CN116120519A - Refining method of ultra-high purity epoxy resin - Google Patents
Refining method of ultra-high purity epoxy resin Download PDFInfo
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- CN116120519A CN116120519A CN202310070650.2A CN202310070650A CN116120519A CN 116120519 A CN116120519 A CN 116120519A CN 202310070650 A CN202310070650 A CN 202310070650A CN 116120519 A CN116120519 A CN 116120519A
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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Abstract
The invention discloses a refining method of ultra-high purity epoxy resin, which comprises the steps of reacting the epoxy resin to be purified in an organic solvent at a temperature of 40-200 ℃ for 0.5-8 hours under the action of an alkali metal and/or alkaline earth metal catalyst A and a basic catalyst B, and obtaining the ultra-high purity epoxy resin with the total chlorine content of below 500ppm after the reaction is completed. The sum of the weight of the catalyst A and the weight of the catalyst B is 0.1-5.0% of the total weight of the epoxy resin to be refined, and the usage amount of the basic catalyst B is 1-15% of the usage amount of the catalyst A. The total chlorine content of the ultra-high purity epoxy resin refined by the refining method is below 500ppm, and the ratio of the epoxy equivalent of the refined epoxy resin to the epoxy equivalent of the epoxy resin before refining is less than or equal to 1.1.
Description
The present application is a divisional application of the title of the invention of "refining method of ultra-high purity epoxy resin" with the application of 2017, 12, 27 and 201711442464.8.
Technical Field
The invention relates to the field of epoxy resin, in particular to a refining method of ultra-high purity epoxy resin.
Background
The epoxy resin has epoxy groups with rich reactivity, active groups such as hydroxyl groups and ether bonds and polar groups, can be matched with various curing agents to obtain various curing systems and cured products with excellent performance and various characteristics, and can also meet the requirements of various different service performances and process conditions. Therefore, the composite material is used in paint, electronic and electric materials, composite materials, building materials, aerospace materials and recently, new energy automobiles and the like have been widely used.
Epoxy resins are generally produced from phenols, amines, carboxylic acids, alcohols, etc., and epichlorohydrin using caustic soda as a catalyst. In the reaction process, impurities such as hydrolyzable chlorine, non-hydrolyzable chlorine and the like are contained in the finished product due to side reactions and incomplete reaction, and the incomplete washing of the finished product leads to chloride ion residues. The sum of hydrolyzable chlorine, non-hydrolyzable chlorine and chloride ions is called total chlorine, and these impurities have adverse effects on the reactivity of the epoxy resin during curing and on the electrical properties, heat resistance, chemical resistance, mechanical properties and the like of the cured product, so that the field of the front end of the ultra-high purity epoxy resin is strongly demanded, for example, industries such as high-end electronics, conductive paste, latent curing agent and the like, and there is a very severe demand for the purity of the epoxy resin, particularly the content of the impurities such as organic chlorine and inorganic chlorine. In the fields of composite materials, building materials, aerospace materials, new energy automobiles and the like, extremely high demands are also made on heat resistance, chemical resistance, mechanical properties and the like of cured epoxy resins, so that the reduction of the purity of epoxy resins, particularly the reduction of the content of impurities such as organic chlorine, inorganic chlorine and the like, is urgent. Generally, phenols and amines have high reactivity with epichlorohydrin, and the total chlorine content of the epoxy resin is about 1500 to 2000ppm even though the epoxy resin is purified several times. Alcohols and carboxylic acids are less reactive with epichlorohydrin, so their total chlorine content of the epoxy resin is higher, about 8000-60000 ppm.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a refining method of ultra-high purity epoxy resin.
The invention aims to provide a refining method of ultra-high purity epoxy resin, which specifically comprises the following steps: the epoxy resin to be purified reacts in an organic solvent under the action of an alkali metal and/or alkaline earth metal catalyst A and a basic catalyst B, and the ultra-high purity epoxy resin is obtained after the reaction is completed.
Further preferably, the reaction is carried out in an organic solvent at a temperature ranging from 40 to 200 ℃ for 0.5 to 8 hours; the addition amount of the alkali metal and/or alkaline earth metal catalyst A and the basic catalyst B satisfies the following conditions: the sum of the weight of the catalyst A and the weight of the catalyst B is 0.1-5.0% of the total weight of the epoxy resin to be refined, and the usage amount of the basic catalyst B is 1-15% of the usage amount of the catalyst A.
Further preferably, the sum of the weight of the catalyst A and the weight of the catalyst B is 0.8 to 4.0% of the total weight of the epoxy resin to be purified.
Further preferably, the alkali metal-based and/or alkaline earth metal-based catalyst a is a mixture of any one or two or more of alkali metal-based catalysts including lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and rubidium bicarbonate; the alkaline earth metal catalyst comprises beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate and barium carbonate.
Further preferably, the basic catalyst B is a tertiary amine catalyst, and/or an ammonium salt catalyst, and/or an imi-on catalyst, and/or a phosphine catalyst, and/or a phosphonium catalyst, and/or a lewis base catalyst, the tertiary amine catalyst comprising trimethylamine, triethylamine, tripropylamine, tributylamine, N-methylmorpholine, tris- (dimethylaminomethyl) phenol, N-methyldiethanolamine and 12 tertiary amines; the imidazole catalyst comprises 1-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, C11-imidazole and C17-imidazole; the ammonium salt catalyst comprises trimethylamine hydrochloride, triethylamine hydrochloride, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, benzyl triethyl ammonium chloride and benzyl triethyl ammonium bromide; the phosphine catalyst comprises triphenylphosphine and tris (2, 6-methoxyphenyl) phosphine; the phosphonium catalyst comprises triphenyl n-butyl phosphonium chloride, triphenyl n-butyl phosphonium bromide, triphenyl n-butyl phosphonium hydroxide, tetra-n-butyl phosphonium chloride, tetra-n-butyl phosphonium bromide and tetra-n-butyl phosphonium hydroxide; the lewis base catalyst comprises ammonium hydroxide and tetramethylammonium hydroxide.
Further preferably, the organic solvent is a non-reactive and/or non-aqueous organic solvent.
Further preferably, the organic solvent is one or a mixture of two or more of toluene, xylene, cyclohexane, n-hexane, diethyl ether, butanone, methyl isobutyl ketone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, and the like.
Further preferably, the epoxy resin to be purified is a compound or mixture having an epoxy group.
Further preferably, the epoxy resin to be purified includes any one or two or more of monofunctional epoxy resin, difunctional aromatic epoxy resin, aliphatic difunctional epoxy resin, trifunctional aromatic epoxy resin, tetrafunctional aromatic epoxy resin and other multifunctional epoxy resin.
Further preferably, the monofunctional epoxy resin includes phenyl glycidyl ether, o-methylphenyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, n-butyl glycidyl ether, benzyl glycidyl ether, and neo-decanoic acid glycidyl ester;
the difunctional aromatic epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol epoxy resin, 2,6 dimethyl bisphenol epoxy resin, tetrabromobisphenol A epoxy resin, naphthalene diphenol epoxy resin, benzene diphenol epoxy resin, diphenol hexafluoropropane epoxy resin and phthalic acid diphenol epoxy resin;
the aliphatic difunctional epoxy resin comprises hydrogenated bisphenol A epoxy resin, tetrahydrophthalic acid diglycidyl resin, hexahydrophthalic acid diglycidyl resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1, 2-propanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 3, 4-epoxycyclohexane carboxylic acid-3 ',4' -epoxycyclohexane methyl ester;
the trifunctional aromatic epoxy resin comprises p-hydroxyaniline trioxyresin, 1, 2-epoxycyclohexane, 4, 5-dicarboxylic acid epoxy resin, phloroglucinol trioxyresin, triphenolalkane trioxyresin, glycerol glycidyl ether, trimethylolpropane glycidyl ether, trimesic acid trioxyresin, triglycidyl isocyanurate and triglycidyl isocyanurate;
the tetrafunctional aromatic epoxy resin comprises 3,3' -diaminodiphenylmethane epoxy resin, 4' -diaminodiphenyl sulfone epoxy resin, 4' -diaminodiphenyl ether epoxy resin, tetraphenolethane tetraepoxy resin, 1,3BAC tetraepoxy resin and resorcinol formaldehyde tetraglycidyl ether;
further preferably, the multifunctional epoxy resin includes novolac epoxy resin, ortho-methylphenol epoxy resin and bisphenol a novolac epoxy resin.
The invention has the advantages that:
the invention provides a refining method of ultra-high purity epoxy resin, wherein the refining reaction is carried out in non-reactive and/or non-aqueous organic solvent. The total chlorine content of the ultra-high purity epoxy resin obtained by the refining method is below 500ppm, and the epoxy equivalent of the refined epoxy resin/the epoxy equivalent of the epoxy resin before refining is less than or equal to 1.1.
Detailed Description
The invention provides a refining method of ultra-high purity epoxy resin, which comprises the following steps:
the epoxy resin is reacted in the presence of alkali metal and/or alkaline earth metal catalyst A in proper amount of basic catalyst B at 40-200 deg.c for 0.5-8 hr to obtain the ultra high purity epoxy resin with total chlorine content below 500 ppm. Specifically, firstly, epoxy resin is added into an organic solvent, stirred, so that the epoxy resin is dissolved, then the temperature is increased to 40 ℃, alkali metal and/or alkaline earth metal catalyst A and basic catalyst B are added, and then the temperature is increased to the temperature required by the reaction, namely 40-200 ℃, and the reaction is carried out for 0.5-8 hours. In the reaction process, a thermometer is inserted into a reaction bottle so as to control the reaction temperature, and the whole reaction process is reacted under the protection of nitrogen while stirring. And after the reaction time is up, obtaining the ultra-high purity epoxy resin through desalination, neutralization, water washing and solvent removal. The process steps of desalting, neutralizing, washing and desolventizing are performed by adopting the prior art, and are not repeated in the invention.
The catalyst is A is an alkali metal catalyst and/or an alkaline earth metal catalyst; the basic catalyst B is tertiary amine catalyst, and/or ammonium salt catalyst, and/or miaow-block catalyst, and/or phosphine catalyst, and/or phosphonium catalyst, and/or Lewis base catalyst. The catalyst A and the basic catalyst B used in the reaction are added in an amount of 0.1-5% of the total weight of the epoxy resin to be reacted. Wherein the usage amount of the salt-based catalyst B is 1-15% of that of the catalyst A.
The above refining method of the ultra-high purity epoxy resin is carried out in a non-reactive and/or non-aqueous organic solvent, namely the organic solvent is a non-reactive organic solvent, a non-aqueous organic solvent or a non-reactive and non-aqueous organic solvent.
In general, the epoxy resin which can be purified according to the present invention is a compound or a mixture having an epoxy group, and specifically includes any one or two or more of monofunctional epoxy resin, difunctional aromatic epoxy resin, aliphatic difunctional epoxy resin, trifunctional aromatic epoxy resin, tetrafunctional aromatic epoxy resin and other multifunctional epoxy resin, and when two types are included, the relative weight ratio is not limited. And the formation of the above epoxy resin may include its modification inducer and distilled purified monomer, or a mixture of both.
The monofunctional epoxy resin comprises phenyl glycidyl ether, o-methylphenyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, n-butyl glycidyl ether, benzyl glycidyl ether, neo-decanoic acid glycidyl ester and the like.
The difunctional aromatic epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol epoxy resin, 2,6 dimethyl bisphenol epoxy resin, tetrabromobisphenol A epoxy resin, naphthalene diphenol epoxy resin, benzene diphenol epoxy resin, diphenol hexafluoropropane epoxy resin, phthalic acid diphenol epoxy resin and the like.
The aliphatic difunctional epoxy resin includes hydrogenated bisphenol a epoxy resin, tetrahydrophthalic acid diglycidyl resin, hexahydrophthalic acid diglycidyl resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1, 2-propanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 3',4' -epoxycyclohexane methyl 3, 4-epoxycyclohexane carboxylate, and the like.
The trifunctional aromatic epoxy resin includes p-hydroxyaniline trioxyresin, 1, 2-epoxycyclohexane, 4, 5-dicarboxylic acid epoxy resin, phloroglucinol trioxyresin, triphenolalkyl trioxyresin, glycerol glycidyl ether, trimethylolpropane glycidyl ether, trimesic acid trioxyresin, triglycidyl isocyanurate and the like.
The tetrafunctional aromatic epoxy resin comprises 3,3' -diaminodiphenylmethane epoxy resin, 4' -diaminodiphenyl sulfone epoxy resin, 4' -diaminodiphenyl ether epoxy resin, tetraphenolethane tetraepoxy resin, 1,3BAC tetraepoxy resin, resorcinol formaldehyde tetraglycidyl ether and the like.
The multifunctional epoxy resin includes novolac epoxy resin, ortho-methylphenol epoxy resin, bisphenol a novolac epoxy resin, and the like.
The catalyst A is alkali metal and/or alkaline earth metal, and the alkali metal catalyst specifically comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate and the like. The alkaline earth metal catalyst includes beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and the like, is not limited to the above list, and one of them can be used alone or two or more of them can be mixed for use, and the specific mixing ratio is not limited. When the catalyst A is selected as a mixture formed by alkali metal and alkaline earth metal, the weight ratio of the alkali metal catalyst to the alkaline earth metal catalyst is 40-60%: 60 to 40% by weight of the two catalysts are preferably equal, and wherein the alkali metal catalyst and the alkaline earth metal catalyst may be a compound or a mixture, and the mixing type is not limited when forming a mixture, and the weight of each component is preferably equal.
The basic catalyst B is tertiary amine catalyst and/or ammonium salt catalyst and/or imidazole catalyst and/or phosphine catalyst and/or phosphonium catalyst and/or Lewis base catalyst. The tertiary amine catalyst specifically comprises trimethyl amine, triethyl amine, tripropyl amine, tributyl amine, N-methylmorpholine, tri- (dimethylaminomethyl) phenol, N-methyldiethanolamine, 12 tertiary amine and the like. The imidazole catalyst comprises 1-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, C11-imidazole, C17-imidazole and the like. The ammonium salt catalyst comprises trimethylamine hydrochloride, triethylamine hydrochloride, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide and the like. The phosphine catalyst comprises triphenylphosphine, tris (2, 6-methoxyphenyl) phosphine and the like. The phosphonium catalyst includes triphenyl n-butyl phosphonium chloride, triphenyl n-butyl phosphonium bromide, triphenyl n-butyl phosphonium hydroxide, tetra-n-butyl phosphonium chloride, tetra-n-butyl phosphonium bromide, tetra-n-butyl phosphonium hydroxide, etc. The Lewis base catalyst comprises ammonium hydroxide, tetramethylammonium hydroxide and the like. The specific choice of the above-mentioned basic catalyst B is not limited to the above list, and any of tertiary amine haloates, ammonium salts, imidazoles, phosphonium salts and the like may be used. Any one of them may be used alone, or two or more of them may be used in combination, and the specific mixing ratio is not limited.
Preferably, when the basic catalyst B is a mixture, it is preferably a mixture of ammonium salt catalyst and phosphonium catalyst, the weight ratio of each other is 20-80%: 80-20%, wherein the ammonium salt catalyst may comprise any 1-3 compounds, preferably the weight of each compound is equal when 2 or 3 compounds are selected to form a mixture; the phosphonium catalyst may contain any 1 to 3 compounds, and when 2 or 3 compounds are selected to form a mixture, it is preferable that the weight of each compound is equal.
The amount of the alkali metal and/or alkaline earth metal catalyst A and the amount of the basic catalyst B used are as follows: the weight of the catalyst A and the weight of the catalyst B are 0.1-5.0 percent of the total weight of the epoxy resin to be refined, and when the addition amount of the catalyst A and the catalyst B is less than 0.1 percent of the total weight of the epoxy resin, the refining effect of the total chlorine content is poor, and the total chlorine content below 500ppm is difficult to reach; when the weight of the catalyst A plus the addition amount of the catalyst B is more than 5.0% of the total weight of the epoxy resin, the polymerization reaction of the epoxy resin is excessively large, the epoxy equivalent and viscosity are greatly increased, and there is a risk of gelation.
The addition amount of the catalyst A and the catalyst B is preferably 0.5 to 4.5% by weight based on the total weight of the epoxy resin to be purified, more preferably 0.8 to 4.0% by weight based on the total weight of the epoxy resin to be purified, still more preferably 2.0 to 3.0% by weight based on the total weight of the epoxy resin to be purified, and the addition amount of the catalyst can be adjusted depending on the total chlorine content of the epoxy resin in the actual addition.
Wherein the amount of the salt-based catalyst B is 1-15% of the total weight of the catalyst A, and the amount of the catalyst B is 1% or less of the weight of the catalyst A, the refining effect is too weak, and the amount of the catalyst B is 15% or more of the weight of the catalyst A, the viscosity of the resin is seriously increased, and the resin may be gelled. The amount of the basic catalyst B used is preferably 2 to 13%, more preferably 3 to 12%, of the amount of the catalyst A used, and the ratio and the amount of the catalyst A and the catalyst B to be added may be adjusted depending on the total chlorine content of the epoxy resin, the concentration of the resin liquid, the purification temperature and the purification time in the actual addition. Generally, the catalyst is used in a large amount when the total chlorine content is high, and the catalyst is used in a small amount when the total chlorine content is low. The reaction time is short when the reaction temperature is high, and the reaction time is long when the reaction temperature is low.
The organic solvent of the present invention is a non-reactive and/or non-aqueous organic solvent, which can avoid the increase of epoxy equivalent and viscosity caused by the hydrolysis of epoxy resin, and specifically includes solvents such as petroleum brains, such as toluene, xylene, cyclohexane, n-hexane, diethyl ether, etc., ketones, such as butanone, methyl isobutyl ketone, etc., ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, etc., but is not limited to this, and any non-reactive and/or non-aqueous organic solvent is a usable solvent of the present invention, either one of the solvents may be used alone or two or more of the usable solvents may be used in combination, and the specific mixing ratio is not limited.
Generally, an epoxy resin having a total chlorine content of 500ppm or less can be obtained by reacting at a temperature of 40 to 200℃for 0.5 to 8.0 hours. The reaction temperature is preferably 50-180 ℃, more preferably 60-160 ℃, and if the temperature is lower than 40 ℃, the refining effect is low, and the reaction time is too long, so that the method is not suitable for industrial production; if the temperature is higher than 200 ℃, the refining reaction is too violent, the energy consumption is large, and the epoxy resin is easy to change color. The reaction time is usually 0.5 to 8.0 hours, preferably 1.0 to 7.0 hours, more preferably 1.0 to 6.0 hours. If the reaction time is less than 0.5 hours, the refining effect is not obvious, the total chlorine of the resin cannot reach 500ppm or less, and if the reaction time is more than 8.0 hours, the production efficiency is low, the epoxy equivalent and viscosity of the epoxy resin are large and discoloration is easy.
The following examples and comparative examples are given to illustrate the present invention, but the present invention is not limited to the examples. The total chlorine and epoxy equivalent weights in the examples were measured on a KYOTOAT510 automatic potential difference titrator, total chlorine was measured according to ISO-21627-3 (2009) standard and epoxy equivalent weights were measured according to ISO-3001 (1999) standard. The viscosity was measured using an NDJ-5S rotational viscometer from Shanghai Changji geological instruments, inc. and a circulating constant temperature water bath THX-05 from Ningbo Tian Heng Instrument Co., ltd. According to ISO-3219 (1999) test method.
Examples and comparative examples
The raw materials described in table 1 were put into a 4-opening 1 liter glass reaction flask equipped with a stirring device, a condenser, a thermometer, and a nitrogen gas injection tube, the conditions described in table 1 were controlled during the reaction, the reaction flask was inserted with the thermometer and stirred under the protection of nitrogen gas to react, and then the resin purified product was obtained after desalting, neutralization, washing with water, and desolventizing, and the results were as follows.
In the table, AM-982 is bisphenol A type epoxy resin of Hui Bai company, FM-880 is bisphenol F type epoxy resin of Hui Bai company, FM-855 is bisphenol A and bisphenol F mixed type epoxy resin of Hui Bai company, and EL-128 is bisphenol A epoxy resin. The weight of the epoxy resin in each example and each comparative example was 300g, and MIBK was methyl isobutyl ketone.
Table 1 refining conditions and refining results of examples and comparative examples
As can be seen from the examples in Table 1 above, according to the conditions of the present invention, the epoxy resin having ultra-high purity can be purified by controlling the reaction time and the reaction temperature in accordance with the amounts of catalyst A and catalyst B.
As described above, the present invention provides a method for purifying an ultra-high purity epoxy resin, which comprises adding a proper amount of a basic catalyst to an epoxy resin in the presence of an alkali metal and/or an alkaline earth metal, and heating the mixture in a nonaqueous solvent to react the mixture, thereby obtaining an ultra-high purity epoxy resin having a total chlorine content of 500ppm or less and an epoxy equivalent rise of 1.1 times or less, which is suppressed before purification. The ultra-high purity epoxy resin can be used in the fields of front-end electronic and electric materials, coatings, composite materials, building materials, aerospace materials, new energy automobiles and the like, can improve the functions of durability, electrical performance, heat resistance, chemical resistance, mechanical property and the like of the materials, and provides high-functionality materials for the front-end technology industry.
The above is only a preferred embodiment of the present invention, and the present invention is not limited thereto, and various modifications and variations such as catalyst amount and reaction conditions may be adjusted according to the purity of each raw material. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The refining method of the ultra-high purity epoxy resin is characterized by comprising the following steps of: the epoxy resin to be purified reacts in an organic solvent under the action of a catalyst A and a catalyst B to obtain the ultra-high purity epoxy resin; the catalyst A is an alkali metal catalyst and/or an alkaline earth metal catalyst, and the catalyst B is a basic catalyst;
the sum of the weight of the catalyst A and the weight of the catalyst B is 0.1-5.0% of the total weight of the epoxy resin to be purified;
the catalyst A is one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide;
the catalyst B is one or more of tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, triphenyl n-butyl phosphonium hydroxide, tetra-n-butyl phosphonium bromide and tetra-n-butyl phosphonium hydroxide;
the organic solvent is a non-reactive organic solvent and/or a non-aqueous organic solvent;
the total chlorine content of the ultra-high purity epoxy resin is below 500 ppm.
2. The method for purifying an ultra-high purity epoxy resin according to claim 1, wherein the reaction in an organic solvent is: reacting in organic solvent at 40-200 deg.c for 0.5-8 hr; the usage amount of the catalyst B is 1-15% of that of the catalyst A.
3. The method for purifying an ultra-high purity epoxy resin according to claim 1 or 2, wherein the reaction in an organic solvent is specifically: firstly, adding epoxy resin into an organic solvent, stirring to dissolve the epoxy resin, then raising the temperature to 40 ℃, adding an alkali metal and/or alkaline earth metal catalyst A and a basic catalyst B, raising the temperature to the temperature required by the reaction, namely, 40-200 ℃, and reacting for 0.5-8 hours.
4. The method for purifying an ultra-high purity epoxy resin according to any one of claims 1 to 3, wherein the method further comprises desalting, neutralizing, washing with water and desolventizing after the completion of the reaction in the organic solvent.
5. The method for purifying an ultra-high purity epoxy resin according to claim 1, wherein the sum of the weight of the catalyst a and the weight of the catalyst B is 0.8 to 4.0% of the total weight of the epoxy resin to be purified.
6. The method for purifying an ultra-high purity epoxy resin according to claim 1, wherein the organic solvent is a mixed solvent of one or more of toluene, xylene, cyclohexane, n-hexane, diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol methyl ether acetate.
7. The method for purifying an ultra-high purity epoxy resin according to claim 1, wherein the epoxy resin to be purified is a compound or a mixture having an epoxy group.
8. The method for refining ultra-high purity epoxy resin according to claim 7, wherein the epoxy resin to be purified comprises any one or two or more of monofunctional epoxy resin, difunctional aromatic epoxy resin, aliphatic difunctional epoxy resin, trifunctional aromatic epoxy resin, tetrafunctional aromatic epoxy resin and other multifunctional epoxy resin.
9. The method for refining ultra-high purity epoxy resin according to claim 8, wherein the monofunctional epoxy resin comprises phenyl glycidyl ether, o-methylphenyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, n-butyl glycidyl ether, benzyl glycidyl ether and neodecanoic acid glycidyl ester;
the difunctional aromatic epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol epoxy resin, 2,6 dimethyl bisphenol epoxy resin, tetrabromobisphenol A epoxy resin, naphthalene diphenol epoxy resin, benzene diphenol epoxy resin, diphenol hexafluoropropane epoxy resin and phthalic acid diphenol epoxy resin;
the aliphatic difunctional epoxy resin comprises hydrogenated bisphenol A epoxy resin, tetrahydrophthalic acid diglycidyl resin, hexahydrophthalic acid diglycidyl resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1, 2-propanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 3, 4-epoxycyclohexane carboxylic acid-3 ',4' -epoxycyclohexane methyl ester;
the trifunctional aromatic epoxy resin comprises p-hydroxyaniline trioxyresin, 1, 2-epoxycyclohexane, 4, 5-dicarboxylic acid epoxy resin, phloroglucinol trioxyresin, triphenolalkane trioxyresin, glycerol glycidyl ether, trimethylolpropane glycidyl ether, trimesic acid trioxyresin, triglycidyl isocyanurate and triglycidyl isocyanurate;
the tetrafunctional aromatic epoxy resin comprises 3,3' -diaminodiphenylmethane epoxy resin, 4' -diaminodiphenyl sulfone epoxy resin, 4' -diaminodiphenyl ether epoxy resin, tetraphenolethane tetraepoxy resin, 1,3BAC tetraepoxy resin and resorcinol formaldehyde tetraglycidyl ether;
the other multifunctional epoxy resins include novolac epoxy resins, ortho-methylphenol epoxy resins, and bisphenol a novolac epoxy resins.
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