Preparation method and application of environment-friendly flame-retardant coolant

Abstract

The invention relates to the technical field of flame-retardant cutting agents, in particular to a preparation method and application of an environment-friendly flame-retardant cooling agent. Comprising the following steps: 1, carrying out an esterification reaction on 2, 2, 2-trichloroethanol and 2, 4, 6-tri (aminocaproic acid)-1, 3, 5-triazine to obtain a triazine polycarboxylic acid ester; (2) grafting the triazine polycarboxylic acid ester and DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) to obtain triazine polycarboxylic acid ester-DOPO; (3) under an alkaline condition, carrying out a hydrolysis reaction on the triazine polycarboxylic acid ester-DOPO, and then carrying out acidizing treatment to obtain triazine polycarboxylic acid-DOPO; step two, (1) reacting hydroxyl-terminated fluorosilicone oil with epoxy chloropropane, and epoxidizing the hydroxyl-terminated fluorosilicone oil to obtain epoxy-terminated fluorosilicone oil; (2) reacting the epoxy-terminated fluorosilicone oil with diethylenetriamine to obtain hyperbranched hydrophilic fluorosilicone oil; and 3, mixing the triazine polycarboxylic acid-DOPO, the hyperbranched hydrophilic fluorosilicone oil and other raw materials to obtain the environment-friendly flame-retardant coolant.

Description

Technical Field

[0001] The invention relates to the technical field of flame retardant cutting agents, in particular to a preparation method and application of an environmentally friendly flame retardant coolant. Background Art

[0002] As metal cutting processing develops towards high speed, high force and high precision in the 21st century, modern harsh processing conditions have put forward higher and higher requirements on the quality of cutting agents. Advanced manufacturing technologies such as CNC machine tools, machining centers and flexible manufacturing systems have been gradually promoted and applied, and advanced manufacturing technologies and cutting processing of difficult-to-process materials are inseparable from cooling and lubrication technology. Therefore, cutting agents are becoming more and more important. Traditional oil-based cutting agents have good lubrication performance, but due to their poor cooling performance, they cannot reduce the temperature of the cutting zone in time during high-speed cutting, resulting in the cutting agent producing smoke, catching fire and other phenomena. This not only threatens the safety of the staff, but also because the working temperature cannot be reduced in time, it causes thermal deformation, which seriously affects the processing accuracy of the workpiece. This undoubtedly shows that traditional cutting agents are difficult to adapt to today's harsh processing conditions.

[0003] In addition, as people's awareness of environmental protection continues to improve and the international community pays more and more attention to the ecological environment, the problem that traditional cutting agents generally cause great pollution to the environment has been raised, and this type of traditional cutting agent is even less accepted by people. Therefore, it is very meaningful to develop an environmentally friendly flame retardant cutting agent without affecting the performance of the cutting agent.

[0004] In summary, the present invention aims at the defects of poor cooling performance and environmental pollution of traditional cutting agents, and proposes a water-based environmentally friendly flame retardant coolant. While making it more adaptable to the needs of today's metal cutting processing, it can also be used as a flame retardant in fire fighting, which has important practical significance. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method and application of an environmentally friendly flame retardant coolant to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions: An environmentally friendly flame retardant coolant comprises the following components: by mass percentage, 2-5% of triazine polycarboxylic acid-DOPO, 2-5% of hyperbranched hydrophilic fluorosilicone oil, 3-5% of triazine polycarboxylic acid, 5-10% of urea, 2-4% of ammonium sulfate, 5-8% of diammonium phosphate, 4-6% of polyethylene glycol, 5-10% of triethanolamine, 2-5% of surfactant, 0.2-0.5% of benzotriazole, 1-2% of antibacterial agent, 0.5-1% of defoaming agent, and the balance is purified water.

[0007] Furthermore, the method for preparing the environmentally friendly flame retardant coolant comprises the following steps: Step 1: (1) esterification reaction of 2,2,2-trichloroethanol and 2,4,6-tris(aminocaproic acid)-1,3,5-triazine to obtain triazine polycarboxylate; The triazine polycarboxylate is grafted with DOPO to obtain triazine polycarboxylate-DOPO; Under alkaline conditions, triazine polycarboxylate-DOPO undergoes hydrolysis reaction and then undergoes acidification treatment to obtain triazine polycarboxylic acid-DOPO; Step 2: (1) After the terminal hydroxyl fluorosilicone oil reacts with epichlorohydrin, it is epoxidized under alkaline conditions to obtain the terminal epoxy fluorosilicone oil; (2) The epoxy-terminated fluorosilicone oil reacts with diethylenetriamine to obtain a hyperbranched hydrophilic fluorosilicone oil; Step 3: Evenly mix triazine polycarboxylic acid-DOPO, hyperbranched hydrophilic fluorosilicone oil, triazine polycarboxylic acid, urea, ammonium sulfate, diammonium phosphate, polyethylene glycol, surfactant, triethanolamine, benzotriazole, antibacterial agent, defoaming agent and purified water, filter and collect the filtrate to obtain an environmentally friendly flame retardant coolant.

[0008] Furthermore, the preparation method of the triazine polycarboxylic acid-DOPO is: 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 2,2,2-trichloroethanol, and 80-85 wt% of phosphoric acid are sequentially added into a reaction kettle and stirred and mixed. After being uniformly mixed, the mixture is stirred and heated to reflux temperature for reaction for 3-20 hours to terminate the reaction. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain a triazine polycarboxylate. DOPO, isopropanol and triethylamine are added to a reaction kettle and stirred to mix. After the mixture is uniformly mixed, the temperature of the reaction system is adjusted to -5 to 10°C, and a chlorinating agent is added dropwise to the reaction system within 0.5 to 1 hour under stirring. After the addition is completed, the reaction is continued under stirring for 1 to 5 hours to obtain a reaction solution I; After adjusting the temperature of the reaction solution I to 30-60° C., adding the triazine polycarboxylate to the reaction solution I, reacting for 24-48 hours, terminating the reaction, and finally distilling under reduced pressure, filtering, washing, and drying to obtain the triazine polycarboxylate-DOPO; The triazine polycarboxylate-DOPO is added to a 25-30wt% sodium hydroxide solution, and the mixture is stirred, heated to 60-80°C, and refluxed for 1-10 hours to terminate the reaction. After naturally cooling to room temperature, a dilute hydrochloric acid solution is added to the reaction system to adjust the pH value to 2-3. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain the triazine polycarboxylic acid-DOPO.

[0009] Furthermore, the molar ratio of the 2,4,6-tris(aminocaproic acid)-1,3,5-triazine to 2,2,2-trichloroethanol is 1:(5-10); the esterification reaction is a reversible reaction, and in order to protect the carboxyl groups in the triazine polycarboxylic acid as completely as possible, the 2,2,2-trichloroethanol should be completely excessive in the reaction.

[0010] Furthermore, the amount of phosphoric acid added is 0.5-5% of the amount of 2,2,2-trichloroethanol added.

[0011] Furthermore, the raw materials required for preparing the triazine polycarboxylate-DOPO include the following components: by weight, 7.5-10 parts of DOPO, 5-7.5 parts of triazine polycarboxylate, 12-18 parts of chlorinating agent, 25 parts of triethylamine, and 100 parts of isopropanol.

[0012] Furthermore, the chlorinating agent includes but is not limited to any one of carbon tetrachloride, sulfuryl chloride, and trichloroisocyanuric acid.

[0013] Furthermore, the mass ratio of the triazine polycarboxylate-DOPO and the sodium hydroxide solution is (1-10):(1-10).

[0014] Furthermore, the preparation method of the hyperbranched hydrophilic fluorosilicone oil is: Add terminal hydroxyl fluorosilicone oil and epichlorohydrin into a reaction kettle and stir and mix. After the mixture is evenly mixed, add sodium hydride thereto, stir and heat to 55-65°C for reaction for 1-3 hours, then reduce pressure to remove excess epichlorohydrin, then add 25-30wt% sodium hydroxide solution to the reaction system, adjust the temperature of the reaction system to 30-40°C for reaction for 1-3 hours, terminate the reaction, and obtain terminal epoxy fluorosilicone oil by vacuum distillation, filtration, washing and drying; Under nitrogen protection, epoxy-terminated fluorosilicone oil, diethylenetriamine and isopropanol are added to a reaction kettle and stirred to mix. After being evenly mixed, the mixture is heated to 80-85°C and reacted for 1-10 hours. The reaction is terminated and vacuum distillation is performed to obtain a hyperbranched hydrophilic fluorosilicone oil.

[0015] Furthermore, the mass ratio of the terminal hydroxy fluorosilicone oil, epichlorohydrin, sodium hydride and sodium hydroxide is 1:(0.2~0.5):(0.1~0.2):(0.1~0.2).

[0016] Furthermore, the mass ratio of the epoxy-terminated fluorosilicone oil to diethylenetriamine is 1:(0.15-0.3).

[0017] Furthermore, the amount of isopropanol added is 25-35% of the total amount of reactants added.

[0018] Furthermore, the surfactant is a combination of one or more of a cationic surfactant, an anionic surfactant, and a nonionic surfactant.

[0019] Preferably, the surfactant is a nonionic surfactant, specifically including but not limited to any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and castor oil polyoxyethylene ether.

[0020] Furthermore, the antibacterial agent is one or a combination of benzisothiazolinone and methylisothiazolinone.

[0021] Furthermore, the defoamer is a polyether-modified silicone defoamer.

[0022] Furthermore, the specific process of step three is: (1) Add some pure water into the stirred tank and heat it to 70~80℃; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir to mix them evenly; (3) Heat the remaining pure water to 45±2℃ and add it to the solution in (2), stirring and mixing for 5 to 10 minutes; this serves to clean the high-level tank, feeding pipeline, particle crushing device, etc.; (4) adding triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stirring and mixing evenly, and then adding to the solution in (3), stirring and mixing for 15 to 30 minutes; wherein the total amount of triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid is in a ratio of 1:1 to the amount of triethanolamine; (5) Add the hyperbranched hydrophilic fluorosilicone oil to polyethylene glycol, stir and mix evenly, then add it to the solution in (4), stir and mix for 15 to 30 minutes, stop stirring, wait for the solution to cool naturally to 40±2°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0023] Furthermore, the environmentally friendly flame retardant coolant is used as a cutting agent in metal cutting and as a flame retardant in fire fighting.

[0024] Triazine polycarboxylic acid (2,4,6-tris(aminocaproic acid)-1,3,5-triazine) is a multifunctional compound with stable chemical properties and environmental friendliness. It is often used in metal rust prevention, water treatment and other fields. Because of its excellent anti-rust performance, it is also often added to cutting agents. In order to enhance the flame retardant properties of cutting coolants, the scheme is designed to make the imino group on the triazine polycarboxylic acid react with the active hydrogen on DOPO, so that DOPO is grafted onto the triazine polycarboxylic acid. However, triethylamine will be introduced during the reaction, which will react with the carboxyl group on the triazine polycarboxylic acid, affecting the performance of the triazine polycarboxylic acid. Therefore, in the present invention, the triazine polycarboxylic acid is protected by an esterification reaction with 2,2,2-trichloroethanol to obtain a triazine polycarboxylic acid ester, thereby protecting the carboxyl group; the triazine polycarboxylic acid ester is then reacted with DOPO to obtain a triazine polycarboxylic acid ester-DOPO; finally, the triazine polycarboxylic acid ester-DOPO is subjected to ester hydrolysis to obtain a triazine polycarboxylic acid-DOPO, thereby achieving the grafting modification of DOPO on the triazine polycarboxylic acid. The obtained triazine polycarboxylic acid-DOPO, while ensuring that the original antirust performance of the triazine polycarboxylic acid is not greatly affected, introduces a DOPO structure to give it flame retardant properties, and is added to a cutting coolant to achieve the purpose of enhancing the flame retardant properties of the cutting coolant.

[0025] Fluorosilicone oil has excellent chemical stability, and its lubrication and heat transfer properties are excellent. At the same time, due to the presence of fluorine, it also has certain flame retardant properties. Adding it to the cutting agent can play a role in lubrication, cooling, and flame retardancy. However, fluorosilicone oil is hydrophobic. If it is directly added to the flame retardant coolant prepared in the present invention, stratification will occur, and it cannot effectively play a related role. Therefore, in the present invention, the fluorosilicone oil is hydrophilic to enhance its hydrophilicity so that it can be better dispersed in the flame retardant coolant, thereby playing a role in lubrication, cooling, and flame retardancy. In the present invention, the terminal hydroxyl fluorosilicone oil is first reacted with epichlorohydrin, and then epoxidized under alkaline conditions to obtain the terminal epoxy fluorosilicone oil; then diethylenetriamine is reacted to obtain a hyperbranched hydrophilic fluorosilicone oil; by introducing a large number of hydrophilic imino groups into the fluorosilicone oil, the hydrophilicity of the fluorosilicone oil is effectively enhanced.

[0026] Among the components, in order to save costs, triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid are selected for compound use. In addition to the rust prevention and lubrication effects of triazine polycarboxylic acid and triethanolamine, triazine polycarboxylic acid-DOPO can also further play a flame retardant role; Hyperbranched hydrophilic fluorosilicone oil: can further improve the lubricity and flame retardancy of flame retardant coolants. In addition, it has excellent thermal conductivity and can play a good cooling role in metal cutting. Urea: On the one hand, it can lower the freezing point of the coolant, enhance the storage capacity and applicability of the flame-retardant coolant, and on the other hand, it can also play a role in rust prevention; in addition, urea can also enhance the flame-retardant performance to a certain extent; Ammonium sulfate: It can cooperate with benzotriazole and antibacterial agents to play a bactericidal role, enhance the storage capacity of flame retardant coolants, and avoid rapid deterioration and failure; Ammonium dihydrogen phosphate: It can cooperate with triazine polycarboxylic acid-DOPO and hyperbranched hydrophilic fluorosilicone oil to enhance the flame retardant properties; Polyethylene glycol: It can improve the cooling efficiency of flame-retardant coolants; it can further improve the anti-rust ability; it can prevent the residual particles from cutting from adhering to the workpiece and affecting the cutting quality of the workpiece; finally, it can also cooperate with surfactants to play an emulsifying role, improving the cooling, lubrication and cleaning effects during the cutting process.

[0027] Compared with the prior art, the present invention has the following beneficial effects: 1. In the present invention, while ensuring that the original effect of triazine polycarboxylic acid is not greatly affected, DOPO is grafted onto triazine polycarboxylic acid to enhance its flame retardant properties, thereby giving the flame retardant coolant excellent flame retardant properties; 2. In order to further enhance the flame retardant properties of the flame retardant coolant, the present invention introduces fluorosilicone oil and performs hydrophilic modification on it; the fluorosilicone oil is used in conjunction with triazine polycarboxylic acid-DOPO to give the flame retardant coolant excellent flame retardant properties and cooling properties; 3. The present invention comprehensively considers the raw materials used in the flame retardant coolant to prepare an environmentally friendly flame retardant coolant, which can well meet the current needs of metal cutting, has little pollution to the environment, and has important practical value; 4. The flame retardant coolant prepared by the present invention can be used not only in metal cutting, but also as a flame retardant and used in fire fighting, and has more application value. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] It should be noted that the purchasers of all raw materials involved in the present invention include, without any special restrictions, illustratively: 2,4,6-tris(aminocaproyl)-1,3,5-triazine with a purity of 98% and 2,2,2-trichloroethanol with a purity of 98%, were purchased from JACS-Zhengzhou Jacks Chemical Products Co., Ltd.; DOPO with a purity of 98%, carbon tetrachloride with a purity of 98%, lauryl alcohol polyoxyethylene ether with a purity of 99%, benzisothiazolinone with a purity of 99%, benzotriazole with a purity of 99%, ammonium sulfate with a purity of 99%, ammonium dihydrogen phosphate with a purity of 99%, and polyethylene glycol with a purity of PEG600 of 99% were purchased from Hubei Yongkuo Technology Co., Ltd.; The purity of the terminal hydroxyl fluorosilicone oil was 99%, CAS number: 63148-56-1, purchased from Wuhan Kanos Technology Co., Ltd. Epichlorohydrin with a purity of 99%, diethylenetriamine with a purity of 99%, isopropanol with a purity of 99%, urea with a purity of 99%, and triethanolamine with a purity of 99%, were all purchased from Shanghai Jinjinle Industrial Co., Ltd.; The polyether modified silicone defoamer model is RW-024, purchased from Shanghai Ruwei Chemical Co., Ltd.; In the following examples, each portion is 100 g.

[0030] Example 1: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of triazine polycarboxylic acid-DOPO: (1) 10 parts of 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 25.6 parts of 2,2,2-trichloroethanol, and 0.8 parts of 80wt% phosphoric acid are added to a reactor in sequence and stirred and mixed. After being evenly mixed, the mixture is stirred and heated to reflux temperature for reaction for 10 hours to terminate the reaction. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain a triazine polycarboxylate; (2) 8 parts of DOPO, 100 parts of isopropanol, and 25 parts of triethylamine are added to a reactor and stirred and mixed. After being evenly mixed, the temperature of the reaction system is adjusted to 0°C, and 15 parts of tetrachloride are added dropwise to the reaction system under stirring within 1 hour. After the addition of carbon, continue stirring and reacting for 3 hours to obtain reaction solution I; (3) after adjusting the temperature of reaction solution I to 45°C, add 6 parts of triazine polycarboxylate to reaction solution I, react for 36 hours, terminate the reaction, and finally distill under reduced pressure, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; (4) add 6 parts of triazine polycarboxylate-DOPO to 6 parts of 25wt% sodium hydroxide solution, stir and heat to 70°C and reflux for 5 hours to terminate the reaction, and after naturally cooling to room temperature, add 10wt% dilute hydrochloric acid solution to the reaction system to adjust the pH value to 2.5, and finally distill, cool, crystallize, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; Step 2: Preparation of hyperbranched hydrophilic fluorosilicone oil: (1) Add 6 parts of terminal hydroxyl fluorosilicone oil and 2 parts of epichlorohydrin into a reactor and stir and mix. After the mixture is evenly mixed, add 0.75 parts of sodium hydride, stir and heat to 60°C for reaction for 2 hours, then reduce pressure to remove excess epichlorohydrin, then add 3 parts of 25wt% sodium hydroxide solution into the reaction system, adjust the temperature of the reaction system to 35°C for reaction for 2 hours, terminate the reaction, distill under reduced pressure, filter, wash and dry to obtain terminal epoxy fluorosilicone oil; (2) Under nitrogen protection, add 5 parts of terminal epoxy fluorosilicone oil, 1.2 parts of diethylenetriamine and 1.86 parts of isopropanol into a reactor and stir and mix. After the mixture is evenly mixed, stir and heat to 80°C for reaction for 5 hours, terminate the reaction, distill under reduced pressure to obtain hyperbranched hydrophilic fluorosilicone oil; Step 3: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid-DOPO 4.2%, hyperbranched hydrophilic fluorosilicone oil 3.5%, triazine polycarboxylic acid 4.2%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 type polyether modified silicone defoamer 0.8%, purified water 52.8%; 2. (1) Add part of the purified water into the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir and mix them uniformly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2), and stir and mix for 10 minutes; (4) Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix uniformly, and then add them to the solution in (3), and stir and mix for another 30 minutes; (5) Add hyperbranched hydrophilic fluorosilicone oil to polyethylene glycol, stir and mix uniformly, and then add it to the solution in (4), stir and mix for another 30 minutes, stop stirring, wait for the solution to cool naturally to 40°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0031] Example 2: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of triazine polycarboxylic acid-DOPO: (1) 10 parts of 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 16 parts of 2,2,2-trichloroethanol, and 0.08 parts of 80wt% phosphoric acid are added to a reactor in sequence and stirred and mixed. After being evenly mixed, the mixture is stirred and heated to reflux temperature for reaction for 3 hours to terminate the reaction. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain a triazine polycarboxylate. (2) 7.5 parts of DOPO, 100 parts of isopropanol, and 25 parts of triethylamine are added to a reactor and stirred and mixed. After being evenly mixed, the temperature of the reaction system is adjusted to 0°C, and 12 parts of tetrachloride are added dropwise to the reaction system under stirring within 1 hour. After the addition is complete, continue stirring and reacting for 1 hour to obtain reaction solution I; (3) after adjusting the temperature of reaction solution I to 45°C, add 6 parts of triazine polycarboxylate to reaction solution I, react for 24 hours, terminate the reaction, and finally distill under reduced pressure, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; (4) add 6 parts of triazine polycarboxylate-DOPO to 1 part of 25wt% sodium hydroxide solution, stir and heat to 70°C and reflux for reaction for 1 hour to terminate the reaction, and after naturally cooling to room temperature, add 10wt% dilute hydrochloric acid solution to the reaction system to adjust the pH value to 2.5, and finally distill, cool, crystallize, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; Step 2: Preparation of hyperbranched hydrophilic fluorosilicone oil: (1) Add 6 parts of terminal hydroxyl fluorosilicone oil and 1.2 parts of epichlorohydrin into a reactor and stir to mix. After the mixture is evenly mixed, add 0.6 parts of sodium hydride, stir and heat to 60°C for reaction for 1 hour, then reduce pressure to remove excess epichlorohydrin, then add 0.6 parts of 25 wt% sodium hydroxide solution into the reaction system, adjust the temperature of the reaction system to 35°C for reaction for 1 hour, terminate the reaction, distill under reduced pressure, filter, wash and dry to obtain terminal epoxy fluorosilicone oil; (2) Under nitrogen protection, add 5 parts of terminal epoxy fluorosilicone oil, 0.75 parts of diethylenetriamine and 1.44 parts of isopropanol into a reactor and stir to mix. After the mixture is evenly mixed, stir and heat to 80°C for reaction for 1 hour, terminate the reaction, distill under reduced pressure to obtain hyperbranched hydrophilic fluorosilicone oil; Step 3: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid-DOPO 4.2%, hyperbranched hydrophilic fluorosilicone oil 3.5%, triazine polycarboxylic acid 4.2%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 type polyether modified silicone defoamer 0.8%, purified water 52.8%; 2. (1) Add part of the purified water into the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir and mix them uniformly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2), and stir and mix for 10 minutes; (4) Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix uniformly, and then add them to the solution in (3), and stir and mix for another 30 minutes; (5) Add hyperbranched hydrophilic fluorosilicone oil to polyethylene glycol, stir and mix uniformly, and then add it to the solution in (4), stir and mix for another 30 minutes, stop stirring, wait for the solution to cool naturally to 40°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0032] Example 3: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of triazine polycarboxylic acid-DOPO: (1) 10 parts of 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 31.8 parts of 2,2,2-trichloroethanol, and 1.59 parts of 85wt% phosphoric acid are added to a reactor in sequence and stirred and mixed. After being evenly mixed, the mixture is stirred and heated to reflux temperature for reaction for 20 hours to terminate the reaction. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain a triazine polycarboxylate. (2) 10 parts of DOPO, 100 parts of isopropanol, and 25 parts of triethylamine are added to a reactor and stirred and mixed. After being evenly mixed, the temperature of the reaction system is adjusted to 0°C, and 18 parts of tetrachloroethylene are added dropwise to the reaction system within 1 hour under stirring. After the addition is complete, continue stirring and reacting for 5 hours to obtain reaction solution I; (3) after adjusting the temperature of reaction solution I to 45°C, add 6 parts of triazine polycarboxylate to reaction solution I, react for 48 hours, terminate the reaction, and finally distill under reduced pressure, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; (4) add 6 parts of triazine polycarboxylate-DOPO to 6 parts of 30wt% sodium hydroxide solution, stir and heat to 70°C and reflux for 10 hours to terminate the reaction, and after naturally cooling to room temperature, add 10wt% dilute hydrochloric acid solution to the reaction system to adjust the pH value to 2.5, and finally distill, cool, crystallize, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; Step 2: Preparation of hyperbranched hydrophilic fluorosilicone oil: (1) Add 6 parts of terminal hydroxyl fluorosilicone oil and 3 parts of epichlorohydrin into a reactor and stir and mix. After the mixture is evenly mixed, add 1.2 parts of sodium hydride, stir and heat to 60°C for reaction for 3 hours, then reduce pressure to remove excess epichlorohydrin, then add 4.8 parts of 30 wt% sodium hydroxide solution into the reaction system, adjust the temperature of the reaction system to 35°C for reaction for 3 hours, terminate the reaction, distill under reduced pressure, filter, wash and dry to obtain terminal epoxy fluorosilicone oil; (2) Under nitrogen protection, add 5 parts of terminal epoxy fluorosilicone oil, 1.5 parts of diethylenetriamine and 2.275 parts of isopropanol into a reactor and stir and mix. After the mixture is evenly mixed, stir and heat to 80°C for reaction for 10 hours, terminate the reaction, distill under reduced pressure to obtain hyperbranched hydrophilic fluorosilicone oil; Step 3: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid-DOPO 4.2%, hyperbranched hydrophilic fluorosilicone oil 3.5%, triazine polycarboxylic acid 4.2%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 type polyether modified silicone defoamer 0.8%, purified water 52.8%; 2. (1) Add part of the purified water into the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir and mix them uniformly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2), and stir and mix for 10 minutes; (4) Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix uniformly, and then add them to the solution in (3), and stir and mix for another 30 minutes; (5) Add hyperbranched hydrophilic fluorosilicone oil to polyethylene glycol, stir and mix uniformly, and then add it to the solution in (4), stir and mix for another 30 minutes, stop stirring, wait for the solution to cool naturally to 40°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0033] Based on Example 1, control experiments are set up below, specifically comparative examples 1 to 4, as described below: Comparative Example 1: Comparative Example 1 is based on Example 1, with the following adjustments: no esterification reaction is performed on the triazine polycarboxylic acid, and other processes remain unchanged, specifically: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of triazine polycarboxylic acid-DOPO: (1) Add 8 parts of DOPO, 100 parts of isopropanol and 25 parts of triethylamine into a reactor and stir to mix. After the mixture is evenly mixed, adjust the temperature of the reaction system to 0°C, and under stirring, drop 15 parts of carbon tetrachloride into the reaction system within 1 hour. After the dropwise addition is completed, continue stirring to react for 3 hours to obtain reaction solution I; (2) After adjusting the temperature of reaction solution I to 45°C, add 6 parts of triazine polycarboxylic acid into reaction solution I, react for 36 hours, terminate the reaction, and finally distill under reduced pressure, filter, wash and dry to obtain triazine polycarboxylic acid-DOPO; Step 2: Preparation of hyperbranched hydrophilic fluorosilicone oil: (1) Add 6 parts of terminal hydroxyl fluorosilicone oil and 2 parts of epichlorohydrin into a reactor and stir and mix. After the mixture is evenly mixed, add 0.75 parts of sodium hydride, stir and heat to 60°C for reaction for 2 hours, then reduce pressure to remove excess epichlorohydrin, then add 3 parts of 25wt% sodium hydroxide solution into the reaction system, adjust the temperature of the reaction system to 35°C for reaction for 2 hours, terminate the reaction, distill under reduced pressure, filter, wash and dry to obtain terminal epoxy fluorosilicone oil; (2) Under nitrogen protection, add 5 parts of terminal epoxy fluorosilicone oil, 1.2 parts of diethylenetriamine and 1.86 parts of isopropanol into a reactor and stir and mix. After the mixture is evenly mixed, stir and heat to 80°C for reaction for 5 hours, terminate the reaction, distill under reduced pressure to obtain hyperbranched hydrophilic fluorosilicone oil; Step 3: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid-DOPO 4.2%, hyperbranched hydrophilic fluorosilicone oil 3.5%, triazine polycarboxylic acid 4.2%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 type polyether modified silicone defoamer 0.8%, purified water 52.8%; 2. (1) Add part of the purified water into the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir and mix them uniformly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2), and stir and mix for 10 minutes; (4) Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix uniformly, and then add them to the solution in (3), and stir and mix for another 30 minutes; (5) Add hyperbranched hydrophilic fluorosilicone oil to polyethylene glycol, stir and mix uniformly, and then add it to the solution in (4), stir and mix for another 30 minutes, stop stirring, wait for the solution to cool naturally to 40°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0034] Comparative Example 2: Comparative Example 2 is based on Example 1, with the following adjustments: the triazine polycarboxylic acid is not modified, and other processes remain unchanged, specifically: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of hyperbranched hydrophilic fluorosilicone oil: (1) Add 6 parts of terminal hydroxyl fluorosilicone oil and 2 parts of epichlorohydrin into a reactor and stir and mix. After the mixture is evenly mixed, add 0.75 parts of sodium hydride, stir and heat to 60°C for reaction for 2 hours, then reduce pressure to remove excess epichlorohydrin, then add 3 parts of 25wt% sodium hydroxide solution into the reaction system, adjust the temperature of the reaction system to 35°C for reaction for 2 hours, terminate the reaction, distill under reduced pressure, filter, wash and dry to obtain terminal epoxy fluorosilicone oil; (2) Under nitrogen protection, add 5 parts of terminal epoxy fluorosilicone oil, 1.2 parts of diethylenetriamine and 1.86 parts of isopropanol into a reactor and stir and mix. After the mixture is evenly mixed, stir and heat to 80°C for reaction for 5 hours, terminate the reaction, distill under reduced pressure to obtain hyperbranched hydrophilic fluorosilicone oil; Step 2: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid 8.4%, hyperbranched hydrophilic fluorosilicone oil 3.5%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 polyether modified silicone defoamer 0.8%, and purified water 52.8%; 2. (1) Add part of the purified water into the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence and stir to mix them evenly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2) and stir to mix for 10 minutes; (4) Add triazine polycarboxylic acid to triethanolamine and stir to mix evenly, then add it to the solution in (3) and stir to mix for another 30 minutes; (5) Add hyperbranched hydrophilic fluorosilicone oil to polyethylene glycol and stir to mix evenly, then add it to the solution in (4) and stir to mix for another 30 minutes, then stop stirring, wait for the solution to cool naturally to 40°C, filter and collect the filtrate to obtain an environmentally friendly flame retardant coolant.

[0035] Comparative Example 3: Comparative Example 3 is based on Example 1, with the following adjustments: directly using terminal hydroxyl fluorosilicone oil as raw material, and other processes remain unchanged, specifically: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of triazine polycarboxylic acid-DOPO: (1) 10 parts of 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 25.6 parts of 2,2,2-trichloroethanol, and 0.8 parts of 80wt% phosphoric acid are added to a reactor in sequence and stirred and mixed. After being evenly mixed, the mixture is stirred and heated to reflux temperature for reaction for 10 hours to terminate the reaction. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain a triazine polycarboxylate; (2) 8 parts of DOPO, 100 parts of isopropanol, and 25 parts of triethylamine are added to a reactor and stirred and mixed. After being evenly mixed, the temperature of the reaction system is adjusted to 0°C, and 15 parts of tetrachloride are added dropwise to the reaction system under stirring within 1 hour. After the addition of carbon, continue stirring and reacting for 3 hours to obtain reaction solution I; (3) after adjusting the temperature of reaction solution I to 45°C, add 6 parts of triazine polycarboxylate to reaction solution I, react for 36 hours, terminate the reaction, and finally distill under reduced pressure, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; (4) add 6 parts of triazine polycarboxylate-DOPO to 6 parts of 25wt% sodium hydroxide solution, stir and heat to 70°C and reflux for 5 hours to terminate the reaction, and after naturally cooling to room temperature, add 10wt% dilute hydrochloric acid solution to the reaction system to adjust the pH value to 2.5, and finally distill, cool, crystallize, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; Step 2: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid-DOPO 4.2%, terminal hydroxy fluorosilicone oil 3.5%, triazine polycarboxylic acid 4.2%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 type polyether modified silicone defoamer 0.8%, purified water 52.8%; 2. (1) Add part of the purified water to the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir and mix them uniformly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2), and stir and mix for 10 minutes; (4) Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix uniformly, and then add them to the solution in (3), and stir and mix for another 30 minutes; (5) Add terminal hydroxyl fluorosilicone oil to polyethylene glycol, stir and mix uniformly, and then add it to the solution in (4), stir and mix for another 30 minutes, stop stirring, wait for the solution to cool naturally to 40°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0036] Comparative Example 4: Comparative Example 4 is based on Example 1, with the following adjustments: no hyperbranched hydrophilic fluorosilicone oil is added, and other processes remain unchanged, specifically: A method for preparing an environmentally friendly flame retardant coolant: Step 1: Preparation of triazine polycarboxylic acid-DOPO: (1) 10 parts of 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 25.6 parts of 2,2,2-trichloroethanol, and 0.8 parts of 80wt% phosphoric acid are added to a reactor in sequence and stirred and mixed. After being evenly mixed, the mixture is stirred and heated to reflux temperature for reaction for 10 hours to terminate the reaction. Finally, the mixture is distilled, cooled, crystallized, filtered, washed, and dried to obtain a triazine polycarboxylate; (2) 8 parts of DOPO, 100 parts of isopropanol, and 25 parts of triethylamine are added to a reactor and stirred and mixed. After being evenly mixed, the temperature of the reaction system is adjusted to 0°C, and 15 parts of tetrachloride are added dropwise to the reaction system under stirring within 1 hour. After the addition of carbon, continue stirring and reacting for 3 hours to obtain reaction solution I; (3) after adjusting the temperature of reaction solution I to 45°C, add 6 parts of triazine polycarboxylate to reaction solution I, react for 36 hours, terminate the reaction, and finally distill under reduced pressure, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; (4) add 6 parts of triazine polycarboxylate-DOPO to 6 parts of 25wt% sodium hydroxide solution, stir and heat to 70°C and reflux for 5 hours to terminate the reaction, and after naturally cooling to room temperature, add 10wt% dilute hydrochloric acid solution to the reaction system to adjust the pH value to 2.5, and finally distill, cool, crystallize, filter, wash, and dry to obtain triazine polycarboxylate-DOPO; Step 2: 1. Weigh the raw materials according to the following mass percentages: triazine polycarboxylic acid-DOPO 4.2%, triazine polycarboxylic acid 4.2%, urea 8%, ammonium sulfate 3%, diammonium phosphate 6.4%, polyethylene glycol 4.5%, triethanolamine 8.4%, lauryl alcohol polyoxyethylene ether 3.5%, benzotriazole 0.3%, benzisothiazolinone 1.4%, RW-024 type polyether modified silicone defoamer 0.8%, purified water 56.3%; 2. (1) Add part of the purified water into the stirring kettle and heat it to 75°C; (2) Add urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent and defoaming agent to the solution in (1) in sequence, and stir and mix them uniformly; (3) Heat the remaining purified water to 45°C and add it to the solution in (2), and stir and mix for 10 minutes; (4) Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix uniformly, and then add them to the solution in (3), and stir and mix for another 30 minutes; (5) Add polyethylene glycol to the solution in (4), stir and mix for another 30 minutes, stop stirring, wait for the solution to cool naturally to 40°C, filter, collect the filtrate, and obtain an environmentally friendly flame retardant coolant.

[0037] Performance test: The environmentally friendly flame retardant coolants prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to metal processing cutting performance tests and flame retardant performance tests, and compared with the commercially available water-based cutting lubricant model M3018. The specific test methods are as follows: Metal processing cutting performance test: A tapping torque test is used to evaluate the cutting performance of the flame retardant coolant and M3018 prepared by the present invention, specifically: a torque force test is performed on a LAPTAB GII8 torque tester to test the average torque force, and the cutting performance of the flame retardant coolant is evaluated based on this; Flame retardant performance test: immerse a piece of paper in flame retardant coolant and M3018, take it out and dry it after it is completely soaked; and measure the limiting oxygen index according to the standard of GB / T 14656-2009, and use this to evaluate the flame retardant performance; The specific test results are shown in Table 1 below: Table 1

[0038] Result analysis: From the data in Table 1 above, it can be seen that the flame retardant coolant prepared by the present invention has good cutting performance and flame retardant performance, and can be well used in metal cutting and fire fighting. Comparing the examples and comparative example 1, it can be known that if the triazine polycarboxylic acid is not esterified, the triazine polycarboxylic acid will cause side reactions, thereby reducing its effect in the cutting process; comparing the examples and comparative example 2, it can be known that the modification of the triazine polycarboxylic acid in the present invention can greatly improve the flame retardant performance of the flame retardant coolant without affecting the application of the triazine polycarboxylic acid in cutting; comparing the examples with comparative examples 3 and 4, it can be known that the comprehensive enhancement of the cutting performance and flame retardant performance of the flame retardant coolant can be achieved after the hydrophilic modification of the fluorosilicone oil; if only the fluorosilicone oil is introduced, due to its hydrophobicity, the raw materials in the flame retardant coolant cannot be fully dispersed, and the cutting performance and flame retardant performance of the flame retardant coolant will deteriorate instead; comparing the examples and the commercially available 3018 water-based cutting lubricant, it can be seen that the flame retardant coolant prepared by the present invention has obvious advantages in cutting performance and flame retardant performance.

[0039] In summary, the present invention prepares a flame retardant coolant that can be used in metal cutting and fire fighting.

[0040] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A method for preparing an environmentally friendly flame retardant coolant, characterized in that: The following steps are involved: Step 1: (1) esterification reaction of 2,2,2-trichloroethanol and 2,4,6-tris(aminocaproic acid)-1,3,5-triazine to obtain triazine polycarboxylate; (2) Grafting triazine polycarboxylate with DOPO to obtain triazine polycarboxylate-DOPO; (3) Under alkaline conditions, triazine polycarboxylate-DOPO undergoes hydrolysis reaction and then undergoes acidification treatment to obtain triazine polycarboxylic acid-DOPO; Step 2: (1) After the terminal hydroxyl fluorosilicone oil reacts with epichlorohydrin, it is epoxidized to obtain the terminal epoxy fluorosilicone oil; (2) The epoxy-terminated fluorosilicone oil reacts with diethylenetriamine to obtain a hyperbranched hydrophilic fluorosilicone oil; Step 3: Evenly mix triazine polycarboxylic acid-DOPO, hyperbranched hydrophilic fluorosilicone oil, triazine polycarboxylic acid, urea, ammonium sulfate, diammonium phosphate, polyethylene glycol, triethanolamine, surfactant, benzotriazole, antibacterial agent, defoaming agent and purified water, filter and collect the filtrate to obtain an environmentally friendly flame retardant coolant.

2. The method for preparing an environmentally friendly flame retardant coolant according to claim 1, characterized in that: The preparation method of the triazine polycarboxylic acid-DOPO is: (1) 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, 2,2,2-trichloroethanol, and 80-85 wt% of phosphoric acid are sequentially added into a reaction kettle and stirred and mixed. After the mixture is uniformly mixed, the mixture is stirred and heated to reflux temperature for reaction for 3-20 hours, the reaction is terminated, and finally purified to obtain a triazine polycarboxylate; DOPO, isopropanol and triethylamine are added to a reaction kettle and stirred to mix. After the mixture is uniformly mixed, the temperature of the reaction system is adjusted to -5 to 10°C, and a chlorinating agent is added dropwise to the reaction system within 0.5 to 1 hour under stirring. After the addition is completed, the reaction is continued under stirring for 1 to 5 hours to obtain a reaction solution I; After adjusting the temperature of the reaction solution I to 30-60° C., adding triazine polycarboxylate to the reaction solution I, reacting for 24-48 hours, terminating the reaction, and finally purifying to obtain triazine polycarboxylate-DOPO; The triazine polycarboxylate-DOPO is added to a 25-30wt% sodium hydroxide solution, heated to 60-80°C with stirring, and refluxed for 1-10 hours to terminate the reaction. After naturally cooling to room temperature, a dilute hydrochloric acid solution is added to the reaction system to adjust the pH value to 2-3, and finally purified to obtain triazine polycarboxylic acid-DOPO.

3. The method for preparing an environmentally friendly flame retardant coolant according to claim 2, characterized in that: The molar ratio of the 2,4,6-tris(aminocaproic acid)-1,3,5-triazine and 2,2,2-trichloroethanol is 1:(5-10); the amount of phosphoric acid added is 0.5-5% of the amount of 2,2,2-trichloroethanol added; the raw materials required for the preparation of the triazine polycarboxylate-DOPO include the following components: by weight, 7.5-10 parts of DOPO, 5-7.5 parts of triazine polycarboxylate, 12-18 parts of chlorinating agent, 25 parts of triethylamine, and 100 parts of isopropanol, wherein the chlorinating agent includes any one of carbon tetrachloride, sulfuryl chloride, and trichloroisocyanuric acid; the mass ratio of the triazine polycarboxylate-DOPO and sodium hydroxide solution is (1-10):(1-10).

4. The method for preparing an environmentally friendly flame retardant coolant according to claim 1, characterized in that: The preparation method of the hyperbranched hydrophilic fluorosilicone oil is: Add terminal hydroxyl fluorosilicone oil and epichlorohydrin into a reaction kettle and stir and mix. After the mixture is evenly mixed, add sodium hydride thereto, stir and heat to 55-65°C for reaction for 1-3 hours, then reduce the pressure to remove excess epichlorohydrin, then add 25-30wt% sodium hydroxide solution to the reaction system, adjust the temperature of the reaction system to 30-40°C for reaction for 1-3 hours, terminate the reaction, and purify to obtain terminal epoxy fluorosilicone oil; Under nitrogen protection, epoxy-terminated fluorosilicone oil, diethylenetriamine and isopropanol are added to a reaction kettle and stirred and mixed. After being evenly mixed, the mixture is stirred and heated to 80-85° C. for reaction for 1-10 hours. The reaction is terminated and purified to obtain hyperbranched hydrophilic fluorosilicone oil.

5. The method for preparing an environmentally friendly flame retardant coolant according to claim 4, characterized in that: The mass ratio of the terminal hydroxyl fluorosilicone oil, epichlorohydrin, sodium hydride and sodium hydroxide is 1:(0.2~0.5):(0.1~0.2):(0.1~0.2); the mass ratio of the terminal epoxy fluorosilicone oil and diethylenetriamine is 1:(0.15~0.3); the amount of isopropanol added is 25~35% of the total amount of reactants added.

6. The method for preparing an environmentally friendly flame retardant coolant according to claim 1, characterized in that: The surfactant is a combination of one or more of a cationic surfactant, an anionic surfactant, and a nonionic surfactant; the antibacterial agent is a combination of one or two of benzisothiazolinone and methylisothiazolinone; and the defoamer is a polyether-modified silicone defoamer.

7. The method for preparing an environmentally friendly flame retardant coolant according to claim 1, characterized in that: The specific process of step three is: Add some pure water into the stirred tank and heat it to 70~80℃; To the solution in (1), urea, ammonium dihydrogen phosphate, ammonium sulfate, benzotriazole, antibacterial agent, and defoaming agent are added in sequence, and stirred to mix evenly; Heat the remaining purified water to 45±2℃ and add it to the solution in (2), stirring for 5-10 minutes; Add triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid to triethanolamine, stir and mix evenly, then add to the solution in (3), and stir and mix for 15 to 30 minutes; wherein the total amount of triazine polycarboxylic acid-DOPO and triazine polycarboxylic acid is in a ratio of 1:1 to the amount of triethanolamine; The hyperbranched hydrophilic fluorosilicone oil is added to the polyethylene glycol, stirred and mixed evenly, and then added to the solution in (4), and stirred and mixed for 15 to 30 minutes, then the stirring is stopped, and the solution is allowed to cool naturally to 40±2°C, filtered, and the filtrate is collected to obtain an environmentally friendly flame retardant coolant.

8. An environmentally friendly flame retardant coolant prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The environmentally friendly flame retardant coolant comprises the following components: by mass percentage, 2-5% of triazine polycarboxylic acid-DOPO, 2-5% of hyperbranched hydrophilic fluorosilicone oil, 3-5% of triazine polycarboxylic acid, 5-10% of urea, 2-4% of ammonium sulfate, 5-8% of diammonium phosphate, 4-6% of polyethylene glycol, 5-10% of triethanolamine, 2-5% of surfactant, 0.2-0.5% of benzotriazole, 1-2% of antibacterial agent, 0.5-1% of defoaming agent, and the balance is purified water.

9. Use of the environmentally friendly flame retardant coolant according to claim 8 in metal cutting and fire fighting.

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