Preparation method and application of low-chlorine epoxy resin

Abstract

The invention belongs to the technical field of epoxy resin production, and particularly relates to a preparation method and application of low-chlorine epoxy resin. The method comprises the following steps: carrying out n times of dechlorination on an epoxy resin organic phase solution, and standing and layering the obtained final dechlorination solution to obtain a final dechlorination organic phase solution; and adjusting the pH value of the final dechlorination organic phase solution to 6-7, and removing the solvent from the obtained neutralized dechlorination organic phase solution to obtain the low-chlorine epoxy resin. According to the method, potassium hydroxide is adopted as an active component of the dechlorination reagent, meanwhile, the dosage of potassium hydroxide is controlled, the dechlorination temperature is larger than or equal to 80 DEG C, potassium hydroxide is used for rapid reaction dechlorination under the action of the phase transfer catalyst, and chloride ions in epoxy resin can be effectively removed. According to the method, the total chlorine content in the low-chlorine epoxy resin product can be effectively controlled through multiple times of chlorine removal operation, controllable adjustment of product indexes is achieved, it is guaranteed that the finally obtained product is good in batch stability, light in color and luster and low in total chlorine content, and the application requirement of photoresist can be met.

Description

Technical Field

[0001] The invention belongs to the technical field of epoxy resin production, and specifically relates to a preparation method and application of a low-chlorine epoxy resin. Background Art

[0002] Due to its excellent properties such as chemical resistance, flexibility, and adhesion, epoxy resin has a wide range of uses in many fields. However, with the development of society, people have higher expectations and performance requirements for epoxy resin, which requires further promotion of epoxy resin improvement and upgrading. Electronics and electrical engineering are important application areas of epoxy resin, but the electrical properties of epoxy resin itself are insufficient, making it difficult to meet the requirements of high-end components. This is mainly due to the inevitable chlorine content in the production process of epoxy resin, which will corrode semiconductor devices and greatly limit the application of epoxy resin.

[0003] The electronics industry has strict restrictions on the chlorine content of epoxy resins, generally requiring the chlorine content to be below 800ppm, and high-end electronics require it to be below 300ppm. Therefore, only by dechlorinating epoxy resins can the application requirements of the electronics field such as photoresists be met.

[0004] Conventional methods for dechlorination of epoxy resin mainly include physical method and chemical method. However, the dechlorination effect of epoxy resin is poor and the dechlorination process is relatively complicated. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method and application of a low-chlorine epoxy resin. The method provided by the present invention has a simple process and an excellent dechlorination effect. The chlorine content of the final product can be controlled by repeated reactions, and the stability between batches is good. The entire reaction process is environmentally friendly, the process cost is low, and the labor intensity of workers can be reduced, so the method can be promoted and used on a large scale.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a low-chlorine epoxy resin, comprising the following steps:

[0008] The epoxy resin organic phase solution is subjected to n dechlorinations, wherein n is a positive integer ≥ 1, and when n = 1, a final dechlorinated solution is directly obtained; when n ≥ 2, an n-1 dechlorinated solution is directly obtained after the n-1 dechlorination, the n-1 dechlorinated solution is allowed to stand for stratification to obtain an n-1 dechlorinated organic phase solution, and the n-1 dechlorinated organic phase solution is subjected to an n-th dechlorination to obtain a final dechlorinated solution; the epoxy resin organic phase solution comprises an epoxy resin, a phase transfer catalyst and an organic solvent, the dechlorination reagent used in the dechlorination is a potassium hydroxide aqueous solution, and the mass of potassium hydroxide in the potassium hydroxide aqueous solution used for each dechlorination accounts for ≥ 2.4% of the mass of the epoxy resin; the dechlorination temperature is ≥ 80°C;

[0009] The final dechlorination solution is allowed to stand for stratification to obtain a final dechlorination organic phase solution;

[0010] The pH value of the final dechlorinated organic phase solution is adjusted to 6-7 to obtain a neutralized dechlorinated organic phase solution;

[0011] The neutralized and dechlorinated organic phase solution is desolventized to obtain the low-chlorine epoxy resin.

[0012] Preferably, the dechlorination time is 3 to 5 minutes each time.

[0013] Preferably, the dechlorination is carried out under high-speed shearing conditions, and the rotation speed of the high-speed shearing is 900-1100 r / min.

[0014] Preferably, the phase transfer catalyst is an alcohol catalyst; the mass of the phase transfer catalyst accounts for 1-3% of the mass of the epoxy resin.

[0015] Preferably, the alcohol catalyst includes one or more of polyethylene glycol 200, polyethylene glycol 800, polyethylene glycol 2000 and polypropylene glycol 400.

[0016] Preferably, the organic solvent comprises one or more of toluene, xylene and methyl isobutyl ketone; the mass of the epoxy resin in the epoxy resin organic phase solution accounts for 40-70% of the total mass of the epoxy resin and the organic solvent.

[0017] Preferably, the temperature of the epoxy resin organic phase solution and the n-1th dechlorination organic phase solution are independently 85-90°C;

[0018] The mass percentage of the potassium hydroxide aqueous solution is 42-48%; the temperature of the potassium hydroxide aqueous solution is 90-95°C.

[0019] Preferably, water is used to terminate each dechlorination to obtain a final dechlorination solution or an n-1th dechlorination solution; the mass of water used at the end of each dechlorination accounts for 15-20% of the total mass of the epoxy resin and the organic solvent.

[0020] Preferably, the total chlorine content of the epoxy resin is ≥1816 ppm, and the total chlorine content of the low-chlorine epoxy resin is ≤800 ppm.

[0021] The present invention provides the application of low-chlorine epoxy resin prepared by the preparation method described in the above technical scheme in electronics or photoresist.

[0022] The invention provides a method for preparing a low-chlorine epoxy resin, comprising the following steps: dechlorinating an epoxy resin organic phase solution for n times, wherein n is a positive integer ≥1, and when n=1, directly obtaining a final dechlorinated solution; when n≥2, directly obtaining an n-1th dechlorinated solution after the n-1th dechlorination, allowing the n-1th dechlorinated solution to stand and decompose to obtain an n-1th dechlorinated organic phase solution, and dechlorinating the n-1th dechlorinated organic phase solution for an nth time to obtain a final dechlorinated solution; the epoxy resin organic phase solution comprises epoxy resin The present invention adopts potassium hydroxide as the active ingredient of the dechlorination reagent, and controls the amount of potassium hydroxide and the dechlorination temperature of ≥80°C. Potassium hydroxide is used to react and dechlorinate rapidly under the action of a phase transfer catalyst to remove chloride, and the effective removal of chloride ions in the epoxy resin can be achieved. The present invention can effectively control the total chlorine content in the low-chlorine epoxy resin product through multiple dechlorination operations, realize controllable adjustment of product indicators, and ensure that the final product batch has good stability, light color, and low total chlorine content, and can meet the application requirements of photoresist.

[0023] Furthermore, in the present invention, the time for each dechlorination is 3 to 5 minutes. The present invention strictly controls the time for each dechlorination to avoid excessive reaction time, which may cause overreaction and gelation of the product.

[0024] In summary, the low-chlorine epoxy resin product obtained by the preparation method provided by the present invention has good batch stability, light color, low total chlorine content, and can meet the application requirements of photoresist. DETAILED DESCRIPTION

[0025] The present invention provides a method for preparing a low-chlorine epoxy resin, comprising the following steps:

[0026] The epoxy resin organic phase solution is subjected to n dechlorinations, wherein n is a positive integer ≥ 1, and when n = 1, a final dechlorinated solution is directly obtained; when n ≥ 2, an n-1 dechlorinated solution is directly obtained after the n-1 dechlorination, the n-1 dechlorinated solution is allowed to stand for stratification to obtain an n-1 dechlorinated organic phase solution, and the n-1 dechlorinated organic phase solution is subjected to an n-th dechlorination to obtain a final dechlorinated solution; the epoxy resin organic phase solution comprises an epoxy resin, a phase transfer catalyst and an organic solvent, the dechlorination reagent used in the dechlorination is a potassium hydroxide aqueous solution, and the mass of potassium hydroxide in the potassium hydroxide aqueous solution used for each dechlorination accounts for ≥ 2.4% of the mass of the epoxy resin; the dechlorination temperature is ≥ 80°C;

[0027] The final dechlorination solution is allowed to stand for stratification to obtain a final dechlorination organic phase solution;

[0028] The pH value of the final dechlorinated organic phase solution is adjusted to 6-7 to obtain a neutralized dechlorinated organic phase solution;

[0029] The neutralized and dechlorinated organic phase solution is desolventized to obtain the low-chlorine epoxy resin.

[0030] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0031] The present invention performs n-time dechlorination on an epoxy resin organic phase solution, wherein n is a positive integer ≥1, and when n=1, a final dechlorinated solution is directly obtained; when n≥2, an n-1th dechlorinated solution is directly obtained after the n-1th dechlorination, the n-1th dechlorinated solution is placed to separate layers to obtain an n-1th dechlorinated organic phase solution, and the n-1th dechlorinated organic phase solution is subjected to an n-time dechlorination to obtain a final dechlorinated solution; the epoxy resin organic phase solution comprises an epoxy resin, a phase transfer catalyst and an organic solvent, the dechlorination reagent used in the dechlorination is a potassium hydroxide aqueous solution, and the mass of potassium hydroxide in the potassium hydroxide aqueous solution used for each dechlorination accounts for ≥2.4% of the mass of the epoxy resin; and the dechlorination temperature is ≥80°C.

[0032] In the present invention, the total chlorine content of the epoxy resin is ≥1816ppm, specifically 1816ppm in the embodiment. The chromaticity of the epoxy resin is ≤11APHA, specifically 11APHA in the embodiment. The phase transfer catalyst is preferably an alcohol catalyst. The alcohol catalyst preferably includes one or more of polyethylene glycol 200 (PEG200), polyethylene glycol 800 (PEG800), polyethylene glycol 2000 (PEG2000) and polypropylene glycol 400 (PEG400). The mass of the phase transfer catalyst accounts for 1 to 3% of the mass of the epoxy resin, specifically 3% or 1% in the embodiment. The organic solvent preferably includes one or more of toluene, xylene and methyl isobutyl ketone (MIBK). The mass of the epoxy resin in the epoxy resin organic phase solution accounts for 40 to 70% of the total mass of the epoxy resin and the organic solvent.

[0033] In the present invention, the preparation method of the epoxy resin organic phase solution comprises the following steps: mixing the epoxy resin with an organic solvent to obtain a resin solution, wherein the mass percentage of the epoxy resin in the resin solution is preferably 40-70%; mixing the resin solution with the phase transfer catalyst. The mixing of the resin solution and the phase transfer catalyst is carried out under stirring. The temperature of the epoxy resin organic phase solution is preferably 85-90°C.

[0034] In the present invention, the mass percentage of the potassium hydroxide aqueous solution is preferably 42-48%, and in the embodiment, it can be 42%, 45% or 48%; the temperature of the potassium hydroxide aqueous solution used for each dechlorination is preferably 90-95° C. The mass percentage of potassium hydroxide in the potassium hydroxide aqueous solution used for each dechlorination to the mass percentage of the epoxy resin is preferably 2.4-3.6%, for example, it can be 2.4%, 3.0% or 3.6%.

[0035] In the present invention, the specific operation method of each dechlorination is preferably: the epoxy resin organic phase solution or the n-1th dechlorination organic phase solution is mixed with a potassium hydroxide aqueous solution for dechlorination. The temperature of the dechlorination is ≥80°C. The temperature of the n-1th dechlorination organic phase solution is preferably 85-90°C. The temperature of the dechlorination is the temperature of the mixed solution obtained by mixing the epoxy resin organic phase solution or the n-1th dechlorination organic phase solution with a potassium hydroxide aqueous solution. The dechlorination is carried out under high-speed shearing conditions, and the speed of the high-speed shearing is preferably 900-1100r / min, and specifically 900r / min, 1000r / min or 1100r / min in the embodiment. The time of each dechlorination is 3-5min. In the present invention, n is specifically 2, 3, 4, 5, 6, 7, 8 or 9.

[0036] In the present invention, water is used to terminate each dechlorination to obtain a final dechlorination solution or an n-1th dechlorination solution. In a specific embodiment of the present invention, water is preferably added to the mixed system after the dechlorination is completed to terminate each dechlorination. The mass of water used at the end of each dechlorination accounts for 15-20% of the total mass of the epoxy resin and the organic solvent.

[0037] After obtaining the final dechlorination solution, the present invention allows the final dechlorination solution to stand for stratification to obtain a final dechlorination organic phase solution.

[0038] After obtaining the final dechlorinated organic phase solution, the present invention adjusts the pH value of the final dechlorinated organic phase solution to 6-7 to obtain a neutralized dechlorinated organic phase solution. In the present invention, the pH adjusting agent used for adjusting the pH value is preferably a sodium dihydrogen phosphate aqueous solution. The present invention has no special requirements for the concentration of the sodium dihydrogen phosphate aqueous solution, and the pH value of the final dechlorinated organic phase solution can be adjusted to 6-7.

[0039] After obtaining the neutralized and dechlorinated organic phase solution, the present invention removes solvent from the neutralized and dechlorinated organic phase solution to obtain the low-chlorine epoxy resin. The present invention has no special requirements for the specific implementation of the desolventizing.

[0040] In summary, the present invention mainly uses potassium hydroxide to remove chloride ions in epoxy resin to achieve the effect of dechlorination of epoxy resin. The present invention first prepares epoxy resin into an organic phase liquid, adds alcohol substances as a phase transfer catalyst, and quickly dechlorinates by controlling the temperature of dechlorination, adds water to terminate the reaction and remove the inorganic phase, and after multiple dechlorination reactions, the organic phase is neutralized and washed with sodium dihydrogen phosphate aqueous solution, and the solvent is removed to obtain a low-chlorine epoxy resin. In the present invention, the total chlorine content of the low-chlorine epoxy resin is ≤873ppm, and is specifically 696ppm, 314ppm, 78ppm, 255ppm or 773ppm in the embodiment. The chromaticity of the low-chlorine epoxy resin is ≥14APHA, and is specifically 17APHA, 18APHA, 62APHA, 29APHA or 14APHA in the embodiment.

[0041] The present invention provides the application of the low-chlorine epoxy resin prepared by the preparation method described in the above technical solution in electronics or photoresist. The present invention has no special requirements on the specific implementation of the application.

[0042] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0043] The same batch of liquid epoxy resin was used in the following examples and comparative examples, and the measured color value was 11APHA and the measured total chlorine value was 1816ppm. The liquid epoxy resin was bisphenol A type epoxy resin, and the resin model used was YN 1828 liquid epoxy resin (Jiangsu Yangnong Jinhu Chemical Co., Ltd.).

[0044] The chromaticity measurement method in the present invention is GB / T 9282.1-2008.

[0045] Among them, the method for determining the total chlorine content in epoxy resin adopts the national standard GB / T12007.3-1989, the principle of which is to oxidize the epoxy resin with oxygen and then measure the content of the generated chloride by potentiometric titration or volumetric titration.

[0046] Example 1

[0047] (1) 400 g of epoxy resin was placed in a 2000 mL reaction bottle, 600 g of xylene was added to prepare an organic phase liquid, 12 g of PEG200 was added, and the mixture was stirred and heated to 85° C. to obtain an epoxy resin organic phase solution.

[0048] (2) Potassium hydroxide is prepared into a potassium hydroxide aqueous solution with a mass percentage of 45%, the temperature is raised to 95° C., 21.3 g of the potassium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, the high-speed shear speed is set to 1100 r / min, and after stirring for 3 min, 150 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0049] (3) The temperature of the first dechlorination organic phase solution was raised to 85°C, 21.3 g of the potassium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at one time, the high-speed shear speed was set to 1100 r / min, and after stirring for 3 min, 150 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0050] (4) Repeat step (3) once with the second dechlorinated organic phase solution to obtain a third dechlorinated organic phase solution.

[0051] (5) The organic phase solution obtained by the third dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product, the actual measured color value of which was 14 APHA and the actual measured total chlorine content was 696 ppm.

[0052] Example 2

[0053] (1) 1400 g of epoxy resin was placed in a 5000 mL reaction bottle, 600 g of MIBK was added to prepare an organic phase liquid, 42 g of polypropylene glycol 400 was added, and the mixture was stirred and heated to 95° C. to obtain an epoxy resin organic phase solution.

[0054] (2) Potassium hydroxide is prepared into a potassium hydroxide aqueous solution with a mass percentage of 48%, and the temperature is raised to 95° C. 105 g of the potassium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, and the high-speed shear speed is set to 900 r / min. After stirring for 5 minutes, 300 g of water is added to terminate the reaction, and the waste water is separated by standing to obtain the first dechlorination organic phase solution.

[0055] (3) The first dechlorination organic phase solution was heated to 95°C, 105 g of the 95°C potassium hydroxide aqueous solution in step (2) was poured into the first dechlorination organic phase solution at once, the high-speed shear speed was set to 900 r / min, and after stirring for 5 min, 300 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0056] (4) Repeat step (3) three times with the second dechlorinated organic phase solution to obtain the fifth dechlorinated organic phase solution.

[0057] (5) The organic phase solution obtained by the fifth dechlorination was added with a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product, the actual measured color value of which was 18 APHA and the actual measured total chlorine content value was 314 ppm.

[0058] Example 3

[0059] (1) 50 g of epoxy resin was placed in a 500 mL reaction bottle, 50 g of toluene was added to prepare an organic phase liquid, 0.5 g of polyethylene glycol 800 was added, and the mixture was stirred and heated to 85° C. to obtain an epoxy resin organic phase solution.

[0060] (2) Potassium hydroxide is prepared into a potassium hydroxide aqueous solution with a mass percentage of 42%, and the temperature is raised to 95° C. 2.9 g of the potassium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, and the high-speed shear speed is set to 1000 r / min. After stirring for 5 minutes, 20 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0061] (3) The temperature of the first dechlorination organic phase solution was raised to 85°C, 2.9 g of the potassium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at one time, the high-speed shear speed was set to 1000 r / min, and after stirring for 5 min, 20 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0062] (4) Repeat step (3) 6 times with the second dechlorinated organic phase solution to obtain the eighth dechlorinated organic phase solution.

[0063] (5) The organic phase solution obtained by the eighth dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product, the actual measured color value of which was 62 APHA and the actual measured total chlorine content value was 78 ppm.

[0064] Example 4

[0065] (1) 4000 g of epoxy resin was placed in a 20000 mL reaction bottle, 6000 g of toluene was added to prepare an organic phase liquid, 40 g of polyethylene glycol 2000 was added, and the mixture was stirred and heated to 85° C. to obtain an epoxy resin organic phase solution.

[0066] (2) Potassium hydroxide is prepared into a potassium hydroxide aqueous solution with a mass percentage of 44%, the temperature is raised to 95° C., 272.7 g of the potassium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, the high-speed shear speed is set to 1100 r / min, and after stirring for 5 min, 1500 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0067] (3) The first dechlorination organic phase solution was heated to 85°C, 272.7 g of the potassium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at once, the high-speed shear speed was set to 1100 r / min, and after stirring for 5 min, 1500 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water to obtain a second dechlorination organic phase solution.

[0068] (4) Repeat step (3) 4 times with the second dechlorinated organic phase solution to obtain the sixth dechlorinated organic phase solution.

[0069] (5) The organic phase solution obtained by the sixth dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product. The actual measured color value was 29 APHA, and the actual measured total chlorine content was 255 ppm.

[0070] Example 5

[0071] (1) 60 g of epoxy resin was placed in a 500 mL reaction bottle, 40 g of toluene was added to prepare an organic phase liquid, 1.8 g of polypropylene glycol 200 was added, and the mixture was stirred and heated to 90° C. to obtain an epoxy resin organic phase solution.

[0072] (2) Potassium hydroxide is prepared into a potassium hydroxide aqueous solution with a mass percentage of 42%, the temperature is raised to 95° C., 4.3 g of the potassium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, the high-speed shear speed is set to 900 r / min, and after stirring for 3 min, 20 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0073] (3) The temperature of the first dechlorination organic phase solution was raised to 90°C, 4.3 g of the potassium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at one time, the high-speed shear speed was set to 900 r / min, and after stirring for 3 min, 20 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0074] (4) The organic phase solution obtained by the second dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product. The actual measured color value was 17 APHA, and the actual measured total chlorine content was 773 ppm.

[0075] Comparative Example 1

[0076] The preparation method is basically the same as that in Example 1, except that potassium hydroxide is replaced by sodium hydroxide. The specific steps are as follows:

[0077] (1) 400 g of epoxy resin was placed in a 2000 mL reaction bottle, 600 g of xylene was added to prepare an organic phase liquid, 12 g of PEG200 was added, and the mixture was stirred and heated to 85° C. to obtain an epoxy resin organic phase solution.

[0078] (2) Sodium hydroxide is prepared into a sodium hydroxide aqueous solution with a mass percentage of 45%, the temperature is raised to 95° C., 21.3 g of the sodium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, the high-speed shear speed is set to 1100 r / min, and after stirring for 3 min, 150 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0079] (3) The first dechlorination organic phase solution was heated to 85°C, 21.3 g of the sodium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at once, the high-speed shear speed was set to 1100 r / min, and after stirring for 3 min, 150 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0080] (4) Repeat step (3) once with the second dechlorinated organic phase solution to obtain a third dechlorinated organic phase solution.

[0081] (5) The organic phase solution obtained by the third dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product, the actual measured color value of which was 16APHA and the actual measured total chlorine content value was 1062ppm.

[0082] Comparative Example 2

[0083] The preparation method is basically the same as that in Example 2, except that potassium hydroxide is replaced by aluminum hydroxide. The specific steps are as follows:

[0084] (1) 1400 g of epoxy resin was placed in a 5000 mL reaction bottle, 600 g of MIBK was added to prepare an organic phase liquid, 42 g of polypropylene glycol 400 was added, and the mixture was stirred and heated to 95° C. to obtain an epoxy resin organic phase solution.

[0085] (2) Prepare aluminum hydroxide into an aluminum hydroxide aqueous solution with a mass percentage of 48%, heat it to 95° C., take 105 g of the aluminum hydroxide aqueous solution and pour it into the epoxy resin organic phase solution prepared in step (1) at one time, and set the high-speed shear speed to 900 r / min. After stirring for 5 minutes, add 300 g of water to terminate the reaction, let it stand and separate the waste water, and obtain the first dechlorination organic phase solution.

[0086] (3) The first dechlorination organic phase solution was heated to 95°C, 105 g of the aluminum hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at once, the high-speed shear speed was set to 900 r / min, and after stirring for 5 min, 300 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water to obtain the second dechlorination organic phase solution.

[0087] (4) Repeat step (3) three times with the second dechlorinated organic phase solution to obtain the fifth dechlorinated organic phase solution.

[0088] (5) The organic phase solution obtained by the fifth dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product. The actual measured color value was 21 APHA, and the actual measured total chlorine content was 1507 ppm.

[0089] Comparative Example 3

[0090] The preparation method is basically the same as that in Example 3, except that potassium hydroxide is replaced by magnesium hydroxide. The specific steps are as follows:

[0091] (1) 50 g of epoxy resin was placed in a 500 mL reaction bottle, 50 g of toluene was added to prepare an organic phase liquid, 0.5 g of polyethylene glycol 800 was added, and the mixture was stirred and heated to 85° C. to obtain an epoxy resin organic phase solution.

[0092] (2) Magnesium hydroxide is prepared into a magnesium hydroxide aqueous solution with a mass percentage of 42%, the temperature is raised to 95° C., 2.9 g of the magnesium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, the high-speed shear speed is set to 1000 r / min, and after stirring for 5 min, 20 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorination organic phase solution.

[0093] (3) The first dechlorination organic phase solution was heated to 85°C, 2.9 g of the magnesium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at one time, the high-speed shear speed was set to 1000 r / min, and after stirring for 5 min, 20 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0094] (4) Repeat step (3) 6 times with the second dechlorinated organic phase solution to obtain the eighth dechlorinated organic phase solution.

[0095] (5) The organic phase solution obtained by the eighth dechlorination was added into a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product, the actual measured color value of which was 35 APHA and the actual measured total chlorine content value was 1419 ppm.

[0096] Comparative Example 4

[0097] The preparation method is basically the same as that in Example 4, except that potassium hydroxide is replaced by sodium hydroxide. The specific steps are as follows:

[0098] (1) 4000 g of epoxy resin was placed in a 20000 mL reaction bottle, 6000 g of toluene was added to prepare an organic phase liquid, 40 g of polyethylene glycol 2000 was added, and the mixture was stirred and heated to 85° C. to obtain an epoxy resin organic phase solution.

[0099] (2) Sodium hydroxide is prepared into a sodium hydroxide aqueous solution with a mass percentage of 44%, the temperature is raised to 95° C., 272.7 g of the sodium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, the high-speed shear speed is set to 1100 r / min, and after stirring for 5 min, 1500 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0100] (3) The first dechlorination organic phase solution was heated to 85°C, 272.7 g of the sodium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at once, the high-speed shear speed was set to 1100 r / min, and after stirring for 5 min, 1500 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water to obtain the second dechlorination organic phase solution.

[0101] (4) Repeat step (3) 4 times with the second dechlorinated organic phase solution to obtain the sixth dechlorinated organic phase solution.

[0102] (5) The organic phase solution obtained by the sixth dechlorination was added with a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product, the actual measured color value of which was 26 APHA and the actual measured total chlorine content value was 582 ppm.

[0103] Comparative Example 5

[0104] The preparation method is basically the same as that in Example 5, except that potassium hydroxide is replaced by sodium hydroxide. The specific steps are as follows:

[0105] (1) 60 g of epoxy resin was placed in a 500 mL reaction bottle, 40 g of toluene was added to prepare an organic phase liquid, 1.8 g of polypropylene glycol 200 was added, and the mixture was stirred and heated to 90° C. to obtain an epoxy resin organic phase solution.

[0106] (2) Sodium hydroxide is prepared into a sodium hydroxide aqueous solution with a mass percentage of 42%, and the temperature is raised to 95° C. 4.3 g of the sodium hydroxide aqueous solution is poured into the epoxy resin organic phase solution prepared in step (1) at one time, and the high-speed shear speed is set to 900 r / min. After stirring for 3 minutes, 20 g of water is added to terminate the reaction, and the solution is allowed to stand to separate the waste water, thereby obtaining the first dechlorinated organic phase solution.

[0107] (3) The temperature of the first dechlorination organic phase solution was raised to 90°C, 4.3 g of the sodium hydroxide aqueous solution at 95°C in step (2) was poured into the first dechlorination organic phase solution at one time, the high-speed shear speed was set to 900 r / min, and after stirring for 3 min, 20 g of water was added to terminate the reaction, and the solution was allowed to stand to separate the waste water, thereby obtaining a second dechlorination organic phase solution.

[0108] (4) The organic phase solution obtained by the second dechlorination was added to a sodium dihydrogen phosphate aqueous solution to neutralize the solution to a pH of 6 to 7, and then the solvent was removed to obtain a low-chlorine epoxy resin product. The actual measured color value was 18 APHA, and the actual measured total chlorine content was 1268 ppm.

[0109] Comparative Example 6

[0110] According to the method disclosed in Example 6 of the specification of Chinese patent CN117903412A:

[0111] A method for reducing the total chlorine content in epoxy resin, the specific method steps are as follows:

[0112] 100g of epoxy resin (bisphenol F type epoxy resin) was dissolved in 100mL of toluene solution, 1g of sodium methoxide was added, and the mixture was heated to 80°C with stirring for 1h. 50g of purified water was added for washing, and the mixture was allowed to stand for separation. The organic phase was concentrated to dryness under reduced pressure to obtain 97.5g of product with a yield of 97.5%. The total chlorine content of the epoxy resin before the reaction was 1864ppm, and the total chlorine content after the reaction was 427ppm. The chromaticity was 114APHA. Since the chromaticity value of the epoxy resin prepared in this comparative example was high, the product color was very dark, which caused trouble for the application of low-chlorine epoxy resin in high-end fields, and it was impossible to perform multiple dechlorination and customized production of products with different total chlorine contents.

[0113] Sodium alcoholate is a highly hygroscopic substance. The reaction in Comparative Example 6 is a normal pressure reaction and will be disturbed by oxygen during the reaction. Sodium alcoholate is highly active and will induce the ring opening of the epoxy resin during the dechlorination reaction. At this time, if the epoxy resin is exposed to oxygen, it is very likely to be oxidized, resulting in a yellowish chromaticity and a darker color.

[0114] Table 1 shows the performance test results of the epoxy resin raw materials and the low-chlorine epoxy resin products in Examples 1 to 5 and Comparative Examples 1 to 6.

[0115] Table 1 Performance test results of epoxy resin raw materials and low-chlorine epoxy resin products in Examples 1 to 5 and Comparative Examples 1 to 6

[0116]

[0117]

[0118] From the above examples, it can be seen that the method provided by the present invention is compared with the sodium alcoholate system used in Comparative Example 6 for dechlorination. The method in Comparative Example 6 can only perform dechlorination once, and the dechlorination efficiency is limited. The present invention uses a potassium hydroxide system to repeatedly dechlorinate, and customized production of products with different total chlorine contents has a large operating space. Moreover, the product made by the method of Comparative Example 6 using the sodium alcoholate system is very dark in color and is not suitable for high-end epoxy application systems.

[0119] Therefore, the dechlorinating agent used in the present invention is potassium hydroxide, and the resin is a conventional liquid epoxy resin, which are both conventional industrial raw materials, low in price and easy to obtain, simple in process and excellent in dechlorination effect, and the chlorine content of the final product can be controlled by repeated reactions, with good stability between batches, environmental friendliness in the entire reaction process, low in process cost, and can also reduce the labor intensity of workers, and can be widely promoted and used. The advantages are summarized and limited.

[0120] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a low-chlorine epoxy resin, characterized in that: The following steps are involved: The epoxy resin organic phase solution is subjected to n dechlorinations, wherein n is a positive integer ≥ 1, and when n = 1, a final dechlorinated solution is directly obtained; when n ≥ 2, an n-1 dechlorinated solution is directly obtained after the n-1 dechlorination, the n-1 dechlorinated solution is allowed to stand for stratification to obtain an n-1 dechlorinated organic phase solution, and the n-1 dechlorinated organic phase solution is subjected to an n-th dechlorination to obtain a final dechlorinated solution; the epoxy resin organic phase solution comprises an epoxy resin, a phase transfer catalyst and an organic solvent, the dechlorination reagent used in the dechlorination is a potassium hydroxide aqueous solution, and the mass of potassium hydroxide in the potassium hydroxide aqueous solution used for each dechlorination accounts for ≥ 2.4% of the mass of the epoxy resin; the dechlorination temperature is ≥ 80°C; The final dechlorination solution is allowed to stand for stratification to obtain a final dechlorination organic phase solution; The pH value of the final dechlorinated organic phase solution is adjusted to 6-7 to obtain a neutralized dechlorinated organic phase solution; The neutralized and dechlorinated organic phase solution is desolventized to obtain the low-chlorine epoxy resin.

2. The preparation method according to claim 1, characterized in that: The time for each dechlorination is 3 to 5 minutes.

3. The preparation method according to claim 1 or 2, characterized in that: The dechlorination is carried out under the condition of high-speed shearing, and the rotation speed of the high-speed shearing is 900-1100r / min.

4. The preparation method according to claim 1, characterized in that: The phase transfer catalyst is an alcohol catalyst; the mass of the phase transfer catalyst accounts for 1-3% of the mass of the epoxy resin.

5. The preparation method according to claim 4, characterized in that: The alcohol catalyst includes one or more of polyethylene glycol 200, polyethylene glycol 800, polyethylene glycol 2000 and polypropylene glycol 400.

6. The preparation method according to claim 1 or 4, characterized in that: The organic solvent comprises one or more of toluene, xylene and methyl isobutyl ketone; the mass of the epoxy resin in the epoxy resin organic phase solution accounts for 40-70% of the total mass of the epoxy resin and the organic solvent.

7. The preparation method according to claim 1, characterized in that: The temperature of the epoxy resin organic phase solution and the n-1th dechlorination organic phase solution are independently 85-90° C.; The mass percentage of the potassium hydroxide aqueous solution is 42-48%; the temperature of the potassium hydroxide aqueous solution is 90-95°C.

8. The preparation method according to claim 1 or 4, characterized in that: After each dechlorination, water is used to terminate the process to obtain a final dechlorination solution or an n-1th dechlorination solution; the mass of the water used to terminate the process after each dechlorination accounts for 15-20% of the total mass of the epoxy resin and the organic solvent.

9. The preparation method according to claim 1, characterized in that: The total chlorine content of the epoxy resin is ≥1816ppm, and the total chlorine content of the low-chlorine epoxy resin is ≤800ppm.

10. Use of the low-chlorine epoxy resin prepared by the preparation method according to any one of claims 1 to 9 in photoresist.

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