A kind of phenolic epoxy resin and preparation method thereof

Abstract

The specific embodiment of the present invention provides a phenolic epoxy resin and a preparation method thereof. The preparation method uses a phenolic resin introduced with a benzene ring or a biphenyl structure and epichlorohydrin as raw materials, and uses an inorganic strong alkaline substance as a catalyst to react in an alcohol ether solution to prepare the phenolic epoxy resin. By introducing the alcohol ether, the contact reaction between the phenolic resin, epichlorohydrin and the inorganic strong alkaline substance in the organic phase and the aqueous phase can be improved, the reaction rate can be increased, the reaction time can be shortened, and thus the by-products in the reaction product phenolic epoxy resin can be reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic materials, and specifically relates to a phenolic epoxy resin and a preparation method thereof. Background Art

[0002] As a semiconductor packaging material, epoxy resin is usually used for curing and sealing, among which resins formed by o-cresol novolac epoxy resin, phenol novolac curing agent and inorganic fillers such as silica are widely used for encapsulation. By introducing benzene rings or biphenyl structures into the epoxy resin and / or phenolic resin curing agent of the epoxy resin curing sealing material, its flame retardancy and high temperature resistance can be greatly improved. However, with the introduction of benzene rings or biphenyl structures, the reaction conversion efficiency is low, the reaction time is long, and impurities are increased, including hydrolyzable chlorine, total chlorine, and α-OH is high, and the epoxy equivalent is high. The total chlorine content of the generally produced phenolic epoxy resin is about 1500ppm, and the phenolic epoxy resin used in electronic materials is required to be below 900ppm. The domestic patent CN 108102075A improves the problem that the medium-polymer phenolic reactant is not easily dissolved in ECH for reaction by introducing an organic solvent. Although the total chlorine can be controlled below 1000ppm, the catalyst sodium hydroxide is in the water phase, and the catalytic efficiency is still low, which still does not meet the requirements of electronic materials. Summary of the invention

[0003] The specific embodiment of the present invention provides a method for preparing a phenolic epoxy resin and a phenolic epoxy resin with a low chlorine content, which shortens the reaction time and reduces the generation of by-products. The specific scheme is as follows:

[0004] A method for preparing a phenolic epoxy resin comprises the following steps:

[0005] The phenolic resin of the following formula (1) and epichlorohydrin are used as raw materials, and an inorganic strong alkaline substance is used as a catalyst. In an alcohol ether solution, the phenolic resin and epichlorohydrin react to prepare the phenolic epoxy resin;

[0006]

[0007] In the above formula (1), R1 is at least one of the following formulas (2) or (3), and n+1 R2 are independently a hydrogen atom, C 1-4 Alkyl or C 1-4 A halogenated alkyl group, wherein n is an integer from 1 to 10,

[0008]

[0009] In the above formula (2), R3 is phenylene, biphenylene, phenylene with a substituent on the benzene ring, or biphenylene with a substituent on the benzene ring;

[0010] In the above formula (3), R4 is a phenyl group, a biphenyl group, a phenyl group having a substituent on the benzene ring, or a biphenyl group having a substituent on the benzene ring.

[0011] Optionally, R4 is p-hydroxyphenyl or o-hydroxyphenyl.

[0012] Optionally, the ether alcohol has a structure of the following formula (4):

[0013]

[0014] In formula (4), R5 is a hydrogen atom, C 1-20 Alkoxy or C 1-20 The aromatic hydrocarbon group, R7 is a hydrogen atom, C 1-20 Alkyl or C 1-20 An aromatic hydrocarbon group, R6 is C 1-4 alkylene, m is an integer from 1 to 100, and m R6O groups are the same or different groups.

[0015] Optionally, R5 is a hydrogen atom, C 1-8 alkoxy, phenoxy or benzyloxy, wherein R7 is a hydrogen atom or C 1-8 R6 is a methylene group or an ethylene group, and m is an integer from 1 to 4.

[0016] Optionally, the alcohol ether is selected from one or more of ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether or diethylene glycol butyl ether.

[0017] Optionally, the alcohol ether is selected from ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol propyl ether or diethylene glycol dimethyl ether.

[0018] Optionally, the boiling point of the alcohol ether is between 140 and 165°C.

[0019] Optionally, based on 100 parts by weight of phenolic resin, the added amount of the alcohol ether is 10 to 100 parts by weight.

[0020] Optionally, a quaternary ammonium salt is added to the alcohol ether solution.

[0021] Optionally, based on 100 parts by weight of phenolic resin, the added amount of the alcohol ether is 20 to 45 parts by weight, and the added amount of the quaternary ammonium salt is 0.05 to 0.5 parts by weight.

[0022] Optionally, the quaternary ammonium salt is selected from at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

[0023] Optionally, the inorganic strong alkaline substance is sodium hydroxide or potassium hydroxide.

[0024] A phenolic epoxy resin having a structure shown in the following formula (5):

[0025]

[0026] In the above formula (5), R1 is at least one of the following formulas (2) or (3), and n+1 R2 are independently a hydrogen atom, C 1-4 Alkyl or C 1-4 A halogenated alkyl group, wherein n is an integer from 1 to 10,

[0027]

[0028] In the above formula (2), R3 is phenylene, biphenylene, phenylene with a substituent on the benzene ring, or biphenylene with a substituent on the benzene ring;

[0029] In the above formula (3), R4 is a phenyl group, a biphenyl group, a phenyl group with a substituent on the benzene ring, or a biphenyl group with a substituent on the benzene ring;

[0030] Wherein, in the phenolic epoxy resin, the total chlorine content is below 900 ppm, and the hydrolyzed chlorine content is below 60 ppm.

[0031] Optionally, in the phenolic epoxy resin, the total chlorine content is below 800 ppm, and the hydrolyzed chlorine is below 50 ppm.

[0032] Optionally, the ortho or para position of R4 has The phenyl group.

[0033] Optionally, the phenolic epoxy resin is prepared by the above-mentioned preparation method of the phenolic epoxy resin.

[0034] An epoxy resin composition comprises the above-mentioned phenolic epoxy resin.

[0035] An electronic product comprises the cured product of the epoxy resin composition described above.

[0036] The phenolic epoxy resin and the preparation method thereof according to the specific embodiment of the present invention are prepared by reacting a phenolic resin introduced with a benzene ring or a biphenyl structure and epichlorohydrin as raw materials and an inorganic strong alkaline substance as a catalyst in an alcohol ether solution to prepare the phenolic epoxy resin. By introducing the alcohol ether, the contact reaction between the phenolic resin, epichlorohydrin and the inorganic strong alkaline substance in the organic phase and the aqueous phase can be improved, the reaction rate can be increased, the reaction time can be shortened, and thus the by-products in the reaction product phenolic epoxy resin can be reduced. DETAILED DESCRIPTION

[0037] A specific embodiment of the present invention provides a method for preparing a phenolic epoxy resin, the preparation method comprising the following steps:

[0038] The phenolic resin of the following formula (1) and epichlorohydrin are used as raw materials, and an inorganic strong alkaline substance is used as a catalyst. In an alcohol ether solution, the phenolic resin and epichlorohydrin react to prepare the phenolic epoxy resin;

[0039]

[0040] In the above formula (1), R1 is at least one of the following formulas (2) or (3), and n+1 R2 are independently a hydrogen atom, C 1-4 Alkyl or C 1-4 A halogenated alkyl group, wherein n is an integer from 1 to 10,

[0041]

[0042] In the above formula (2), R3 is phenylene, biphenylene, phenylene with a substituent on the benzene ring, or biphenylene with a substituent on the benzene ring;

[0043] In the above formula (3), R4 is a phenyl group, a biphenyl group, a phenyl group having a substituent on the benzene ring, or a biphenyl group having a substituent on the benzene ring.

[0044] The inventors of the present invention have found that, due to the introduction of the benzene ring or biphenyl structure shown in formula (2) or formula (3) into the phenolic resin of formula (1), when the phenolic resin is reacted with epichlorohydrin to prepare the phenolic epoxy resin, the reaction conversion efficiency is low, the reaction time is long, and the by-products, especially the chlorine content, are increased, and the application requirements of electronic materials cannot be met. However, by adding an alcohol ether solvent to the reaction system, the contact reaction between the phenolic resin, epichlorohydrin and the inorganic strong alkaline substance in the organic phase and the aqueous phase can be improved, the reaction rate can be increased, the reaction time can be shortened, and the by-products in the reaction product phenolic epoxy resin can be reduced.

[0045] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, in formula (1), the R1 group is connected to phenol at the ortho position, and in some specific embodiments, in formula (1), the R1 group is connected to phenol at the meta position or the para position.

[0046] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, the R2 is a hydrogen atom, in some specific embodiments, the R2 is a methyl group, an ethyl group, a propyl group, a butyl group or an isobutyl group, and in some specific embodiments, the R2 is a halogenated methyl group, a halogenated ethyl group, a halogenated propyl group, a halogenated butyl group or a halogenated isobutyl group.

[0047] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, the R1 is a structure shown in formula (2), and in some specific embodiments, the R1 is a structure shown in formula (3).

[0048] In some specific embodiments of the preparation method of the phenolic epoxy resin of the present invention, the substituent is C 1-4 Alkyl, C 1-4 of halogenated alkyl, hydroxy or alkoxy groups.

[0049] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, the phenolic resin of formula (1) is a phenyl phenolic resin, a biphenyl phenolic resin and a trisphenol phenolic resin as shown in the following structure.

[0050]

[0051] In some specific embodiments of the preparation method of the phenolic epoxy resin of the present invention, in formula (3), R4 is p-hydroxyphenyl or o-hydroxyphenyl.

[0052] In some specific embodiments, the phenolic resin of formula (1) can be prepared by referring to the prior art, for example, by reacting Y-R1-Y and phenol of the following formula (6) as raw materials, wherein Y-R1-Y is a halogen atom, a hydroxyl group or a C 1-4 of alkoxy.

[0053]

[0054] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, the ether alcohol has a structure of the following formula (4):

[0055]

[0056] In formula (4), R5 is a hydrogen atom, C 1-20 Alkoxy or C 1-20 The aromatic hydrocarbon group, R7 is a hydrogen atom, C 1-20 Alkyl or C 1-20 An aromatic hydrocarbon group, R6 is C 1-4 alkylene, m is an integer from 1 to 100, and m R6O are the same or different groups. In some specific embodiments, R5 is a hydrogen atom, C 1-8 In some embodiments, R5 is phenoxy or benzyloxy, and in some embodiments, R7 is a hydrogen atom. In some embodiments, R7 is C 1-8alkyl, for example, methyl, ethyl, propyl or butoxy, etc. In some specific embodiments, R6 is methylene or ethylene, and in some specific embodiments, m is an integer of 1 to 4, that is, m is 1, 2, 3 or 4.

[0057] In the preparation method of the novolac epoxy resin of the present invention, in some specific embodiments, the alcohol ether is selected from one or more of ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether or diethylene glycol butyl ether.

[0058] In some specific embodiments, the method for preparing the phenolic epoxy resin of the present invention comprises the following steps:

[0059] an etherification step, wherein the phenolic resin of formula (1), epichlorohydrin, an inorganic strong base and an ether alcohol are reacted at a temperature of 40 to 90° C., preferably 50 to 80° C., for a reaction time of 1 to 10 hours, preferably 3 to 6 hours;

[0060] Epoxy ring closing step: add strong base, the temperature is between 40 and 90°C, further 50 to 80°C, reflux dehydration reaction under negative pressure, the reaction time is 1 to 10 hours, further 3 to 6 hours.

[0061] In some specific embodiments of the preparation method of the phenolic epoxy resin of the present invention, based on 100 parts by weight of the phenolic resin of the structure of formula (1), the amount of epichlorohydrin added is 50 to 500 parts by weight, further 100 to 300 parts by weight, and further 150 to 250 parts by weight.

[0062] The preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, based on 100 parts by weight of the phenolic resin of the structure of formula (1), the addition amount of the inorganic strong base in the etherification step and the epoxy ring closure step is 10 to 200 parts by weight, and further 50 to 100 parts by weight. In some specific embodiments, the inorganic strong base is 30 to 70wt%, and further 40 to 60wt% of an aqueous solution, which is added to the reaction by dropwise addition, and the speed of the dropwise addition can be adjusted according to the actual experimental situation. In some specific embodiments, in the etherification step, the addition amount of the inorganic strong base in the etherification step accounts for 5 to 30wt%, and the addition amount of the inorganic strong base in the epoxy ring closure step accounts for 70 to 95wt%.

[0063] In some specific embodiments of the preparation method of the phenolic epoxy resin of the present invention, based on 100 parts by weight of the phenolic resin of the structure of formula (1), the amount of the ether alcohol added is 5 to 200 parts by weight, further 10 to 100 parts by weight, and further 20 to 45 parts by weight.

[0064] The preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, further comprises the following roughing step and refining step after the epoxy ring closing step:

[0065] The rough preparation step is to remove the ether alcohol, water and epichlorohydrin in the system, dissolve the phenolic epoxy resin prepared in the epoxy ring closure step in a solvent, such as methyl ethyl ketone, methyl isobutyl ketone, etc., and then add an inorganic strong base accounting for 3-15wt% of the inorganic strong base in the etherification step and the epoxy ring closure step and a small amount of ether alcohol, and continue to react at 60-90°C for 1-3 hours.

[0066] Refining step: neutralize the residual inorganic strong base in the system and remove the solvent, etc.

[0067] In the preparation method of the phenolic epoxy resin of the present invention, since the added alcohol ether is hydrophilic, it is difficult to remove the water in the system in the epoxy ring closing step, which is easy to cause side reactions. In some specific embodiments, the boiling point of the alcohol ether is between 140 and 165° C. For example, the alcohol ether is ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol propyl ether or diethylene glycol dimethyl ether. When the boiling point of the alcohol ether is between 140 and 165° C., the influence of water in the system formed by the alcohol ether and water is relatively small, which is conducive to reducing the occurrence of side reactions.

[0068] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, a quaternary ammonium salt is added to the alcohol ether solution. After the quaternary ammonium salt is added, the amount of ether alcohol can be reduced, thereby reducing the influence of the hydrophilic effect of the ether alcohol. In some specific embodiments, based on 100 parts by weight of the phenolic resin, the amount of the alcohol ether added is 20 to 45 parts by weight, and the amount of the quaternary ammonium salt added is 0.05 to 0.5 parts by weight.

[0069] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, the quaternary ammonium salt is selected from one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.

[0070] In the preparation method of the phenolic epoxy resin of the present invention, in some specific embodiments, the inorganic strong alkaline substance is a hydroxide of an alkali metal or an alkaline earth metal, and in some specific embodiments, the inorganic strong alkaline substance is sodium hydroxide or potassium hydroxide.

[0071] The specific embodiment of the present invention further provides a phenolic epoxy resin, wherein the phenolic epoxy resin has a structure shown in the following formula (5):

[0072]

[0073] In the above formula (5), R1 is at least one of the following formulas (2) or (3), and n+1 R2 are independently a hydrogen atom, C 1-4 Alkyl or C 1-4 A halogenated alkyl group, wherein n is an integer from 1 to 10,

[0074]

[0075] In the above formula (2), R3 is phenylene, biphenylene, phenylene with a substituent on the benzene ring, or biphenylene with a substituent on the benzene ring;

[0076] In the above formula (3), R4 is a phenyl group, a biphenyl group, a phenyl group with a substituent on the benzene ring, or a biphenyl group with a substituent on the benzene ring;

[0077] Wherein, in the phenolic epoxy resin, the total chlorine content is below 900 ppm, and the hydrolyzed chlorine content is below 60 ppm.

[0078] The total chlorine content of the phenolic epoxy resin in the specific embodiment of the present invention is below 900 ppm, which can meet the requirements of electronic materials. In some specific embodiments, the total chlorine content of the phenolic epoxy resin is below 800 ppm, and the hydrolyzed chlorine is below 50 ppm.

[0079] In the phenolic epoxy resin of the specific embodiment of the present invention, in some specific embodiments, the R2 is a hydrogen atom, in some specific embodiments, the R2 is a methyl group, an ethyl group, a propyl group, a butyl group or an isobutyl group, and in some specific embodiments, the R2 is a halogenated methyl group, a halogenated ethyl group, a halogenated propyl group, a halogenated butyl group or a halogenated isobutyl group.

[0080] In the phenolic epoxy resin of the specific embodiment of the present invention, in some specific embodiments, the R1 is a structure shown in formula (2), and in some specific embodiments, the R1 is a structure shown in formula (3).

[0081] In some embodiments of the phenolic epoxy resin of the present invention, the substituent is C 1-4 Alkyl, C 1-4 The halogenated alkyl or alkoxy, etc.

[0082] In some specific embodiments of the preparation method of the phenolic epoxy resin of the present invention, in formula (3), R4 is an ortho or para position having The phenyl group.

[0083] The phenolic epoxy resin of the specific embodiment of the present invention, in some specific embodiments, is prepared by the above-mentioned preparation method of phenolic epoxy resin.

[0084] A specific embodiment of the present invention further provides an epoxy resin composition, wherein the epoxy resin composition comprises the above-mentioned phenolic epoxy resin.

[0085] The epoxy resin composition of the specific embodiment of the present invention, in some specific embodiments, the epoxy resin composition may also include other phenolic resins, such as phenol novolac resin, cresol novolac resin or trisphenol methane resin, etc. In some specific embodiments, the epoxy resin composition may also include other epoxy resins, such as o-cresol novolac epoxy resin, trisphenol methane epoxy resin, naphthol epoxy resin, naphthol aralkyl resin, etc.

[0086] The epoxy resin composition of the specific embodiment of the present invention, in some specific embodiments, the epoxy resin composition also includes a curing accelerator for curing the epoxy resin through the phenolic resin, as a curing accelerator, for example, organic phosphine compounds and boron salts thereof, tertiary amines, quaternary ammonium salts, imidazoles and tetraphenyl boron salts thereof, and the like, specifically triphenylphosphine.

[0087] The epoxy resin composition of the specific embodiment of the present invention, in some specific embodiments, further includes other components, such as inorganic fillers, other resin compositions, additives, and the like.

[0088] The specific embodiment of the present invention further provides an electronic product, which comprises the cured product of the epoxy resin composition described above. The electronic product may be, for example, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, a solid-state imaging element, and the like.

[0089] The following examples are for further illustrating the effects of the present invention, but are not limited thereto and are only for illustration and to enhance understanding.

[0090] Example

[0091] Test description:

[0092] Epoxy equivalent

[0093] Refer to GB / T 4612-2008 Determination of epoxy equivalent of plastic epoxy compounds.

[0094] Take 0.1-0.5g of the sample to be tested, add 20ml of dichloromethane, 20ml of acetic acid and 10ml of tetraethylammonium bromide (C8H20NBr) / acetic acid (HAc) solution, stir and dissolve, put it into a potentiometric titrator, select the epoxy equivalent test method, and perform titration analysis with perchloric acid solution.

[0095] Hydrolyzed chlorine content:

[0096] Refer to GB / T 4618.2-2008 Determination of chlorine content of plastic epoxy resin Part 2: Saponifiable chlorine.

[0097] Take 2.0-5.0g of the sample to be tested, add 25ml 1,4-dioxane and stir to dissolve, then add 25ml potassium hydroxide / methanol solution and heat to reflux for 10min. After cooling, rinse the residue with 25ml 1,4-dioxane, add 0.5ml glacial acetic acid, put it into a potentiometric titrator, select the hydrolysis chlorine test method, and perform titration analysis with silver nitrate solution.

[0098] Total chlorine content

[0099] Refer to GB / T 12007.3-1989 Determination method for total chlorine content of epoxy resin.

[0100] Take 2.0-3.0g of the sample to be tested, add 25ml of ethylene glycol monobutyl ether and stir to dissolve, then add 25ml of potassium hydroxide / propylene glycol solution and heat to reflux at high temperature for 60min. After cooling, use 25ml of 1,4-dioxane to rinse the residue, add 25ml of glacial acetic acid, put it into a potentiometric titrator, select the total chlorine test method, and use silver nitrate solution for titration analysis.

[0101] Example 1

[0102] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, and 80 parts of propylene glycol methyl ether were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a set temperature of 50°C and a vacuum degree of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. The unreacted epichlorohydrin / propylene glycol methyl ether in the bottle is recovered under the conditions of temperature 130° C. and pressure below 3Kpa to obtain a crude trisphenol novolac epoxy resin product, and then 300 parts of methyl isobutyl ketone are added to dissolve it, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize to pH 5.5-6.5. After multiple water washings, the methyl isobutyl ketone is removed at 170° C. and pressure below 3Kpa to obtain a trisphenol novolac epoxy resin.

[0103] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 165 g / eq, hydrolyzable chlorine = 58 ppm, total chlorine = 955 ppm.

[0104] Example 2

[0105] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, 40 parts of propylene glycol methyl ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a temperature of 50°C and a vacuum of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. hours; the unreacted epichlorohydrin / propylene glycol methyl ether in the four-necked flask is recovered under the conditions of temperature 130° C. and pressure below 3Kpa to obtain a crude trisphenol novolac epoxy resin, and then 300 parts of methyl isobutyl ketone are added to dissolve, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize to pH 5.5-6.5. After repeated water washing, the methyl isobutyl ketone is removed at 170° C. and pressure below 3Kpa to obtain a trisphenol novolac epoxy resin.

[0106] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 165 g / eq, hydrolyzable chlorine = 45 ppm, total chlorine = 784 ppm.

[0107] Example 3

[0108] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, 40 parts of ethylene glycol ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30g of 50% aqueous sodium hydroxide solution was added, and the mixture was reacted at 55°C for 3 hours. After the reaction was completed, 55 parts of 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of setting the temperature to 50°C and the vacuum degree to 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. hours; the unreacted epichlorohydrin / ethylene glycol ether in the four-necked flask is recovered at a temperature of 130° C. and a pressure of less than 3Kpa to obtain a crude trisphenol novolac epoxy resin product, and then 300 parts of methyl isobutyl ketone are added to dissolve it, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize the solution to pH 5.5-6.5, and after multiple water washings, the methyl isobutyl ketone is removed at 170° C. and a pressure of less than 3Kpa to obtain a trisphenol novolac epoxy resin.

[0109] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 165 g / eq, hydrolyzable chlorine = 39 ppm, total chlorine = 721 ppm.

[0110] Example 4

[0111] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, 40 parts of ethylene glycol propyl ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a temperature of 50°C and a vacuum of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. hours; the unreacted epichlorohydrin / ethylene glycol propyl ether in the four-necked flask is recovered at a temperature of 130° C. and a pressure of less than 3Kpa to obtain a crude trisphenol novolac epoxy resin product, and then 300 parts of methyl isobutyl ketone are added to dissolve it, 3.5 parts of a 50wt.% aqueous solution of NaOH and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize the solution to pH 5.5-6.5, and after multiple water washings, the methyl isobutyl ketone is removed at 170° C. and a pressure of less than 3Kpa to obtain a trisphenol novolac epoxy resin.

[0112] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 165 g / eq, hydrolyzable chlorine = 35 ppm, total chlorine = 698 ppm.

[0113] Example 5

[0114] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, 40 parts of diethylene glycol dimethyl ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a temperature of 50°C and a vacuum of 10KPa. After the addition was completed, the mixture was refluxed for dehydration. 1 hour; unreacted epichlorohydrin / propylene glycol methyl ether in the four-necked flask is recovered under the conditions of temperature 130°C and pressure below 3Kpa to obtain a crude product of trisphenol novolac epoxy resin, and then 300 parts of methyl isobutyl ketone are added to dissolve, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80°C for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize to pH 5.5-6.5, and after repeated water washing, the methyl isobutyl ketone is removed at 170°C and the pressure is below 3Kpa to obtain trisphenol novolac epoxy resin.

[0115] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 165 g / eq, hydrolyzable chlorine = 35 ppm, total chlorine = 705 ppm.

[0116] Example 6

[0117] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, 40 parts of ethylene glycol phenyl ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a temperature of 50°C and a vacuum of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. hours; the unreacted epichlorohydrin / ethylene glycol phenyl ether in the four-necked flask is recovered under the conditions of temperature 130° C. and pressure below 3Kpa to obtain a crude trisphenol novolac epoxy resin product, and then 300 parts of methyl isobutyl ketone are added to dissolve it, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize to pH 5.5-6.5. After multiple water washings, the methyl isobutyl ketone is removed at 170° C. and pressure below 3Kpa to obtain a trisphenol novolac epoxy resin.

[0118] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 165 g / eq, hydrolyzable chlorine = 65 ppm, total chlorine = 805 ppm.

[0119] Example 7

[0120] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of biphenyl phenolic resin (softening point 75°C, hydroxyl equivalent 210g / eq), 150 parts of epichlorohydrin, 25 parts of ethylene glycol propyl ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 10 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 35 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a temperature of 50°C and a vacuum of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. hours; the unreacted epichlorohydrin / ethylene glycol propyl ether in the four-necked flask was recovered at a temperature of 130° C. and a pressure of less than 3Kpa to obtain a crude biphenyl phenolic epoxy resin, and then 300 parts of methyl isobutyl ketone were added to dissolve, 3 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol were added, and the reaction was carried out at 80° C. for 2 hours; 100 parts of pure water were added, and 2wt.% of sodium hydrogen phosphate was added to neutralize the solution to pH 5.5-6.5, and after repeated water washing, the methyl isobutyl ketone was removed at 170° C. and a pressure of less than 3Kpa to obtain a biphenyl phenolic epoxy resin.

[0121] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the biphenyl novolac epoxy resin were tested: epoxy equivalent = 278 g / eq, hydrolyzable chlorine = 35 ppm, total chlorine = 605 ppm.

[0122] Example 8

[0123] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of biphenyl phenolic resin (softening point 75°C, hydroxyl equivalent 210g / eq), 150 parts of epichlorohydrin, 25 parts of diethylene glycol dimethyl ether, and 0.1 parts of tetrabutylammonium chloride were added, and stirred at 50°C to completely dissolve. Under stirring, 10 parts of a 50% aqueous sodium hydroxide solution were added, and the reaction was carried out at a temperature of 55°C for 3 hours. After the reaction was completed, 35 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a set temperature of 50°C and a vacuum degree of 10KPa. After the addition was completed, the mixture was refluxed for dehydration and reacted for 1 hour. The unreacted epichlorohydrin / diethylene glycol dimethyl ether in the four-necked flask was recovered at a temperature of 130°C and a pressure of 3Kpa or less to obtain a crude biphenyl phenolic epoxy resin, and then 300 parts of methyl isobutyl ketone were added to dissolve, 3 parts of a 50wt.% aqueous solution of NaOH, 2 parts of polyethylene glycol were added, and the reaction was carried out at 80°C for 2 hours; 100 parts of pure water were added, 2wt.% of sodium hydrogen phosphate was added to neutralize the solution to pH 5.5-6.5, and after repeated washing at 170°C and a pressure of 3Kpa↓, the methyl isobutyl ketone was removed to obtain a biphenyl phenolic epoxy resin.

[0124] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the biphenyl novolac epoxy resin were tested: epoxy equivalent = 277 g / eq, hydrolyzable chlorine = 26 ppm, total chlorine = 580 ppm.

[0125] Example 9

[0126] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of biphenyl phenol formaldehyde (softening point 75°C, hydroxyl equivalent 210g / eq), 150 parts of epichlorohydrin, 25 parts of ethylene glycol ethyl ether, and 0.1 parts of tetrabutylammonium bromide were added, and stirred at 50°C to completely dissolve. Under stirring, 10 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 35 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a set temperature of 50°C and a vacuum degree of 10KPa. After the addition was completed, the mixture was refluxed for dehydration and reacted for 1 hour. ; The unreacted epichlorohydrin / ethylene glycol ether in the four-necked flask is recovered at a temperature of 130° C. and a pressure of less than 3Kpa to obtain a crude biphenyl phenolic epoxy resin, and then 300 parts of methyl isobutyl ketone are added to dissolve it, 3 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize the solution to pH 5.5-6.5, and after multiple water washings, the methyl isobutyl ketone is removed at 170° C. and a pressure of 3Kpa↓ to obtain a biphenyl phenolic epoxy resin.

[0127] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the biphenyl novolac epoxy resin were tested: epoxy equivalent = 279 g / eq, hydrolyzable chlorine = 29 ppm, total chlorine = 612 ppm.

[0128] Example 10

[0129] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of phenylphenol (softening point 70°C, hydroxyl equivalent 165g / eq), 200 parts of epichlorohydrin, 30 parts of ethylene glycol propyl ether, and 0.1 parts of benzyltriethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 10 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 45 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a set temperature of 50°C and a vacuum degree of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. The unreacted epichlorohydrin / ethylene glycol propyl ether in the four-necked flask was recovered at a temperature of 130°C and a pressure of less than 3Kpa to obtain a crude phenyl phenolic epoxy resin, and then 300 parts of methyl isobutyl ketone were added to dissolve it, 3 parts of a 50wt.% aqueous solution of NaOH and 2 parts of polyethylene glycol were added, and the reaction was carried out at 80°C for 2 hours; 100 parts of pure water were added, and 2wt.% of sodium hydrogen phosphate was added to neutralize the solution to pH 5.5-6.5, and after repeated water washing, the methyl isobutyl ketone was removed at 170°C and a pressure of less than 3Kpa to obtain a phenyl phenolic epoxy resin.

[0130] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the phenyl novolac epoxy resin were tested: epoxy equivalent = 232 g / eq, hydrolyzable chlorine = 46 ppm, total chlorine = 765 ppm.

[0131] Embodiment 11

[0132] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of phenyl phenolic resin (softening point 70°C, hydroxyl equivalent 165g / eq), 200 parts of epichlorohydrin, 30 parts of diethylene glycol dimethyl ether, and 0.1 parts of dodecyltrimethylammonium chloride were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 10 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 55°C for 3 hours. After the reaction was completed, 45 parts of a 50% aqueous sodium hydroxide solution were added continuously for 3 hours under the conditions of a set temperature of 50°C and a vacuum of 10KPa. After the addition was completed, the mixture was refluxed for dehydration. 1 hour; unreacted epichlorohydrin / diethylene glycol dimethyl ether in the four-necked flask is recovered under the conditions of temperature 130°C and pressure below 3Kpa to obtain a crude phenyl phenolic epoxy resin, and then 300 parts of methyl isobutyl ketone are added to dissolve, 3 parts of 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80°C for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize to pH 5.5-6.5, and after multiple water washings, methyl isobutyl ketone is removed at 170°C and pressure below 3Kpa to obtain a phenyl phenolic epoxy resin.

[0133] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the phenyl novolac epoxy resin were tested: epoxy equivalent = 233 g / eq, hydrolyzable chlorine = 43 ppm, total chlorine = 750 ppm.

[0134] Comparative Example 1

[0135] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq) and 250 parts of epichlorohydrin were added, and the mixture was completely dissolved by stirring at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at a temperature of 64°C for 4 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 4 hours under the conditions of a set temperature of 60°C and a vacuum degree of 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. The four-necked flask was placed in a vacuum flask. The unreacted epichlorohydrin is recovered under the conditions of temperature of 130° C. and pressure below 3Kpa to obtain a crude trisphenol novolac epoxy resin, and then 300 parts of methyl isobutyl ketone is added to dissolve it, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize to pH 5.5-6.5. After multiple water washings, the methyl isobutyl ketone is removed at 170° C. and pressure below 3Kpa to obtain a trisphenol novolac epoxy resin.

[0136] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 169 g / eq, hydrolyzable chlorine = 105 ppm, total chlorine = 1538 ppm.

[0137] Comparative Example 2

[0138] In a four-necked flask equipped with a stirrer, a temperature probe and a condenser, 100 parts of trisphenol-formaldehyde resin (softening point 100°C, hydroxyl equivalent 100g / eq), 250 parts of epichlorohydrin, and 80 parts of methyl isobutyl ketone were added, and the mixture was completely dissolved at 50°C. Under stirring, 30 parts of a 50% aqueous sodium hydroxide solution were added, and the mixture was reacted at 60°C for 4 hours. After the reaction was completed, 55 parts of a 50% aqueous sodium hydroxide solution were added continuously for 4 hours under the conditions of setting the temperature to 50°C and the vacuum degree to 10KPa. After the addition was completed, the mixture was refluxed for dehydration for 1 hour. The unreacted epichlorohydrin / methyl isobutyl ketone in the bottle is recovered at a temperature of 130° C. and a pressure of less than 3Kpa to obtain a crude trisphenol novolac epoxy resin product, and then 300 parts of methyl isobutyl ketone are added to dissolve it, 3.5 parts of a 50wt.% NaOH aqueous solution and 2 parts of polyethylene glycol are added, and the reaction is carried out at 80° C. for 2 hours; 100 parts of pure water are added, and 2wt.% of sodium hydrogen phosphate is added to neutralize the solution to pH 5.5-6.5. After multiple water washings, the methyl isobutyl ketone is removed at 170° C. and a pressure of less than 3Kpa to obtain a trisphenol novolac epoxy resin.

[0139] The epoxy equivalent, hydrolyzable chlorine and total chlorine of the trisphenol novolac epoxy resin were tested: epoxy equivalent = 166 g / eq, hydrolyzable chlorine = 75 ppm, total chlorine = 1080 ppm.

[0140] It can be seen from the test results of the above embodiment 1 and comparative examples 1 to 2 that the alcohol ether compound of propylene glycol methyl ether can effectively shorten the reaction time and reduce the content of by-product hydrolysis chlorine and total chlorine in the preparation of trisphenol novolac epoxy resin with the same epoxy equivalent. In particular, as in embodiments 2 to 11, when a quaternary ammonium salt is added, the amount of alcohol ether can be reduced. The total chlorine content of the novolac epoxy resin in the embodiment can be reduced to below 900ppm, which meets the requirements of electronic materials. In particular, when the alcohol ether is ethylene glycol ethyl ether, ethylene glycol propyl ether and diethylene glycol dimethyl ether with a boiling point between 140 and 165°C, the effect is better. The total chlorine content of the novolac epoxy resin in the embodiment can be reduced to 800ppm, or even below 700ppm.

[0141] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.

Claims

1. A method for preparing a phenolic epoxy resin, characterized in that: The following steps are involved: The phenolic resin of the following formula (1) and epichlorohydrin are used as raw materials, and an inorganic strong alkaline substance is used as a catalyst. In an alcohol ether solution, the phenolic resin and epichlorohydrin react to prepare the phenolic epoxy resin; In the above formula (1), R1 is at least one of the following formulas (2) or (3), and n+1 R2 are independently a hydrogen atom, C 1-4 Alkyl or C 1-4 A halogenated alkyl group, wherein n is an integer from 1 to 10, In the above formula (2), R3 is phenylene or biphenylene; In the above formula (3), R4 is phenyl or biphenyl; A quaternary ammonium salt is added to the alcohol ether solution; The alcohol ether is selected from one or more of ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether or diethylene glycol butyl ether; Based on 100 parts by weight of phenolic resin, the added amount of the alcohol ether is 20 to 45 parts by weight, and the added amount of the quaternary ammonium salt is 0.05 to 0.1 parts by weight.

2. The method for preparing a novolac epoxy resin according to claim 1, wherein The R4 is p-hydroxyphenyl or o-hydroxyphenyl.

3. The method for preparing a novolac epoxy resin according to claim 1, wherein The alcohol ether is selected from ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol propyl ether or diethylene glycol dimethyl ether.

4. The method for preparing a novolac epoxy resin according to claim 1, wherein: The boiling point of the alcohol ether is between 140 and 165°C.

5. The method for preparing a novolac epoxy resin according to claim 1, wherein: The quaternary ammonium salt is selected from at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.

6. The method for preparing a novolac epoxy resin according to claim 1, characterized in that: The inorganic strong alkaline substance is sodium hydroxide or potassium hydroxide.

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