catalytic liquid is refluxed to the electrolysis device, the above steps can be circulated to continuously synthesize the phosphate triester compound. The present invention uses a catalytic liquid as a medium participating in a cyclic reaction. The synthesis route overcomes the production interruption caused by the reaction of white phosphorus and a monovalent hydroxyl compound in an electrolytic cell under the action of an electric current and the separation of products in the existing electrolytic synthesis system. The present invention is particularly suitable for industrial production, improves the production capacity of triester phosphate compounds, and has good application prospects.

[0080] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A low-energy consumption electric synthesis method for triester phosphate compounds, characterized in that: The steps include: Step (1), flowing the catalytic liquid into an electrolysis device, causing the catalyst therein to lose electrons on the anode surface through electrolysis, thereby obtaining an oxidized catalytic liquid; the components of the catalytic liquid include a solvent, an electrolyte, and a catalyst; Step (2), the oxidized catalyst liquid is flowed into the reaction device, and white phosphorus and an excess of 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 liquid and reacts with a monohydroxy compound to obtain a crude reaction liquid; the monohydroxy compound is an alcohol or a phenol compound; Step (3), separating the target product triester phosphate compound, residual catalyst liquid and unreacted monohydroxy compound from the crude reaction liquid, returning the residual catalyst liquid to the electrolysis device for recycling, recovering the unreacted monohydroxy compound as a reaction raw material and adding it to the reaction device to continuously synthesize triester phosphate 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 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 hydrogen sulfide; The catalyst includes at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, ferric sulfate, and 2,2,6,6-tetramethylpiperidinyl oxide; Additives are added to the catalyst liquid, and the additives include one or two of sulfuric acid, hydrochloric acid, lithium perchlorate, lithium chloride, and trifluoroacetic acid; the molar ratio of the white phosphorus to the additive is 0.01-10:

1.

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

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

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

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

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

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