阅读说明：本技术 一种高纯度tgddm环氧树脂的合成方法 (Synthetic method of high-purity TGDDM epoxy resin ) 是由 张玮 辛昭 马少波 陈黎 王罡 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种高纯度TGDDM环氧树脂的合成方法,该方法包括：一、环氧氯丙烷、催化剂和助剂升温后加入4,4’-二氨基二苯甲烷固体颗粒搅拌进行开环反应,得到混合物；二、将混合物降温后滴加NaOH水溶液进行闭环反应,经洗涤蒸馏得到粗料液；三、向粗料液中加入甲苯升温搅拌并滴加NaOH水溶液反应,经洗涤蒸馏后得到TGDDM环氧树脂。本发明通过对闭环反应体系进行洗涤并采用短程蒸馏装置脱除溶剂,并对粗料液加碱反应除杂后进行洗涤并采用短程薄膜蒸发装置脱除溶剂,有效控制并减少副反应的发生,缩短了TGDDM环氧树脂的高温停留时间,避免了TGDDM环氧树脂在高温下自固化,提高了TGDDM环氧树脂的质量纯度。(The invention discloses a method for synthesizing high-purity TGDDM epoxy resin, which comprises the following steps: heating epichlorohydrin, a catalyst and an auxiliary agent, adding 4, 4' -diaminodiphenylmethane solid particles, stirring, and carrying out ring-opening reaction to obtain a mixture; secondly, cooling the mixture, then dropwise adding NaOH aqueous solution to carry out a ring-closing reaction, and washing and distilling to obtain a crude feed liquid; and thirdly, adding toluene into the crude material liquid, heating, stirring, dropwise adding NaOH aqueous solution for reaction, and washing and distilling to obtain the TGDDM epoxy resin. According to the method, a closed-loop reaction system is washed, a short-path distillation device is used for removing the solvent, the crude material liquid is washed after alkali is added for reaction and impurity removal, and the solvent is removed by a short-path thin film evaporation device, so that the side reaction is effectively controlled and reduced, the high-temperature retention time of the TGDDM epoxy resin is shortened, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality and purity of the TGDDM epoxy resin are improved.)

1. A synthetic method of high-purity TGDDM epoxy resin is characterized by comprising the following steps:

step one, ring opening reaction: adding epoxy chloropropane, a catalyst and an auxiliary agent into a double-layer reaction kettle, heating to 50 ℃, slowly and uniformly adding 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 6-15 h, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding a diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4-5 h;

step two, ring closure reaction: reducing the temperature of the mixture obtained in the step one to 45-52 ℃, then dropwise adding a NaOH aqueous solution with the mass concentration of 20-40% at the speed of 3-8 mL/min, reacting at the same temperature for 1-3 h after dropwise adding to complete a ring-closing reaction, washing with deionized water, and continuously transferring into a short-path distillation device to remove the solvent through distillation to obtain a crude material liquid;

step three, refining: adding methylbenzene into the crude material liquid obtained in the step two, heating to 50-55 ℃, stirring and dissolving for 15min, then dropwise adding a NaOH aqueous solution with the mass concentration of 5-15%, continuously reacting for 1-3 h at the temperature after dropwise adding, washing by using deionized water, continuously transferring into a short-range thin film evaporation device, and removing the solvent by distillation to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is not less than 92 percent.

2. The method according to claim 1, wherein the catalyst in step one is one or a mixture of more than two of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate and tetrabutylammonium phosphate, and the mass of the catalyst is 0.2-2% of that of the 4, 4' -diaminodiphenylmethane in step one.

3. The method as claimed in claim 1, wherein the assistant is one or a mixture of more than two of ethylene glycol, propylene glycol, glycerol and pentaerythritol in the first step, and the weight of the assistant is 5-20% of that of the 4, 4' -diaminodiphenylmethane in the first step.

4. The method for synthesizing TGDDM epoxy resin of claim 1, wherein the ratio of the amount of sodium hydroxide in the sodium hydroxide solution in step two to the amount of 4, 4' -diaminodiphenylmethane in step one is (1.0-1.5): 1.

5. The method for synthesizing TGDDM epoxy resin of high purity as claimed in claim 1, wherein the washing in step two and step three is performed by centrifugal extractor.

6. The method for synthesizing TGDDM epoxy resin of high purity as claimed in claim 1, wherein the distillation temperature in step two and step three is 110-180 ℃ and the pressure is 0.01-0.03 MPa.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of high-purity TGDDM epoxy resin.

Background

N, N, N, N '-tetraglycidyl-4, 4' -diaminodiphenylmethane (hereinafter abbreviated as TGDDM) is a tetrafunctional epoxy resin, the structure of the resin contains benzene rings, and one epoxy resin molecule contains four amino groups, so that the resin has higher rigidity, high reaction activity and high crosslinking density after curing, not only has good heat resistance and solvent resistance, but also has the advantages of good radiation resistance, stable size after heating, high mechanical property and the like.

At present, two-step methods are mostly adopted for industrially preparing glycidylamine epoxy resin. However, there are many side reactions in the synthesis of TGDDM resin, and even though the commercial grades of TGDDM resin are not pure TGDDM monomers, they contain various impurities. The presence of these impurities lowers the epoxy value of TGDDM resins, shortens pot life, shortens gel time, changes curing kinetics, and lowers mechanical properties of the cured resins, thus making the production of high purity TGDDM resins commercially valuable.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a synthetic method of high-purity TGDDM epoxy resin aiming at the defects of the prior art. The method obtains crude feed liquid by washing a closed-loop reaction system and removing a solvent by adopting a short-range distillation device, washes the crude feed liquid after adding alkali for reaction and removing impurities, and removes the solvent by adopting a short-range thin film evaporation device, thereby effectively controlling and reducing the occurrence of side reactions, greatly shortening the high-temperature retention time of the TGDDM epoxy resin, avoiding the self-curing of the TGDDM epoxy resin at high temperature, and improving the quality purity of the TGDDM epoxy resin.

In order to solve the technical problems, the invention adopts the technical scheme that: a synthetic method of high-purity TGDDM epoxy resin is characterized by comprising the following steps:

step one, ring opening reaction: adding epoxy chloropropane, a catalyst and an auxiliary agent into a double-layer reaction kettle, heating to 50 ℃, slowly and uniformly adding 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 6-15 h, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding a diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4-5 h;

step two, ring closure reaction: reducing the temperature of the mixture obtained in the step one to 45-52 ℃, then dropwise adding a NaOH aqueous solution with the mass concentration of 20-40% at the speed of 3-8 mL/min, reacting at the same temperature for 1-3 h after dropwise adding to complete a ring-closing reaction, washing with deionized water, and continuously transferring into a short-path distillation device to remove the solvent through distillation to obtain a crude material liquid;

step three, refining: adding methylbenzene into the crude material liquid obtained in the step two, heating to 50-55 ℃, stirring and dissolving for 15min, then dropwise adding a NaOH aqueous solution with the mass concentration of 5-15%, continuously reacting for 1-3 h at the temperature after dropwise adding, washing by using deionized water, continuously transferring into a short-range thin film evaporation device, and removing the solvent by distillation to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is not less than 92 percent.

The chemical reaction process of the invention is as follows:

the TGDDM epoxy resin is prepared by a three-step method, firstly, raw materials and epoxy chloropropane are subjected to ring-opening reaction under the action of a catalyst and an auxiliary agent, then alkali liquor is added for ring-closing reaction, high-purity TGDDM epoxy resin is obtained after refining, side reactions are effectively controlled and reduced, the quality purity of the TGDDM epoxy resin is improved, a ring-closing reaction system is washed, a short-path distillation device is adopted to remove a solvent to obtain a crude material liquid, the crude material liquid is subjected to alkali addition reaction to remove impurities, then washing is carried out, and the solvent is removed by a short-path thin film evaporation device, so that the high-temperature retention time of the TGDDM epoxy resin is greatly shortened while the solvent and the TGDDM epoxy resin are effectively separated, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality purity of the TGDDM epoxy resin is.

The method for synthesizing the high-purity TGDDM epoxy resin is characterized in that in the first step, the catalyst is one or a mixture of more than two of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate and tetrabutylammonium phosphate, and the mass of the catalyst is 0.2-2% of that of the 4, 4' -diaminodiphenylmethane in the first step. The adoption of the catalyst is beneficial to shortening the reaction time and reducing the occurrence of side reactions, thereby reducing the quality of impurities in the product TGDDM epoxy resin and improving the epoxy value of the product TGDDM epoxy resin.

The method for synthesizing the high-purity TGDDM epoxy resin is characterized in that in the first step, the auxiliary agent is one or a mixture of more than two of ethylene glycol, propylene glycol, glycerol and pentaerythritol, and the mass of the auxiliary agent is 5-20% of that of the 4, 4' -diaminodiphenylmethane in the first step. The adjuvant is more preferably ethylene glycol and/or glycerol. The alcohol auxiliary agent is adopted to effectively inhibit the hydrolysis of epoxy chloropropane, reduce the occurrence of side reaction and be beneficial to improving the epoxy value of the TGDDM epoxy resin product, thereby reducing the content of inorganic chlorine and easily saponified chlorine in the product.

The method for synthesizing the high-purity TGDDM epoxy resin is characterized in that the ratio of the amount of sodium hydroxide in the sodium hydroxide solution in the second step to the amount of the 4, 4' -diaminodiphenylmethane in the first step is (1.0-1.5): 1. The degree of dehydration ring-closing reaction is controlled by controlling the amount of sodium hydroxide added, so that the main reaction in the reaction system is carried out towards the direction of dehydration ring-closing reaction, the generation of side reaction is reduced, and the improvement of the quality purity of the product TGDDM epoxy resin is facilitated.

The synthesis method of the high-purity TGDDM epoxy resin is characterized in that the washing in the second step and the third step is carried out by adopting a centrifugal extractor. By adopting the centrifugal extraction machine, the washing water consumption is reduced, the washing time is shortened, the wastewater discharge is reduced, the impurity amount is reduced, and the problems of long reaction time, large epoxy equivalent of the product and high impurity content in the prior art are solved.

The synthesis method of the high-purity TGDDM epoxy resin is characterized in that the distillation temperature in the second step and the distillation pressure in the third step are both 110-180 ℃ and 0.01-0.03 MPa. The distillation process parameters are favorable for separating the organic solvent from the TGDDM epoxy resin, and simultaneously, the high-temperature retention time of the TGDDM epoxy resin is shortened, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality of the TGDDM epoxy resin is further improved.

Compared with the prior art, the invention has the following advantages:

1. the TGDDM epoxy resin is prepared by a three-step method, a closed-loop reaction system is washed, a short-path distillation device is used for removing a solvent to obtain a crude material liquid, the crude material liquid is subjected to alkali reaction for impurity removal, then the crude material liquid is washed, and the solvent is removed by a short-path thin film evaporation device, so that the occurrence of side reactions is effectively controlled and reduced, the high-temperature retention time of the TGDDM epoxy resin is greatly shortened while the solvent and the TGDDM epoxy resin are effectively separated, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality purity of the TGDDM epoxy resin is further improved.

2. The invention adopts the diluent to dilute the ring-opening reaction system and then carry out ring-closing reaction, thereby reducing the occurrence of side reaction, effectively reducing the content of inorganic chlorine and easy saponification chlorine in the product and solving the problem of high content of inorganic chlorine and organic chlorine in the product TGDDM epoxy resin.

3. The deionized water, the extracting agent and the diluent in the synthetic process can be recycled, so that the treatment cost is reduced, the waste liquid amount is greatly reduced, and the whole synthetic process hardly causes pollution to the environment.

4. The invention uses a short-path evaporator to separate the organic solvent and the TGDDM epoxy resin product, thereby improving the recovery rate of the organic solvent, reducing the discharge of synthetic waste liquid, improving the production efficiency and reducing the energy consumption in the production process.

The technical solution of the present invention is further described in detail by examples below.

Detailed Description

Example 1

The preparation method of this example includes the following steps:

step one, ring opening reaction: adding 951mL of epoxy chloropropane and 282mL of ethylene glycol into a double-layer reaction kettle, heating to 50 ℃, adding 1.2g of tetrabutylammonium chloride and 29.74g of glycerol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 6 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, 753mL of ethanol diluent is added to reduce the viscosity of the reaction system; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4 hours;

step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 45 ℃, then dropwise adding 600g of a 20% NaOH aqueous solution at a speed of 5mL/min, reacting at the same temperature for 3h after dropwise adding to complete a ring-closing reaction, washing in a centrifugal extractor by using deionized water with the same volume and at 90 ℃, continuously transferring into a short-distance distillation device, and distilling to remove the solvent under the conditions that the temperature is 110 ℃ and the pressure is 0.01MPa to obtain 1209g of crude material liquid;

step three, refining: adding 800mL of toluene into the crude material liquid obtained in the step two, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 120g of NaOH aqueous solution with the mass concentration of 5%, continuing to react for 1h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuing to transfer into a short-path thin film evaporation device, and distilling and removing the solvent under the conditions of the temperature of 110 ℃ and the pressure of 0.01MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.8 percent.

It was found that the TGDDM epoxy resin prepared in this example had a mass of 1152g, a yield of 91%, an epoxy equivalent of 132, an inorganic chlorine content of 13.3ppm, an easily saponifiable chlorine content of 486ppm, and a viscosity (50 ℃ C.) of 3429 mPaS.

The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.

The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium chloride.

Example 2

The preparation method of this example includes the following steps:

step one, ring opening reaction: adding 951mL of epoxy chloropropane and 282mL of acetone into a double-layer reaction kettle, heating to 50 ℃, adding 11.9g of tetrabutylammonium hydrogen sulfate and 119g of ethylene glycol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction at a temperature not exceeding 55 ℃, continuing stirring at 50-55 ℃ for ring-opening reaction for 15 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding 423mL of ethanol diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 5 hours;

step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 52 ℃, then dripping 337.5g of NaOH aqueous solution with the mass concentration of 40% at the speed of 3mL/min, reacting at the same temperature for 1h after finishing dripping, washing in a centrifugal extractor by deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and removing the solvent by distillation under the conditions of the temperature of 140 ℃ and the pressure of 0.02MPa to obtain 1174g of crude material liquid;

step three, refining: adding 3174mL of toluene into the crude material liquid obtained in the second step, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 125g of NaOH aqueous solution with the mass concentration of 10%, continuously reacting for 1.5h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuously transferring into a short-distance thin film evaporation device, and removing the solvent by distillation under the conditions of the temperature of 140 ℃ and the pressure of 0.02MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 93.1%.

It was found that the TGDDM epoxy resin prepared in this example had a mass of 1127g, a yield of 89%, an epoxy equivalent of 119, an inorganic chlorine content of 9.5ppm, an easily saponifiable chlorine content of 305ppm, and a viscosity (50 ℃ C.) of 4120 mPaS.

The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.

The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium hydrogen sulfate.

Example 3

The preparation method of this example includes the following steps:

step one, ring opening reaction: adding 951mL of epoxy chloropropane and 282mL of ethylene glycol into a double-layer reaction kettle, heating to 50 ℃, adding 8.92g of tetrabutyl ammonium phosphate and 89g of glycerol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for carrying out ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for carrying out ring-opening reaction for 13 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding 226mL of ethanol diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4 hours;

step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 50 ℃, then dripping 342.9g of NaOH aqueous solution with the mass concentration of 35% at the speed of 8mL/min, reacting at the same temperature for 3h after finishing dripping, washing in a centrifugal extractor by deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and distilling to remove the solvent under the conditions that the temperature is 150 ℃ and the pressure is 0.02MPa to obtain 1192g of crude material liquid;

step three, refining: adding 2260mL of toluene into the crude material liquid obtained in the step two, heating to 50 ℃, stirring and dissolving for 15min, then dropwise adding 280g of NaOH aqueous solution with the mass concentration of 10%, continuously reacting for 3h at the temperature after dropwise adding, washing in a centrifugal extractor by deionized water with the volume equal to that of the volume of 90 ℃, continuously transferring into a short-path thin film evaporation device, and distilling to remove the solvent under the conditions of the temperature of 150 ℃ and the pressure of 0.02MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.3 percent.

The TGDDM epoxy resin prepared in this example was found to have a mass of 1147g, a yield of 90.5%, an epoxy equivalent of 112, an inorganic chlorine content of 8.2ppm, an easily saponifiable chlorine content of 217ppm, and a viscosity (50 ℃ C.) of 3250 mPaS.

The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.

The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium phosphate.

Example 4

The preparation method of this example includes the following steps:

step one, ring opening reaction: adding 951mL of epoxy chloropropane and 221mL of ethylene glycol into a double-layer reaction kettle, heating to 50 ℃, adding 3.0g of tetrabutylammonium sulfate and 119g of ethylene glycol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 10 hours, and ending the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; reducing the viscosity of a reaction system by adding 442mL of ethanol diluent after the ring-opening reaction is finished; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4.5 h;

step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 50 ℃, then dripping 520g of NaOH aqueous solution with the mass concentration of 25% at the speed of 5mL/min, reacting at the same temperature for 1.5h after finishing dripping, washing in a centrifugal extractor by deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and removing the solvent by distillation under the conditions that the temperature is 160 ℃ and the pressure is 0.02MPa to obtain 1225g of crude material liquid;

step three, refining: adding 2765mL of toluene into the crude material liquid obtained in the step two, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 500g of a 10% NaOH aqueous solution, continuously reacting for 1.5h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuously transferring into a short-distance thin film evaporation device, and removing the solvent by distillation under the conditions of the temperature of 180 ℃ and the pressure of 0.02MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.5 percent.

The TGDDM epoxy resin prepared in this example was found to have a mass of 1216g, a yield of 96%, an epoxy equivalent of 112, an inorganic chlorine content of 3.0ppm, an easily saponified chlorine content of 134ppm, and a viscosity (50 ℃ C.) of 3960 mPaS.

The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.

The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium sulfate.

Example 5

The preparation method of this example includes the following steps:

step one, ring opening reaction: adding 951mL of epoxy chloropropane, 176mL of ethanol and 176mL of acetone into a double-layer reaction kettle, heating to 50 ℃, adding 3.0g of tetrabutylammonium bromide and 59.5g of ethylene glycol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 10 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, 294mL of ethanol and 294mL of acetone diluent are added to reduce the viscosity of the reaction system; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4 hours;

step two, ring closure reaction: cooling the temperature of the mixture obtained in the first step to 45 ℃, then dropwise adding 435g of NaOH aqueous solution with the mass concentration of 28% at the speed of 5mL/min, reacting at the same temperature for 1.5h after dropwise adding to complete a ring-closing reaction, washing in a centrifugal extractor by using deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and distilling to remove the solvent under the conditions of the temperature of 160 ℃ and the pressure of 0.01MPa to obtain 1211g of crude material liquid;

step three, refining: adding 3528mL of toluene into the crude material liquid obtained in the step two, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 500g of 8% NaOH aqueous solution, continuing to react for 1h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuing to transfer into a short-path thin film evaporation device, and distilling and removing the solvent under the conditions of 160 ℃ and 0.01MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.5 percent.

The TGDDM epoxy resin prepared in this example was found to have a mass of 1183g, a yield of 93.3%, an epoxy equivalent of 117, an inorganic chlorine content of 3.2ppm, an easily saponifiable chlorine content of 204ppm, and a viscosity (50 ℃ C.) of 3633 mPaS.

The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.

The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide other than tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.