Thiophosphoric acid triphenyltriamine and preparation process thereof

Abstract

The invention provides triphenyltriamine thiophosphate and a preparation process thereof. The triphenyltriamine thiophosphate is prepared from the following raw materials in parts by weight: 33 to 40 parts of aniline derivative, 25 to 35 parts of halogenated phosphorylation reagent, 3 to 8 parts of catalyst, 190 to 210 parts of aprotic polar solvent, 10 to 20 parts of alkaline neutralizer, 0.5 to 1.5 parts of antioxidant, 10 to 18 parts of novel composite acid-binding agent and 240 to 300 parts of mixed organic solvent. According to the preparation method, the phenolic hydroxyl group in the aniline derivative and the halogenated phosphorylation reagent are subjected to substitution reaction under the action of the catalyst and the acid-binding agent to generate the target product triphenyltriamine thiophosphate, so that the yield of the target product is ensured.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, specifically to a triphenyltriamine thiophosphate and its preparation process. Background Technology

[0002] Triphenyltriamine thiophosphate, an important organic compound, is widely used as an intermediate in pharmaceuticals, pesticides, and dyes. It also plays a crucial role as a chain extender in high-grade polyurethanes, and its excellent properties have led to a continuous increase in market demand. With the development of related industries, the requirements for the quality and yield of triphenyltriamine thiophosphate are also increasing. Therefore, how to prepare this compound efficiently, environmentally friendly, and at low cost has become a research hotspot.

[0003] Existing methods for preparing triphenyltriamine thiophosphate present numerous problems. In terms of production processes, some existing methods require harsh reaction conditions, such as high temperature and high pressure. This not only increases equipment investment and energy costs but also places extremely high demands on the performance and stability of the reaction equipment, while also increasing safety risks during production. Furthermore, the post-processing is complex, solvent recovery is difficult, and product separation and purification efficiency is low, resulting in high production costs and hindering large-scale industrial production. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention provides a triphenyltriamine thiophosphate and its preparation process.

[0005] To achieve the above objectives, the present invention provides the following technical solution: This application discloses a triphenyltriamine thiophosphate, which comprises the following raw materials in parts by weight: 33-40 parts of aniline derivative, 25-35 parts of halophosphorylating agent, 3-8 parts of catalyst, 190-210 parts of aprotic polar solvent, 10-20 parts of alkaline neutralizing agent, 0.5-1.5 parts of antioxidant, 10-18 parts of novel composite acid-binding agent, and 240-300 parts of mixed organic solvent.

[0006] Preferably, the aniline derivative is composed of p-aminophenol and p-aminophenol-graphene nanocomposite in a mass ratio of 3:1. The p-aminophenol-graphene nanocomposite is prepared by the following method: 0.5g of graphene oxide is added to 100mL of ethanol and ultrasonically dispersed for 1h to achieve uniform dispersion. Then, 5g of p-aminophenol and 0.1g of sodium borohydride are added, and the mixture is stirred and reacted at room temperature for 12h. The product is then separated by centrifugation, washed multiple times with ethanol and water, and finally dried in a vacuum drying oven at 60℃ for 12h to obtain the final product.

[0007] By employing the aforementioned technical approach, p-aminophenol's hydroxyl group (-OH) undergoes a phosphorylation reaction with PSBr3 to form a thiophosphate bond, while the amino group (-NH2) remains in the product, endowing it with biological activity (such as acting as a urease inhibitor). Using graphene (GO) as a support, p-aminophenol (AP) can be loaded via π-π stacking or covalent bonding, thereby improving the reaction rate and product stability. GO's high specific surface area may promote reagent dispersion and enhance local reaction concentration.

[0008] Preferably, the halogenated phosphorylation reagent is thiophosphoryl bromide or thiophosphoryl chloride.

[0009] Preferably, the catalyst is one of triethylamine or N,N-dimethylaniline, the aprotic polar solvent is one of N,N-dimethylformamide or dimethyl sulfoxide, the alkaline neutralizing agent is one of sodium carbonate or potassium carbonate, and the antioxidant is one of 2,6-di-tert-butyl-p-cresol or butyl hydroxyanisole.

[0010] Preferably, the novel composite acid-binding agent is composed of triethylamine, amino-modified silica gel, and modified montmorillonite in a mass ratio of 5:3:2.

[0011] Preferably, the preparation method of amino-modified silica gel is as follows: 100g of silica gel is added to 800mL of toluene, ultrasonically dispersed for 30min, 50g of γ-aminopropyltriethoxysilane is added, and the mixture is refluxed at 80℃ for 12h. After the reaction is completed, the mixture is cooled, filtered, washed with toluene and ethanol in sequence, and then dried in a vacuum drying oven at 100℃ for 8h to obtain amino-modified silica gel.

[0012] The preferred method for preparing modified montmorillonite is as follows: 50g of montmorillonite is added to 1000mL of water and stirred to disperse evenly. 30g of cetyltrimethylammonium bromide is added and stirred at 60℃ for 6h. After the reaction is completed, the mixture is filtered, washed with deionized water until no bromide ions are present, and then dried in a vacuum drying oven at 80℃ for 10h. The mixture is then ground into powder to obtain modified montmorillonite.

[0013] By setting up the above technical solution, the amino-modified silica gel and modified montmorillonite in the novel composite acid binder, with their special structure and properties, adsorb residual acidic substances and impurities, more accurately maintain the pH stability of the reaction system, and ensure that the reaction proceeds under suitable conditions.

[0014] Preferably, the mixed organic solvent is composed of acetone, dichloroethane, and toluene in a volume ratio of 4:3:3.

[0015] By setting up the above technical solution, a mixed organic solvent composed of acetone, dichloroethane, and toluene can be used to expand the solubility range of raw materials and products by utilizing the different solubility properties and boiling points of each solvent, which facilitates reaction control and product separation and purification.

[0016] This application also discloses a preparation process for triphenyltriamine thiophosphate, which includes the following steps: S1. Add the aprotic polar solvent and the mixed organic solvent to a reactor equipped with a stirrer, thermometer and reflux condenser, control the temperature at 25-35℃, stir at a speed of 200-250r / min, then add the aniline derivative, antioxidant and catalyst in sequence, stir evenly to fully dissolve the raw materials; S2. Heat the reaction system to 70-80℃, slowly add the halophosphorylating reagent, and control the addition time to 1-2 hours. During the addition process, keep stirring at a speed of 200-250 r / min. After the addition is completed, continue stirring and react for 4-6 hours. During this period, check the pH value of the reaction system every 30 minutes. If the pH value drops, add an alkaline neutralizing agent and a new composite acid-binding agent in time to adjust it so that the pH value of the system is maintained between 7 and 9. S3. After the reaction is complete, cool the reaction solution to room temperature, pour it into a separatory funnel, let it stand to separate the layers, separate the organic phase, wash the organic phase with deionized water, each time the water volume is 1 / 3 of the organic phase volume, wash 3-5 times until the aqueous phase is neutral, transfer the washed organic phase to a distillation flask, and remove the solvent by distillation under reduced pressure to obtain the crude product. S4. Dissolve the crude product in an appropriate amount of acetone, add activated carbon for decolorization, stir at 100-110 r / min for 30 min, filter while hot, cool the filtrate to crystallize, wash the crystals 2-3 times with a small amount of cold acetone, place the crystals in a vacuum drying oven and dry to constant weight to obtain triphenyltriamine thiophosphate.

[0017] By setting up the above technical solution, in a weakly alkaline environment with pH 7-9, organic base catalysis, and aprotic solvent system, the phenolic hydroxyl group can significantly enhance the reactivity by dissociating into phenolic anions. Its nucleophilicity is sufficient to exceed that of amino groups, preferentially reacting with PSBr3 (or PSCl3) to generate the target product (triphenyltriamine thiophosphate) containing a PO bond. The antioxidants 2,6-di-tert-butyl-p-cresol or butyl hydroxyanisole contain phenolic hydroxyl structures, which can freely capture free radicals, preventing the oxidation of raw materials and products. During the reaction, they can more effectively protect the raw materials and products, improving the quality and stability of the product. The components work together to produce a significant synergistic effect, enabling the entire reaction system to operate efficiently and obtain a high-quality target product. The special functional groups of aniline derivatives synergistically interact with the active groups of halophosphorylating agents, providing diverse reaction sites, enriching the product structure, and optimizing the reaction pathway, thereby improving the selectivity and yield of the reaction.

[0018] Preferably, the vacuum drying temperature is 65-75℃.

[0019] The beneficial effects of this invention are as follows: Taking thiophosphoryl bromide as an example, the reaction equation is: 3H₂N-C₆H₄-OH + PSBr₃ → (H₂N-C₆H₄-O)₃P=S + 3HBr. p-Aminophenol and thiophosphoryl bromide undergo a substitution reaction under the action of a catalyst and a novel composite acid-binding agent to generate the target product C. 18 H 18 N3O3PS (triphenyltriamine thiophosphate, containing three amino groups, three benzene rings and one thiophosphate group, with the thiophosphate group and the amino group located at the para position of the benzene ring).

[0020] In p-aminophenol (H2N-C6H4-OH), both the amino group (-NH2) and the phenolic hydroxyl group (-OH) are nucleophilic groups, but their nucleophilicity differs fundamentally: the oxygen atom has high electronegativity and its lone pair electrons are more bound, resulting in weaker nucleophilicity than the amino group; however, under alkaline conditions, the phenolic hydroxyl group can dissociate into a phenoxide anion (-O). - The negative charge enhances its nucleophilicity, potentially reversing the reaction priority with amino groups. While amino groups primarily exist in a free state (-NH2) under weakly basic conditions, exhibiting strong nucleophilicity, the negative charge effect of the phenoxy anion makes its reactivity more dominant. Furthermore, using triethylamine or N,N-dimethylaniline (organic base) as a catalyst can further promote the dissociation of the phenolic hydroxyl group into the phenoxy anion, enhancing its nucleophilicity. Aprotic polar solvents (such as DMF and DMSO) have a stabilizing effect on the phenoxy anion (solvation effect), further enhancing its reactivity while reducing solvation interference with amino groups and inhibiting the reaction between amino groups and phosphorus. Finally, controlling the reaction temperature at 70-80℃ and slowly adding the halophosphorylating agent (PSBr3 / PSCl3) (1-2 h) can avoid non-selective reactions caused by excessively high local concentrations; mild temperature conditions can also reduce excessive reaction of amino groups (high temperatures may enhance the nucleophilic activity of amino groups). The components and conditions in the reaction system work together to generate the target product (triphenyltriamine thiophosphate) containing three amino groups, three benzene rings, and one thiophosphate ester group, thus inhibiting the occurrence of side reactions.

[0021] p-Aminophenol provides a hydroxyl group (-OH) that undergoes phosphorylation with PSBr3 / PSCl3 to form a thiophosphate bond. The amino group (-NH2) is retained in the product, conferring its biological activity (such as its role as a urease inhibitor). Graphene (GO) can be used as a support to load p-aminophenol (AP) via π-π stacking or covalent bonding, thereby improving the reaction rate and product stability. The high specific surface area of ​​GO may also promote reagent dispersion and enhance local reaction concentration.

[0022] Alkaline neutralizing agents composed of sodium carbonate or potassium carbonate work synergistically with novel composite acid-binding agents to neutralize most acidic substances. The amino-modified silica gel and modified montmorillonite in the novel composite acid-binding agent, with their unique structures and properties, adsorb residual acidic substances and impurities, more precisely maintaining the pH stability of the reaction system and ensuring the reaction proceeds under suitable conditions. Antioxidants effectively prevent the oxidation of raw materials and products during the reaction process, significantly improving the purity and stability of the products, preventing discoloration or degradation due to oxidation during storage and use, and extending shelf life.

[0023] In preparing triphenyltriamine thiophosphate in this application, thiophosphoryl bromide or thiophosphoryl chloride are chosen as the raw material instead of phosphoric acid because the hydroxyl group (-OH) in phosphoric acid is a weak leaving group (because O - (It has poor stability). If used directly in phosphorylation reactions, it requires extremely strong reaction conditions (such as high temperature and strong acid catalysis), and the reaction rate is extremely slow, or even impossible to occur. Taking thiophosphoryl bromide as an example, the bromine atom (-Br) in thiophosphoryl bromide is a strong leaving group (Br). - High stability allows for rapid reaction with nucleophiles under mild conditions (such as room temperature and weak base catalysis), significantly improving reaction efficiency. Furthermore, phosphoric acid is a tribasic acid (containing three -OH groups), and direct use in substitution reactions easily leads to multiple substitution side reactions, potentially generating mixtures of monoesters, diesters, and trimers, making it difficult to obtain a single target product. In contrast, all three bromine atoms in thiophosphoryl bromide (such as PSBr3) can be substituted. By controlling the stoichiometry and conditions, the degree of substitution can be precisely controlled, significantly reducing byproducts and improving the purity of the target product. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] Example 1: This embodiment discloses a triphenyltriamine thiophosphate, which comprises the following raw materials by weight: 30 parts of aniline derivative, 20 parts of halophosphorylating agent, 3 parts of catalyst, 190 parts of aprotic polar solvent, 10 parts of alkaline neutralizer, 0.5 parts of antioxidant, 8 parts of novel composite acid-binding agent, and 240 parts of mixed organic solvent.

[0026] The aniline derivative is composed of p-aminophenol and p-aminophenol-graphene nanocomposite in a mass ratio of 3:1. The p-aminophenol-graphene nanocomposite is prepared by the following method: 0.5 g of graphene oxide is added to 100 mL of ethanol and ultrasonically dispersed for 1 h to achieve uniform dispersion. Then, 5 g of p-aminophenol and 0.1 g of sodium borohydride are added, and the mixture is stirred and reacted at room temperature for 12 h. The product is then separated by centrifugation, washed multiple times with ethanol and water, and finally dried in a vacuum drying oven at 60 °C for 12 h to obtain the final product.

[0027] The halophosphorylating agent is thiophosphoryl bromide. The method for synthesizing the pentaphosphine-cyclodextrin inclusion complex is as follows: add pentaphosphine and β-cyclodextrin to a 95% ethanol solution at a molar ratio of 1:2, stir and react at 50°C for 6 hours. After the reaction is complete, cool and crystallize, filter and collect the crystals, wash the crystals with ethanol, and vacuum dry at 40°C for 8 hours to obtain the pentaphosphine-cyclodextrin inclusion complex.

[0028] The catalyst is triethylamine, the aprotic polar solvent is N,N-dimethylformamide, the alkaline neutralizer is sodium carbonate, and the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0029] The novel composite acid-binding agent is composed of triethylamine, amino-modified silica gel, and modified montmorillonite in a mass ratio of 5:3:2. The mixed organic solvent is composed of acetone, dichloroethane, and toluene in a volume ratio of 4:3:3.

[0030] The preparation method of amino-modified silica gel is as follows: 100g of silica gel is added to 800mL of toluene and ultrasonically dispersed for 30min. Then, 50g of γ-aminopropyltriethoxysilane is added and refluxed at 80℃ for 12h. After the reaction is completed, the mixture is cooled, filtered, washed with toluene and ethanol in sequence, and then dried in a vacuum drying oven at 100℃ for 8h to obtain amino-modified silica gel.

[0031] The preparation method of modified montmorillonite is as follows: 50g of montmorillonite is added to 1000mL of water and stirred to disperse evenly. 30g of cetyltrimethylammonium bromide is added and stirred at 60℃ for 6h. After the reaction is completed, the mixture is filtered, washed with deionized water until no bromide ions are present, and then dried in a vacuum drying oven at 80℃ for 10h. The mixture is then ground into powder to obtain modified montmorillonite.

[0032] This embodiment also discloses a preparation process for triphenyltriamine thiophosphate, which includes the following steps: S1. Add the aprotic polar solvent and the mixed organic solvent to a reactor equipped with a stirrer, thermometer and reflux condenser, control the temperature at 25°C, stir at 200 r / min, then add the aniline derivative, antioxidant and catalyst in sequence, stir evenly to fully dissolve the raw materials; S2. Heat the reaction system to 70℃, slowly add the halophosphorylating reagent, control the feeding time to 1 hour, and keep stirring at 200 r / min during the feeding process. After the feeding is completed, continue stirring and react for 4 hours. During this period, check the pH value of the reaction system every 30 minutes. If the pH value drops, add an alkaline neutralizing agent and a new composite acid-binding agent in time to adjust it so that the pH value of the system is maintained at 7-9. S3. After the reaction is complete, cool the reaction solution to room temperature, pour it into a separatory funnel, let it stand to separate the layers, separate the organic phase, wash the organic phase with deionized water, each time the water volume is 1 / 3 of the organic phase volume, wash 3-5 times until the aqueous phase is neutral, transfer the washed organic phase to a distillation flask, and remove the solvent by distillation under reduced pressure to obtain the crude product. S4. Dissolve the crude product in an appropriate amount of acetone, add activated carbon for decolorization, stir at 100 r / min for 30 min, filter while hot, cool the filtrate to crystallize, wash the crystals 2-3 times with a small amount of cold acetone, and dry the crystals in a vacuum drying oven at 65℃ to constant weight to obtain triphenyltriamine thiophosphate.

[0033] Example 2: This embodiment discloses a triphenyltriamine thiophosphate, which comprises the following raw materials in parts by weight: 40 parts of aniline derivative, 30 parts of halophosphorylating agent, 8 parts of catalyst, 210 parts of aprotic polar solvent, 20 parts of alkaline neutralizer, 1.5 parts of antioxidant, 15 parts of novel composite acid-binding agent, and 300 parts of mixed organic solvent.

[0034] The aniline derivative is composed of p-aminophenol and p-aminophenol-graphene nanocomposite in a mass ratio of 3:1. The p-aminophenol-graphene nanocomposite is prepared by the following method: 0.5 g of graphene oxide is added to 100 mL of ethanol and ultrasonically dispersed for 1 h to achieve uniform dispersion. Then, 5 g of p-aminophenol and 0.1 g of sodium borohydride are added, and the mixture is stirred and reacted at room temperature for 12 h. The product is then separated by centrifugation, washed multiple times with ethanol and water, and finally dried in a vacuum drying oven at 60 °C for 12 h to obtain the final product.

[0035] The halogenated phosphorylating agent is thiophosphoryl chloride. The method for synthesizing the pentaphosphine-cyclodextrin inclusion complex is as follows: add pentaphosphine and β-cyclodextrin to a 95% ethanol solution at a molar ratio of 1:2, stir and react at 50°C for 6 hours. After the reaction is complete, cool and crystallize, filter and collect the crystals, wash the crystals with ethanol, and dry under vacuum at 40°C for 8 hours to obtain the pentaphosphine-cyclodextrin inclusion complex.

[0036] The catalyst is N,N-dimethylaniline, the aprotic polar solvent is dimethyl sulfoxide, the alkaline neutralizer is potassium carbonate, and the antioxidant is butylated hydroxyanisole.

[0037] The novel composite acid-binding agent is composed of triethylamine, amino-modified silica gel, and modified montmorillonite in a mass ratio of 5:3:2. The mixed organic solvent is composed of acetone, dichloroethane, and toluene in a volume ratio of 4:3:3.

[0038] The preparation method of amino-modified silica gel is as follows: 100g of silica gel is added to 800mL of toluene and ultrasonically dispersed for 30min. Then, 50g of γ-aminopropyltriethoxysilane is added and refluxed at 80℃ for 12h. After the reaction is completed, the mixture is cooled, filtered, washed with toluene and ethanol in sequence, and then dried in a vacuum drying oven at 100℃ for 8h to obtain amino-modified silica gel.

[0039] The preparation method of modified montmorillonite is as follows: 50g of montmorillonite is added to 1000mL of water and stirred to disperse evenly. 30g of cetyltrimethylammonium bromide is added and stirred at 60℃ for 6h. After the reaction is completed, the mixture is filtered, washed with deionized water until no bromide ions are present, and then dried in a vacuum drying oven at 80℃ for 10h. The mixture is then ground into powder to obtain modified montmorillonite.

[0040] This embodiment also discloses a preparation process for triphenyltriamine thiophosphate, which includes the following steps: S1. Add the aprotic polar solvent and the mixed organic solvent to a reactor equipped with a stirrer, thermometer and reflux condenser, control the temperature at 35℃, stir at 250r / min, then add the aniline derivative, antioxidant and catalyst in sequence, stir evenly to fully dissolve the raw materials; S2. Heat the reaction system to 80℃, slowly add the halophosphorylating agent, control the feeding time to 2h, and keep stirring at 250r / min during the feeding process. After the feeding is completed, continue stirring and react for 6h. During this period, check the pH value of the reaction system every 30min. If the pH value drops, add an alkaline neutralizer and a new composite acid-binding agent in time to adjust it so that the pH value of the system is maintained at 7-9. S3. After the reaction is complete, cool the reaction solution to room temperature, pour it into a separatory funnel, let it stand to separate the layers, separate the organic phase, wash the organic phase with deionized water, each time the water volume is 1 / 3 of the organic phase volume, wash 3-5 times until the aqueous phase is neutral, transfer the washed organic phase to a distillation flask, and remove the solvent by distillation under reduced pressure to obtain the crude product. S4. Dissolve the crude product in an appropriate amount of acetone, add activated carbon for decolorization, stir at 110 r / min for 30 min, filter while hot, cool the filtrate to crystallize, wash the crystals 2-3 times with a small amount of cold acetone, and dry the crystals in a vacuum drying oven at 75℃ to constant weight to obtain triphenyltriamine thiophosphate.

[0041] Example 3: This embodiment discloses a triphenyltriamine thiophosphate, which comprises the following raw materials in parts by weight: 35 parts of aniline derivative, 25 parts of halophosphorylating agent, 5 parts of catalyst, 200 parts of aprotic polar solvent, 15 parts of alkaline neutralizer, 1 part of antioxidant, 12 parts of novel composite acid-binding agent, and 270 parts of mixed organic solvent.

[0042] The aniline derivative is composed of p-aminophenol and p-aminophenol-graphene nanocomposite in a mass ratio of 3:1. The p-aminophenol-graphene nanocomposite is prepared by the following method: 0.5 g of graphene oxide is added to 100 mL of ethanol and ultrasonically dispersed for 1 h to achieve uniform dispersion. Then, 5 g of p-aminophenol and 0.1 g of sodium borohydride are added, and the mixture is stirred and reacted at room temperature for 12 h. The product is then separated by centrifugation, washed multiple times with ethanol and water, and finally dried in a vacuum drying oven at 60 °C for 12 h to obtain the final product.

[0043] The halogenated phosphorylating agent is thiophosphoryl chloride. The method for synthesizing the pentaphosphine-cyclodextrin inclusion complex is as follows: add pentaphosphine and β-cyclodextrin to a 95% ethanol solution at a molar ratio of 1:2, stir and react at 50°C for 6 hours. After the reaction is complete, cool and crystallize, filter and collect the crystals, wash the crystals with ethanol, and dry under vacuum at 40°C for 8 hours to obtain the pentaphosphine-cyclodextrin inclusion complex.

[0044] The catalyst is N,N-dimethylaniline, the aprotic polar solvent is N,N-dimethylformamide, the alkaline neutralizer is potassium carbonate, and the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0045] The novel composite acid-binding agent is composed of triethylamine, amino-modified silica gel, and modified montmorillonite in a mass ratio of 5:3:2. The mixed organic solvent is composed of acetone, dichloroethane, and toluene in a volume ratio of 4:3:3.

[0046] The preparation method of amino-modified silica gel is as follows: 100g of silica gel is added to 800mL of toluene and ultrasonically dispersed for 30min. Then, 50g of γ-aminopropyltriethoxysilane is added and refluxed at 80℃ for 12h. After the reaction is completed, the mixture is cooled, filtered, washed with toluene and ethanol in sequence, and then dried in a vacuum drying oven at 100℃ for 8h to obtain amino-modified silica gel.

[0047] The preparation method of modified montmorillonite is as follows: 50g of montmorillonite is added to 1000mL of water and stirred to disperse evenly. 30g of cetyltrimethylammonium bromide is added and stirred at 60℃ for 6h. After the reaction is completed, the mixture is filtered, washed with deionized water until no bromide ions are present, and then dried in a vacuum drying oven at 80℃ for 10h. The mixture is then ground into powder to obtain modified montmorillonite.

[0048] This embodiment also discloses a preparation process for triphenyltriamine thiophosphate, which includes the following steps: S1. Add the aprotic polar solvent and the mixed organic solvent to a reactor equipped with a stirrer, thermometer and reflux condenser, control the temperature at 30℃, stir at 230r / min, then add the aniline derivative, antioxidant and catalyst in sequence, stir evenly to fully dissolve the raw materials; S2. Heat the reaction system to 75℃, slowly add the halophosphorylating reagent, and control the feeding time to 1.5h. During the feeding process, keep stirring at a speed of 225r / min. After the feeding is completed, continue stirring and react for 5h. During this period, check the pH value of the reaction system every 30min. If the pH value drops, add an alkaline neutralizer and a new composite acid-binding agent in time to adjust it so that the pH value of the system is maintained at 7-9. S3. After the reaction is complete, cool the reaction solution to room temperature, pour it into a separatory funnel, let it stand to separate the layers, separate the organic phase, wash the organic phase with deionized water, each time the water volume is 1 / 3 of the organic phase volume, wash 3-5 times until the aqueous phase is neutral, transfer the washed organic phase to a distillation flask, and remove the solvent by distillation under reduced pressure to obtain the crude product. S4. Dissolve the crude product in an appropriate amount of acetone, add activated carbon for decolorization, stir at 105 r / min for 30 min, filter while hot, cool the filtrate to crystallize, wash the crystals 2-3 times with a small amount of cold acetone, and dry the crystals in a vacuum drying oven at 70℃ to constant weight to obtain triphenyltriamine thiophosphate.

[0049] Comparative Example 1: A triphenyltriamine thiophosphate, which differs from Example 3 only in that: no novel composite acid-binding agent is added, only sodium carbonate is used as the acid-binding agent, and other raw materials and process conditions are the same as in Example 3.

[0050] Comparative Example 2: A triphenyltriamine thiophosphate, which differs from Example 3 only in that: no amino-modified silica gel is added to the novel composite acid binder, the other two components are increased in proportion, and other raw materials and process conditions are the same as in Example 3.

[0051] Comparative Example 3: A triphenyltriamine thiophosphate, which differs from Example 3 only in that: no modified montmorillonite is added to the novel composite acid binder, the other two components are increased in proportion, and other raw materials and process conditions are the same as in Example 3.

[0052] Comparative Example 4: A triphenyltriamine thiophosphate, which differs from Example 3 only in that: no mixed organic solvent is used, only acetone is used as the organic solvent, and the other raw materials and process conditions are the same as in Example 3.

[0053] Comparative Example 5: A triphenyltriamine thiophosphate, which differs from Example 3 only in that the aniline derivative is made from only p-aminophenol, while the other raw materials and process conditions are the same as in Example 3.

[0054] Comparative Example 6: A triphenyltriamine thiophosphate, which differs from Example 3 only in that the aniline derivative uses only p-aminophenol-graphene nanocomposite, while the other raw materials and process conditions are the same as in Example 3.

[0055] Comparative Example 7: A triphenyltriamine thiophosphate, which differs from Example 3 only in that the novel composite acid binder contains only triethylamine, without the addition of amino-modified silica gel and modified montmorillonite, while the other raw materials and process conditions are the same as in Example 3.

[0056] The triphenyltriamine thiophosphate obtained in Examples 1-3 and Comparative Examples 1-7 were subjected to performance tests. The comprehensive performance of the triphenyltriamine thiophosphate was measured, and the results are shown in Table 1.

[0057] Table 1 Performance parameters of triphenyltriamine thiophosphate obtained in Examples 1-3 and Comparative Examples 1-7

[0058] Compared to Example 3, as shown in Table 1: Comparative Example 1, without the addition of the novel composite acid-binding agent, used only sodium carbonate as the acid-binding agent. Its acid-binding rate was slower than triethylamine, and unlike the composite acid-binding agent, it could not adsorb impurities through a porous / layered structure, resulting in some acid residue and triggering side reactions. The yield (79.3% vs 91.1%) and purity (93.2% vs 99.5%) decreased significantly. The sodium carbonate neutralization reaction may generate more water, and it cannot adsorb water from the system, leading to a significant increase in water content (1.04% vs 0.18%). Byproducts and residual acid accelerate oxidation, resulting in weakened antioxidant performance (absorbance 0.25 vs 0.09; higher absorbance indicates poorer antioxidant properties).

[0059] In Comparative Example 2, the novel composite acid-binding agent did not contain amino-modified silica gel, relying solely on triethylamine and modified montmorillonite. This resulted in decreased acid-binding efficiency (due to the lack of active acid binding with amino groups) and weakened impurity adsorption capacity (due to the absence of a porous structure), leading to increased side reactions and reduced yield (80.4% vs 91.1%) and purity (94.1% vs 99.5%). Increased moisture and impurity residues led to a higher moisture content (0.99% vs 0.18%) and a lower melting point (150.7℃ vs 152.9℃). Impurities accelerated oxidation, weakening antioxidant properties (absorbance 0.23 vs 0.09).

[0060] The novel composite acid-binding agent in Comparative Example 3 lacked modified montmorillonite, resulting in a lack of layered structure for interception. Consequently, some large molecular impurities could not be removed, leading to a decrease in purity (94.7% vs 99.5%). The acid-binding synergy was weakened, acid residue increased slightly, triggering a small number of side reactions and reducing the yield (81.2% vs 91.1%). Increased moisture and impurity residues led to a higher moisture content (0.91% vs 0.18%), a lower melting point (150.1℃ vs 152.9℃), and weakened antioxidant properties (absorbance 0.22 vs 0.09).

[0061] Comparative Example 4 did not use a mixed organic solvent, but only acetone. Acetone has poor solubility for the halophosphorylating agent (thiophosphoryl chloride), leading to uneven dispersion of the raw materials, incomplete reaction, and a significant decrease in yield (78.9% vs 91.1%). Undissolved raw materials formed impurities, resulting in a decrease in purity (93.1% vs 99.5%). Uneven reaction caused localized moisture residue, increasing the moisture content (1.02% vs 0.18%). Impurities and unreacted raw materials accelerated oxidation, weakening the antioxidant properties (absorbance 0.26 vs 0.09), and the product had an irregular crystal structure and a decreased melting point (149.9℃ vs 152.9℃).

[0062] In Comparative Example 5, the aniline derivative used only p-aminophenol lacked the loading and dispersing effect of active sites, resulting in a slower and incomplete reaction rate and a lower yield (84.4% vs 91.1%). Without graphene-assisted stabilization, the product was prone to introducing small amounts of impurities, leading to a decrease in purity (97.1% vs 99.5%). Water in the reaction system was more difficult to adsorb and remove, resulting in an increased water content (1.01% vs 0.18%). Antioxidant stability was weakened (absorbance 0.19 vs 0.09), and the crystal structure was slightly affected, leading to a decrease in melting point (150.0℃ vs 152.9℃).

[0063] Comparative Example 6, using only p-aminophenol-graphene nanocomposite, exhibited uneven dispersion leading to incomplete reaction and increased side reactions. The yield (82.6% vs 91.1%) and purity (95.2% vs 99.5%) were both lower than in Example 3. Excessive hydrophobicity made water difficult to remove through washing, resulting in an increased water content (1.09% vs 0.18%). Byproducts accelerated oxidation, weakening antioxidant properties (absorbance 0.28 vs 0.09), and the irregular crystal structure led to a significant decrease in melting point (147.9℃ vs 152.9℃).

[0064] The novel composite acid-binding agent in Comparative Example 7 contained only triethylamine, without the addition of amino-modified silica gel and modified montmorillonite. Due to the lack of the active acid-binding effect of amino-modified silica gel and the impurity adsorption capacity of both, the acid-binding efficiency decreased, side reactions increased, the yield decreased to 82.3%, and the purity dropped to 94.8%. Residual moisture and impurities increased, with the moisture content rising to 0.89% and the melting point decreasing from 152.9℃ to 150.1℃. The presence of impurities accelerated the oxidation process, weakened the antioxidant properties, and reduced the absorbance to 0.22.

[0065] The optimal performance of Example 3 (high yield, high purity, low moisture, high melting point, and strong antioxidant) stems from the synergistic effect of the raw material composition (composite acid-binding agent, mixed solvent, and aniline derivative ratio). Each comparative example, by disrupting this synergy, resulted in a comprehensive decline in performance.

[0066] In the reaction system of this invention, taking thiophosphoryl bromide as an example, the reaction of p-aminophenol with thiophosphoryl bromide theoretically only produces the target product, triphenyltriamine thiophosphate, and hydrogen bromide. From the reaction mechanism, the phenolic hydroxyl group is converted to a phenoxy anion under alkaline conditions, which enhances its nucleophilicity and preferentially undergoes a substitution reaction with the bromine atom in thiophosphoryl bromide. Due to the mild reaction conditions (70-80℃) and the slow addition of the halophosphorylating reagent, excessive reaction of the amino group and other possible side reactions are avoided. Simultaneously, the alkaline neutralizing agent and the novel composite acid-binding agent promptly neutralize the hydrogen bromide generated in the reaction, maintaining the system pH at 7-9, further suppressing side reactions that might be caused by increased acidity. Comparison of the results from the examples and comparative examples also demonstrates that under optimized reaction conditions and reactant ratios, the reaction can proceed efficiently and selectively, with no obvious byproduct formation detected.

[0067] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A triphenyltriamine thiophosphate, characterized in that, The components of triphenyltriamine thiophosphate include the following raw materials in parts by weight: 33-40 parts of aniline derivative, 25-35 parts of halophosphorylating agent, 3-8 parts of catalyst, 190-210 parts of aprotic polar solvent, 10-20 parts of alkaline neutralizer, 0.5-1.5 parts of antioxidant, 10-18 parts of novel composite acid-binding agent, and 240-300 parts of mixed organic solvent.

2. The triphenyltriamine thiophosphate according to claim 1, characterized in that, The aniline derivative is composed of p-aminophenol and p-aminophenol-graphene nanocomposite in a mass ratio of 3:

1. The p-aminophenol-graphene nanocomposite is prepared by the following method: 0.5 g of graphene oxide is added to 100 mL of ethanol and ultrasonically dispersed for 1 h to achieve uniform dispersion. Then, 5 g of p-aminophenol and 0.1 g of sodium borohydride are added, and the mixture is stirred and reacted at room temperature for 12 h. The product is then separated by centrifugation, washed multiple times with ethanol and water, and finally dried in a vacuum drying oven at 60 °C for 12 h to obtain the final product.

3. The triphenyltriamine thiophosphate according to claim 2, characterized in that, The halogenated phosphorylation reagent is thiophosphoryl bromide or thiophosphoryl chloride.

4. The triphenyltriamine thiophosphate according to claim 3, characterized in that, The catalyst is one of triethylamine or N,N-dimethylaniline, the aprotic polar solvent is one of N,N-dimethylformamide or dimethyl sulfoxide, the alkaline neutralizer is one of sodium carbonate or potassium carbonate, and the antioxidant is one of 2,6-di-tert-butyl-p-cresol or butyl hydroxyanisole.

5. The triphenyltriamine thiophosphate according to claim 3, characterized in that, The novel composite acid-binding agent is composed of triethylamine, amino-modified silica gel, and modified montmorillonite in a mass ratio of 5:3:

2.

6. The triphenyltriamine thiophosphate according to claim 5, characterized in that, The preparation method of amino-modified silica gel is as follows: 100g of silica gel is added to 800mL of toluene and ultrasonically dispersed for 30min. Then, 50g of γ-aminopropyltriethoxysilane is added and refluxed at 80℃ for 12h. After the reaction is completed, the mixture is cooled, filtered, washed with toluene and ethanol in sequence, and then dried in a vacuum drying oven at 100℃ for 8h to obtain amino-modified silica gel.

7. The triphenyltriamine thiophosphate according to claim 5, characterized in that, The preparation method of modified montmorillonite is as follows: 50g of montmorillonite is added to 1000mL of water and stirred to disperse evenly. 30g of cetyltrimethylammonium bromide is added and stirred at 60℃ for 6h. After the reaction is completed, the mixture is filtered, washed with deionized water until no bromide ions are present, and then dried in a vacuum drying oven at 80℃ for 10h. The mixture is then ground into powder to obtain modified montmorillonite.

8. The triphenyltriamine thiophosphate according to claim 3, characterized in that, The mixed organic solvent consists of acetone, dichloroethane, and toluene in a volume ratio of 4:3:

3.

9. A process for preparing triphenyltriamine thiophosphate according to any one of claims 1-8, characterized in that, The preparation process includes the following steps: S1. Add the aprotic polar solvent and the mixed organic solvent to a reactor equipped with a stirrer, thermometer and reflux condenser, control the temperature at 25-35℃, stir at a speed of 200-250r / min, then add the aniline derivative, antioxidant and catalyst in sequence, stir evenly to fully dissolve the raw materials; S2. Heat the reaction system to 70-80℃, slowly add the halophosphorylating reagent, and control the addition time to 1-2 hours. During the addition process, keep stirring at a speed of 200-250 r / min. After the addition is completed, continue stirring and react for 4-6 hours. During this period, check the pH value of the reaction system every 30 minutes. If the pH value drops, add an alkaline neutralizing agent and a new composite acid-binding agent in time to adjust it so that the pH value of the system is maintained between 7 and 9. S3. After the reaction is complete, cool the reaction solution to room temperature, pour it into a separatory funnel, let it stand to separate the layers, separate the organic phase, wash the organic phase with deionized water, each time the water volume is 1 / 3 of the organic phase volume, wash 3-5 times until the aqueous phase is neutral, transfer the washed organic phase to a distillation flask, and remove the solvent by distillation under reduced pressure to obtain the crude product. S4. Dissolve the crude product in an appropriate amount of acetone, add activated carbon for decolorization, stir at 100-110 r / min for 30 min, filter while hot, cool the filtrate to crystallize, wash the crystals 2-3 times with a small amount of cold acetone, place the crystals in a vacuum drying oven and dry to constant weight to obtain triphenyltriamine thiophosphate.

10. The preparation process of triphenyltriamine thiophosphate according to claim 9, characterized in that, In step S4, the vacuum drying temperature is 65-75℃.

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