Enhanced electronic grade phenol formaldehyde resin with heat resistance and preparation method thereof

Abstract

The application discloses a reinforced electronic-grade phenolic resin with heat resistance and a preparation method thereof, and belongs to the field of electronic-grade phenolic resin. The preparation method comprises the following steps: phenol and formaldehyde are mixed according to a weight ratio of 2.55-2.85:10, then the pH is adjusted by acetic acid, and the mixture is heated to 95-130 DEG C and reacted for 3-4 hours; then 3-mercapto propyl (dimethoxy) silane is added, and the mixture is heated to 150-160 DEG C and reacted for 1-2 hours to obtain mercapto phenolic resin; the mercapto phenolic resin, modified polyether amine, modified silicon dioxide and azobis isobutyronitrile are reacted at 90-120 DEG C according to a weight ratio of 40-60:4.5-5.5:2.5-4.5:0.07-0.2 for 8-12 hours to obtain the reinforced electronic-grade phenolic resin. The prepared reinforced electronic-grade phenolic resin with heat resistance has good flame retardance, insulation and heat resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electronic grade phenolic resin, and particularly relates to a reinforced electronic grade phenolic resin with heat resistance and a preparation method thereof. BACKGROUND

[0002] As a classic product in the field of high polymer materials, phenolic resin is generally a high polymer material prepared by dehydration condensation of phenol and formaldehyde under heated acidic or basic conditions. As an important member of the phenolic resin family, electronic grade phenolic resin has higher requirements in purity, electrical insulation, etc. in addition to the remarkable characteristics of ordinary phenolic resin, such as low price, heat resistance, ablation resistance, flame resistance, and low smoke generation during combustion. The low price of electronic grade phenolic resin provides a cost advantage in large-scale electronic material production; its excellent heat resistance meets the stable working requirements of electronic components in a high temperature environment; its good flame resistance and low smoke generation play an important role in the safety of electronic equipment.

[0003] Phenolic resin exhibits excellent compatibility with various organic / inorganic fillers due to its unique molecular structure, which makes it an important technical path to form high-performance composites by compounding with functional materials during modification. This compatibility advantage provides a wide space for precise control of material performance, and specific functional filler components can be introduced according to different application scenarios. However, the deficiencies of electronic grade phenolic resin produced by existing technologies in heat resistance, flame resistance, and insulation performance have become increasingly prominent, which has become a key problem restricting the reliability and service life of high-end electronic devices.

[0004] Patent CN 102181026A discloses a production method of electronic grade phenolic resin, which is prepared by adding formaldehyde aqueous solution in batches for reaction, and then through water washing, vacuum dehydration, distillation, vacuum dehydration again, and finally refining treatment, to obtain high-purity electronic grade phenolic resin. Although the electronic grade phenolic resin prepared by the present application has good electrical properties, the electronic grade phenolic resin prepared may have problems such as insufficient heat resistance and flame resistance.

[0005] Therefore, it is an important problem to be solved in the field to provide a reinforced electronic grade phenolic resin with good heat resistance, insulation, and flame resistance. SUMMARY

[0006] To solve the problems in the prior art, the present application provides a reinforced electronic grade phenolic resin with heat resistance and a preparation method thereof. Specifically, the technical scheme of the present application includes the following contents.

[0007] A preparation method of a reinforced electronic grade phenolic resin with heat resistance, the preparation method comprising the following steps:

[0008] phenol and formaldehyde are mixed in a weight ratio of 2.55-2.85:10, then the pH is adjusted with acetic acid, and then the mixture is heated to 95-130°C and reacted for 3-4 hours, then 3-mercaptopropyl(dimethoxy)silane is added, and the mixture is heated to 150-160°C and reacted for 1-2 hours to obtain the mercaptanized phenolic resin;

[0009] The mercaptanized phenolic resin, the modified polyether amine, the modified silica, and the azobisisobutyronitrile are reacted in a weight ratio of 40-60:4.5-5.5:2.5-4.5:0.07-0.2 at 90-120°C for 8-12 hours to obtain the enhanced electronic-grade phenolic resin.

[0010] Further, the preparation method of the modified polyether amine comprises the following steps:

[0011] Phosphorus oxychloride and hydroxyethyl acrylate are reacted in a weight ratio of 1.5-2.1:1.3-1.9 to obtain an intermediate;

[0012] The intermediate, polyether amine D230, 4-dimethylaminopyridine, and triethylamine are reacted in a weight ratio of 1.4-1.9:0.5-0.7:0.08-0.1:0.5-1.5 to obtain the modified polyether amine.

[0013] Further, the reaction conditions of the phosphorus oxychloride and the hydroxyethyl acrylate comprise reacting at 0-4°C for 3-4 hours, and then heating to 23-25°C and stirring for 8-12 hours.

[0014] Further, the reaction conditions of the intermediate, the polyether amine D230, the 4-dimethylaminopyridine, and the triethylamine comprise reacting at 0-4°C for 3-5 hours, and then heating to 23-25°C and stirring for 16-18 hours.

[0015] Further, the preparation method of the modified silica comprises the following steps:

[0016] γ-glycidoxypropyltrimethoxysilane, p-aminobenzenesulfonic acid, and triethylamine are reacted in a weight ratio of 2.2-2.8:1.2-1.5:0.002-0.008 to obtain an intermediate A;

[0017] The intermediate A, benzyl chloride, and potassium carbonate are reacted in a weight ratio of 3-4:1.2-1.7:0.9-1.2 to obtain an intermediate B;

[0018] The intermediate B, methacryloyl chloride, and triethylamine are reacted in a weight ratio of 4-5:0.9-1.2:1.2-1.5 to obtain an intermediate C;

[0019] Nano-silica and the intermediate C are reacted in a weight ratio of 10-15:2-5 to obtain the modified silica.

[0020] Further, the reaction conditions of the gamma-glycidyl ether propyltrimethoxysilane and p-aminobenzenesulfonic acid include a reaction temperature of 80-100 DEG C and a reaction time of 4-6h.

[0021] Further, the reaction conditions of the intermediate A, benzyl chloride and potassium carbonate include a reaction temperature of 70-90 DEG C and a reaction time of 8-12h.

[0022] Further, the reaction conditions of the intermediate B, methacryloyl chloride and triethylamine include a reaction temperature of 40-60 DEG C and a reaction time of 5-7h.

[0023] Further, the reaction conditions of the nanosilica and the intermediate C include a reaction temperature of 60-80 DEG C and a reaction time of 12-18h.

[0024] Further, the acetic acid is a 5% acetic acid solution by mass fraction.

[0025] Further, the acetic acid adjusts the pH value to 1-2.

[0026] Further, the amount of the 3-mercaptopropyl (dimethoxy) silane is 10% of the total weight of the phenol and formaldehyde.

[0027] Further, the modified silica is uniformly dispersed in the resin matrix, and strong interface bonding is generated with the resin matrix through chemical bonding, effectively bearing and dispersing stress as a rigid reinforcing point to prevent crack propagation; the long-chain polyether segment in the modified polyether amine is inserted into the rigid network as a flexible component, which can deform to absorb energy when stressed, effectively toughening and avoiding excessive brittleness of the material due to increased strength; the ingenious combination of "rigid particle reinforcement" and "flexible chain segment toughening" realizes uniform dispersion and strong interface adhesion through covalent crosslinking network, improving the tensile properties of the reinforced electronic-grade phenolic resin.

[0028] Compared with the prior art, the beneficial effects of the present application are as follows:

[0029] (1) The chlorine atom of the phosphorus oxychloride and the hydroxyl group of the hydroxyethyl acrylate in the application are reacted by phosphorus esterification to obtain an intermediate, the chlorine atom of the intermediate and the amino group of the polyether amine D23 are reacted by phosphoric acid to obtain a modified polyether amine; the epoxy group of the gamma-glycidyloxypropyl trimethoxysilane and the amino group of the p-aminobenzenesulfonic acid are reacted to obtain an intermediate A, the sulfonic acid group in the intermediate A and the chlorine atom in the benzyl chloride are reacted to obtain an intermediate B, the hydroxyl group in the intermediate B and the acyl chloride in the methacryloyl chloride are reacted by esterification to obtain an intermediate C, and the intermediate C and the silicon hydroxyl group on the surface of the nano silicon dioxide are reacted to obtain modified silicon dioxide; the acrylate groups in the modified polyether amine and the acrylate groups in the modified silicon dioxide can be crosslinked with the mercapto groups in the mercapto-phenolic resin to obtain an electronic grade phenolic resin, a three-dimensional crosslinked network structure is formed, and the heat resistance and tensile strength of the electronic grade phenolic resin are improved.

[0030] (2) In the application, a dense three-dimensional network is formed to limit the movement of molecular chains at high temperatures; the modified silicon dioxide acts as a high-thermal-stability nanoparticle, is uniformly dispersed, and plays a physical reinforcing and heat-insulating role; the phosphorus in the modified polyether amine and the silicon in the modified silicon dioxide synergistically promote the formation of a stable and dense silicon-phosphorus-carbon composite carbon layer, effectively insulate heat and oxygen, delay decomposition, and improve the carbon residue rate; chemical bonding helps to improve the compatibility of the nano silicon dioxide and the modified phenolic resin, improve the heat resistance and tensile properties thereof, and prevent molecular migration and exudation.

[0031] (3) In the application, the uniformly dispersed nano silicon dioxide particles can hinder the migration path of charges in the material, thereby improving the insulation strength; in addition, the high-crosslinking-density three-dimensional network structure greatly reduces the free volume and ion migration channels in the material, limits the mobility of charge carriers, and further improves the insulation performance of the reinforced electronic grade phenolic resin; the phosphorus, nitrogen, sulfur, and silicon multiple flame-retardant elements coexist in the same system in the application, and synergistically act through multiple mechanisms such as condensed phase and gas phase, thereby significantly improving the flame-retardant performance of the reinforced electronic grade phenolic resin. DETAILED DESCRIPTION

[0032] The technical solutions of the application will be clearly and completely described below through embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0033] Unless otherwise specified, the raw materials and reagents used in the application below are commercially available or can be prepared by known methods.

[0034] Preparation Example 1:

[0035] The preparation method of the modified polyether amine comprises the following steps:

[0036] 1.5 parts by weight of phosphorus oxychloride were added to a flask, 1.3 parts by weight of hydroxyethyl acrylate were added under a nitrogen atmosphere, after stirring at 0°C for 3 h, the temperature was raised to 23°C and stirring was continued for 8 h, after the reaction was completed, the intermediate was obtained by distillation under reduced pressure;

[0037] 1.4 parts by weight of the intermediate were dispersed in 50 parts by weight of acetone, 0.5 parts by weight of polyetheramine D230, 0.08 parts by weight of 4-dimethylaminopyridine and 0.5 parts by weight of triethylamine were added under a nitrogen atmosphere, after stirring at 0°C for 3 h, the temperature was raised to 23°C and stirring was continued for 16 h, after the reaction was completed, the product was collected by filtration and the modified polyetheramine was obtained by distillation under reduced pressure.

[0038] Preparation Example 2:

[0039] The method for preparing the modified polyetheramine comprises the following steps:

[0040] 1.5 parts by weight of phosphorus oxychloride were added to a flask, 1.3 parts by weight of hydroxyethyl acrylate were added under a nitrogen atmosphere, after stirring at 0°C for 3 h, the temperature was raised to 23°C and stirring was continued for 8 h, after the reaction was completed, the intermediate was obtained by distillation under reduced pressure;

[0041] 1.5 parts by weight of the intermediate were dispersed in 50 parts by weight of acetone, 0.5 parts by weight of polyetheramine D230, 0.08 parts by weight of 4-dimethylaminopyridine and 0.5 parts by weight of triethylamine were added under a nitrogen atmosphere, after stirring at 0°C for 3 h, the temperature was raised to 23°C and stirring was continued for 16 h, after the reaction was completed, the product was collected by filtration and the modified polyetheramine was obtained by distillation under reduced pressure.

[0042] Preparation Example 3:

[0043] The method for preparing the modified polyetheramine comprises the following steps:

[0044] 1.5 parts by weight of phosphorus oxychloride were added to a flask, 1.3 parts by weight of hydroxyethyl acrylate were added under a nitrogen atmosphere, after stirring at 0°C for 3 h, the temperature was raised to 23°C and stirring was continued for 8 h, after the reaction was completed, the intermediate was obtained by distillation under reduced pressure;

[0045] 1.5 parts by weight of the intermediate were dispersed in 50 parts by weight of acetone, 0.5 parts by weight of polyetheramine D230, 0.08 parts by weight of 4-dimethylaminopyridine and 0.5 parts by weight of triethylamine were added under a nitrogen atmosphere, after stirring at 0°C for 3 h, the temperature was raised to 23°C and stirring was continued for 16 h, after the reaction was completed, the product was collected by filtration and the modified polyetheramine was obtained by distillation under reduced pressure.

[0046] Preparation Example 4:

[0047] The method for preparing the modified polyetheramine comprises the following steps:

[0048] 1.9 parts by weight of phosphorus oxychloride were added to a flask, 1.8 parts by weight of hydroxyethyl acrylate were added under a nitrogen atmosphere, after stirring at 3°C for 3.7 h, the temperature was raised to 23°C and stirring was continued for 10 h, after the reaction was completed, the intermediate was obtained by distillation under reduced pressure;

[0049] 1.8 parts by weight of the intermediate were dispersed in 50 parts by weight of acetone, 0.65 parts by weight of polyetheramine D230, 0.095 parts by weight of 4-dimethylaminopyridine and 1.2 parts by weight of triethylamine were added under a nitrogen atmosphere, after stirring at 3°C for 4.5 h, the temperature was raised to 23°C and stirring was continued for 17.5 h, after the reaction was completed, the product was collected by filtration and the modified polyetheramine was obtained by distillation under reduced pressure.

[0050] Preparation Example 5:

[0051] The method for preparing the modified polyetheramine comprises the following steps:

[0052] 1.9 parts by weight of phosphorus oxychloride were added to a flask, 1.9 parts by weight of hydroxyethyl acrylate were added under a nitrogen atmosphere, after stirring at 4°C for 4 h, the temperature was raised to 25°C and stirring was continued for 12 h, after the reaction was completed, the intermediate was obtained by distillation under reduced pressure;

[0053] 1.9 parts by weight of the intermediate were dispersed in 50 parts by weight of acetone, 0.7 parts by weight of polyetheramine D230, 0.1 parts by weight of 4-dimethylaminopyridine and 1.5 parts by weight of triethylamine were added under a nitrogen atmosphere, after stirring at 4°C for 5 h, the temperature was raised to 25°C and stirring was continued for 18 h, after the reaction was completed, the product was collected by filtration and the modified polyetheramine was obtained by distillation under reduced pressure.

[0054] Preparation Example 6:

[0055] The method for preparing the modified polyetheramine comprises the following steps:

[0056] 1.9 parts by weight of phosphorus oxychloride were added to a flask, 1.9 parts by weight of hydroxyethyl acrylate were added under a nitrogen atmosphere, after stirring at 4°C for 4 h, the temperature was raised to 25°C and stirring was continued for 12 h, after the reaction was completed, the intermediate was obtained by distillation under reduced pressure;

[0057] Preparation Example 7:

[0058] The method for preparing the modified silica comprises the following steps:

[0059] In a nitrogen environment, 2.2 parts by weight of γ-glycidoxypropyltrimethoxysilane and 1.2 parts by weight of p-aminobenzenesulfonic acid were dispersed in 10 parts by weight of dimethyl sulfoxide, and the mixture was stirred at 80°C for 4 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixture of acetonitrile and n-hexane at a volume ratio of 1:1) to obtain the intermediate A.

[0060] 3 parts by weight of the intermediate, 1.2 parts by weight of benzyl chloride, and 0.9 parts by weight of potassium carbonate were dispersed in 50 parts by weight of tetrahydrofuran, and the mixture was stirred at 70°C for 8 hours in a nitrogen environment. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixture of ethyl acetate and n-hexane at a volume ratio of 1:2) to obtain the intermediate B.

[0061] 4 parts by weight of the intermediate B, 0.9 parts by weight of methacryloyl chloride, and 1.2 parts by weight of triethylamine were dispersed in 100 parts by weight of dichloromethane, and the mixture was stirred at 40°C for 5 hours in a nitrogen environment. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixture of dichloromethane and methanol at a volume ratio of 9:1) to obtain the intermediate C.

[0062] 10 parts by weight of nanosilica were dispersed in 100 parts by weight of anhydrous ethanol, and ultrasonic dispersion was performed for 30 minutes. Then, 2 parts by weight of the intermediate C were added, and the mixture was stirred at 60°C for 12 hours. After the reaction was completed, the precipitate was separated by centrifugation, and then vacuum dried and ground into a powder to obtain the modified silica.

[0063] Preparation Example 8:

[0064] A method for preparing the modified silica includes the following steps:

[0065] In a nitrogen environment, 2.3 parts by weight of γ-glycidoxypropyltrimethoxysilane and 1.3 parts by weight of p-aminobenzenesulfonic acid were dispersed in 10 parts by weight of dimethyl sulfoxide, and the mixture was stirred at 85°C for 4.5 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixture of acetonitrile and n-hexane at a volume ratio of 1:1) to obtain the intermediate A.

[0066] 3.2 parts by weight of the intermediate, 1.3 parts by weight of benzyl chloride, and 1.0 parts by weight of potassium carbonate were dispersed in 50 parts by weight of tetrahydrofuran, and the mixture was stirred at 75°C for 9 hours in a nitrogen environment. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixture of ethyl acetate and n-hexane at a volume ratio of 1:2) to obtain the intermediate B.

[0067] 4.2 parts by weight of intermediate B, 1.0 parts by weight of methacryloyl chloride and 1.3 parts by weight of triethylamine were dispersed in 100 parts by weight of dichloromethane. The mixture was heated to 45°C and stirred for 5.5 h under nitrogen protection. After the reaction was completed, the solvent was removed by vacuum distillation and purified by column chromatography (the eluent was a mixed solvent of dichloromethane and methanol in a volume ratio of 9:1) to obtain intermediate C.

[0068] 11 parts by weight of nano-silica were dispersed in 100 parts by weight of anhydrous ethanol and ultrasonically dispersed for 30 min. Then, 3 parts by weight of intermediate C were added, and the mixture was heated to 65°C and stirred for 13 h. After the reaction was completed, the precipitate was obtained by centrifugation, and then the precipitate was dried under vacuum and ground into powder to obtain modified silica.

[0069] Preparation Example 9:

[0070] The method for preparing modified silica includes the following steps:

[0071] Under nitrogen protection, 2.4 parts by weight of γ-glycidyl oxypropyltrimethoxysilane and 1.4 parts by weight of p-aminobenzenesulfonic acid were dispersed in 10 parts by weight of dimethyl sulfoxide. The mixture was heated to 90°C and stirred for 5 hours. After the reaction was completed, the solvent was removed by vacuum distillation and purified by column chromatography (the eluent was a mixed solvent of acetonitrile and n-hexane in a volume ratio of 1:1) to obtain intermediate A.

[0072] 3.5 parts by weight of intermediate, 1.4 parts by weight of benzyl chloride and 1.0 parts by weight of potassium carbonate were dispersed in 50 parts by weight of tetrahydrofuran. The mixture was heated to 80°C and stirred for 10 h under nitrogen protection. After the reaction was completed, part of the solvent was removed by vacuum distillation and purified by column chromatography (the eluent was a mixed solvent of ethyl acetate and n-hexane in a volume ratio of 1:2) to obtain intermediate B.

[0073] 4.4 parts by weight of intermediate B, 1.0 parts by weight of methacryloyl chloride and 1.4 parts by weight of triethylamine were dispersed in 100 parts by weight of dichloromethane. The mixture was heated to 50°C and stirred for 6 hours under nitrogen protection. After the reaction was completed, the solvent was removed by vacuum distillation and purified by column chromatography (the eluent was a mixed solvent of dichloromethane and methanol in a volume ratio of 9:1) to obtain intermediate C.

[0074] 13 parts by weight of nano-silica were dispersed in 100 parts by weight of anhydrous ethanol and ultrasonically dispersed for 30 min. Then, 3 parts by weight of intermediate C were added, and the mixture was heated to 70°C and stirred for 15 h. After the reaction was completed, the precipitate was obtained by centrifugation, and then the precipitate was dried under vacuum and ground into powder to obtain modified silica.

[0075] Preparation Example 10:

[0076] The method for preparing modified silica includes the following steps:

[0077] In a nitrogen environment, 2.6 parts by weight of γ-glycidoxypropyltrimethoxysilane and 1.4 parts by weight of p-aminobenzenesulfonic acid were dispersed in 10 parts by weight of dimethyl sulfoxide, and the mixture was stirred at 95°C for 5.5 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the intermediate was purified by column chromatography (eluent: a mixture of acetonitrile and n-hexane at a volume ratio of 1:1) to obtain intermediate A.

[0078] 3.7 parts by weight of the intermediate, 1.6 parts by weight of benzyl chloride, and 1.1 parts by weight of potassium carbonate were dispersed in 50 parts by weight of tetrahydrofuran, and the mixture was stirred at 85°C for 11 hours in a nitrogen environment. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and the intermediate was purified by column chromatography (eluent: a mixture of ethyl acetate and n-hexane at a volume ratio of 1:2) to obtain intermediate B.

[0079] 4.7 parts by weight of intermediate B, 1.1 parts by weight of methacryloyl chloride, and 1.4 parts by weight of triethylamine were dispersed in 100 parts by weight of dichloromethane, and the mixture was stirred at 55°C for 6.5 hours in a nitrogen environment. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the intermediate was purified by column chromatography (eluent: a mixture of dichloromethane and methanol at a volume ratio of 9:1) to obtain intermediate C.

[0080] 14 parts by weight of nanosilica were dispersed in 100 parts by weight of anhydrous ethanol, and the mixture was ultrasonically dispersed for 30 minutes. Then, 4 parts by weight of intermediate C was added, and the mixture was stirred at 75°C for 16 hours. After the reaction was completed, the precipitate was separated by centrifugation, and then dried in a vacuum to obtain a modified silica.

[0081] Preparation Example 11:

[0082] A method for preparing a modified silica includes the following steps:

[0083] In a nitrogen environment, 2.8 parts by weight of γ-glycidoxypropyltrimethoxysilane and 1.5 parts by weight of p-aminobenzenesulfonic acid were dispersed in 10 parts by weight of dimethyl sulfoxide, and the mixture was stirred at 100°C for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the intermediate was purified by column chromatography (eluent: a mixture of acetonitrile and n-hexane at a volume ratio of 1:1) to obtain intermediate A.

[0084] 4 parts by weight of intermediate A, 1.7 parts by weight of benzyl chloride, and 1.2 parts by weight of potassium carbonate were dispersed in 50 parts by weight of tetrahydrofuran, and the mixture was stirred at 90°C for 12 hours in a nitrogen environment. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and the intermediate was purified by column chromatography (eluent: a mixture of ethyl acetate and n-hexane at a volume ratio of 1:2) to obtain intermediate B.

[0085] 5 parts by weight of the intermediate B, 1.2 parts by weight of methacryloyl chloride and 1.5 parts by weight of triethylamine were dispersed in 100 parts by weight of dichloromethane, and the reaction was stirred at 60°C for 7 hours in a nitrogen environment. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixed solvent of dichloromethane and methanol, volume ratio 9:1) to obtain the intermediate C.

[0086] 15 parts by weight of nanometer-sized silicon dioxide were dispersed in 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 30 minutes, 5 parts by weight of the intermediate C was then added, and the reaction was stirred at 80°C for 18 hours. After the reaction was completed, the precipitate was separated by centrifugation, and then vacuum dried and ground into powder to obtain the modified silicon dioxide.

[0087] Preparation Example 12:

[0088] The preparation method of the modified silicon dioxide comprises the following steps:

[0089] 15 parts by weight of nanometer-sized silicon dioxide were dispersed in 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 30 minutes, 5 parts by weight of the intermediate C was then added, and the reaction was stirred at 80°C for 18 hours. After the reaction was completed, the precipitate was separated by centrifugation, and then vacuum dried and ground into powder to obtain the modified silicon dioxide.

[0090] Preparation Example 13:

[0091] The preparation method of the modified silicon dioxide comprises the following steps:

[0092] In a nitrogen environment, 2.8 parts by weight of γ-glycidoxypropyltrimethoxysilane and 1.5 parts by weight of p-aminobenzenesulfonic acid were dispersed in 10 parts by weight of dimethyl sulfoxide, and the reaction was stirred at 100°C for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixed solvent of acetonitrile and n-hexane, volume ratio 1:1) to obtain the intermediate A.

[0093] 4 parts by weight of the intermediate, 1.7 parts by weight of benzyl chloride and 1.2 parts by weight of potassium carbonate were dispersed in 50 parts by weight of tetrahydrofuran, and the reaction was stirred at 90°C for 12 hours in a nitrogen environment. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and column chromatography was used for purification (eluent: a mixed solvent of ethyl acetate and n-hexane, volume ratio 1:2) to obtain the intermediate B.

[0094] 15 parts by weight of nanometer-sized silicon dioxide were dispersed in 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 30 minutes, 5 parts by weight of the intermediate C was then added, and the reaction was stirred at 80°C for 18 hours. After the reaction was completed, the precipitate was separated by centrifugation, and then vacuum dried and ground into powder to obtain the modified silicon dioxide.

[0095] Example 1

[0096] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0097] 2.55 parts by weight of phenol and 10 parts by weight of formaldehyde are added into a three-necked flask, the pH is adjusted to 1 with 5% acetic acid, and the temperature is raised to 95°C for stirring reaction for 3 hours. Then, 1.255 parts by weight of 3-mercaptopropyl (dimethoxy) silane is added, the temperature is raised to 150°C for stirring reaction for 1 hour. After the reaction is completed, the pH is adjusted to 7.0 with 5% sodium hydroxide, 100 parts by weight of deionized water is used for washing and stirring for 10 minutes, and then the mixture is left to stand for layer separation. The upper water layer is sucked out, and the lower resin is left. After repeated washing for 3 times, the mercapto-modified phenolic resin is obtained through vacuum dehydration under the condition of 145°C and -0.08 MPa.

[0098] 40 parts by weight of the mercapto-modified phenolic resin, 4.5 parts by weight of the modified polyether amine prepared in Preparation Example 1, and 2.5 parts by weight of the modified silica prepared in Preparation Example 7 are dispersed in 50 parts by weight of dimethylbenzene, and then stirred and mixed for 15 minutes. Then, 0.07 parts by weight of azobisisobutyronitrile is added, and the temperature is raised to 90°C for stirring reaction for 8 hours under the protection of nitrogen. After the reaction is completed, the residual solvent is removed through distillation under reduced pressure to obtain the reinforced electronic-grade phenolic resin.

[0099] Example 2

[0100] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0101] 2.6 parts by weight of phenol and 10 parts by weight of formaldehyde are added into a three-necked flask, the pH is adjusted to 1.2 with 5% acetic acid, and the temperature is raised to 105°C for stirring reaction for 3.2 hours. Then, 1.26 parts by weight of 3-mercaptopropyl (dimethoxy) silane is added, the temperature is raised to 152°C for stirring reaction for 1.2 hours. After the reaction is completed, the pH is adjusted to 7.0 with 5% sodium hydroxide, 100 parts by weight of deionized water is used for washing and stirring for 10 minutes, and then the mixture is left to stand for layer separation. The upper water layer is sucked out, and the lower resin is left. After repeated washing for 3 times, the mercapto-modified phenolic resin is obtained through vacuum dehydration under the condition of 145°C and -0.08 MPa.

[0102] 45 parts by weight of the mercapto-modified phenolic resin, 4.7 parts by weight of the modified polyether amine prepared in Preparation Example 2, and 2.7 parts by weight of the modified silica prepared in Preparation 8 are dispersed in 50 parts by weight of dimethylbenzene, and then stirred and mixed for 18 minutes. Then, 0.09 parts by weight of azobisisobutyronitrile is added, and the temperature is raised to 95°C for stirring reaction for 9 hours under the protection of nitrogen. After the reaction is completed, the residual solvent is removed through distillation under reduced pressure to obtain the reinforced electronic-grade phenolic resin.

[0103] Example 3

[0104] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0105] 2.65 parts by weight of phenol and 10 parts by weight of formaldehyde are added into a three-necked flask, the pH is adjusted to 1.4 by using 5% acetic acid, and the temperature is raised to 110°C for stirring reaction for 3.4 hours. Then, 1.265 parts by weight of 3-mercaptopropyl(dimethoxy)silane is added, the temperature is raised to 155°C for stirring reaction for 1.5 hours. After the reaction is completed, the pH is adjusted to 7.0 by using 5% sodium hydroxide, 100 parts by weight of deionized water is used for washing and stirring for 10 minutes, and the layers are separated after standing. The upper water layer is sucked out, and the lower resin is left. After repeated washing for 3 times, the mercapto-modified phenolic resin is obtained by vacuum dehydration under the environment of 145°C and -0.08 MPa pressure.

[0106] 50 parts by weight of the mercapto-modified phenolic resin, 4.9 parts by weight of the modified polyether amine prepared in Preparation Example 3, and 2.9 parts by weight of the modified silica prepared in Preparation Example 9 are dispersed in 50 parts by weight of dimethylbenzene, and after stirring and mixing for 22 minutes, 0.12 parts by weight of azobisisobutyronitrile is added. The temperature is raised to 105°C for stirring reaction for 10 hours under the nitrogen protection environment. After the reaction is completed, the residual solvent is removed by distillation under reduced pressure to obtain the reinforced electronic-grade phenolic resin.

[0107] Example 4:

[0108] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0109] 2.7 parts by weight of phenol and 10 parts by weight of formaldehyde are added into a three-necked flask, the pH is adjusted to 1.7 by using 5% acetic acid, and the temperature is raised to 120°C for stirring reaction for 3.7 hours. Then, 1.27 parts by weight of 3-mercaptopropyl(dimethoxy)silane is added, the temperature is raised to 158°C for stirring reaction for 1.6 hours. After the reaction is completed, the pH is adjusted to 7.0 by using 5% sodium hydroxide, 100 parts by weight of deionized water is used for washing and stirring for 10 minutes, and the layers are separated after standing. The upper water layer is sucked out, and the lower resin is left. After repeated washing for 3 times, the mercapto-modified phenolic resin is obtained by vacuum dehydration under the environment of 145°C and -0.08 MPa pressure.

[0110] 55 parts by weight of the mercapto-modified phenolic resin, 5.2 parts by weight of the modified polyether amine prepared in Preparation Example 4, and 4.3 parts by weight of the modified silica prepared in Preparation Example 10 are dispersed in 50 parts by weight of dimethylbenzene, and after stirring and mixing for 27 minutes, 0.07-0.2 parts by weight of azobisisobutyronitrile is added. The temperature is raised to 110°C for stirring reaction for 11 hours under the nitrogen protection environment. After the reaction is completed, the residual solvent is removed by distillation under reduced pressure to obtain the reinforced electronic-grade phenolic resin.

[0111] Example 5:

[0112] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0113] 2.85 parts by weight of phenol and 10 parts by weight of formaldehyde are added into a three-necked flask, the pH is adjusted to 2 with 5% acetic acid, and the temperature is increased to 130°C for stirring reaction for 4 hours. Then, 1.285 parts by weight of 3-mercaptopropyl (dimethoxy) silane is added, the temperature is increased to 160°C for stirring reaction for 2 hours. After the reaction is completed, the pH is adjusted to 7.0 with 5% sodium hydroxide, and the mixture is washed with 100 parts by weight of deionized water for 10 minutes. After standing and layering, the upper water layer is removed, and the lower resin is left. After repeated washing for 3 times, the mercaptan-modified phenolic resin is obtained by vacuum dehydration at a temperature of 145°C and a pressure of -0.08 MPa.

[0114] 60 parts by weight of the mercaptan-modified phenolic resin, 5.5 parts by weight of the modified polyether amine prepared in Preparation Example 5, and 4.5 parts by weight of the modified silica prepared in Preparation Example 11 are dispersed in 50 parts by weight of dimethylbenzene, and the mixture is stirred and mixed for 130 minutes. Then, 0.2 parts by weight of azobisisobutyronitrile is added, and the temperature is increased to 120°C for stirring reaction for 12 hours in a nitrogen protection environment. After the reaction is completed, the residual solvent is removed by distillation under reduced pressure to obtain the reinforced electronic-grade phenolic resin.

[0115] Comparative Example 1:

[0116] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0117] In the preparation method of the reinforced electronic-grade phenolic resin with heat resistance, the modified polyether amine prepared in Preparation Example 5 in Example 5 is replaced by the modified polyether amine prepared in Preparation Example 6, and the other operations are consistent with those in Example 5.

[0118] Comparative Example 2:

[0119] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0120] In the preparation method of the reinforced electronic-grade phenolic resin with heat resistance, the modified polyether amine prepared in Preparation Example 5 in Example 5 is replaced by polyether amine D230, and the other operations are consistent with those in Example 5.

[0121] Comparative Example 3:

[0122] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0123] In the preparation method of the reinforced electronic-grade phenolic resin with heat resistance, the modified silica prepared in Preparation Example 11 in Example 5 is replaced by the modified silica prepared in Preparation Example 12, and the other operations are consistent with those in Example 5.

[0124] Comparative Example 4:

[0125] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0126] The modified silica prepared in Preparation Example 11 in Example 5 is replaced with the modified silica prepared in Preparation Example 13, and the other operations remain the same as in Example 5.

[0127] Comparative Example 5:

[0128] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0129] The modified silica prepared in Preparation Example 11 in Example 5 is replaced with nano-silica, and the other operations remain the same as in Example 5.

[0130] Comparative Example 6:

[0131] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0132] 2.85 parts by weight of phenol and 10 parts by weight of formaldehyde are added to a three-necked flask, the pH is adjusted to 2 with 5% acetic acid, and the temperature is raised to 130°C for stirring reaction for 6h. After the reaction is completed, the pH is adjusted to 7.0 with 5% sodium hydroxide, 100 parts by weight of deionized water is used for washing and stirring for 10 min, and then the layers are separated after standing. The upper water layer is sucked off, and the lower resin is left. After repeated washing for 3 times, the reinforced electronic-grade phenolic resin is prepared by vacuum dehydration at a temperature of 145°C and a pressure of -0.08 MPa.

[0133] Comparative Example 7:

[0134] A preparation method of a reinforced electronic-grade phenolic resin with heat resistance, comprising the following steps:

[0135] 2.85 parts by weight of phenol and 10 parts by weight of formaldehyde are added to a three-necked flask, the pH is adjusted to 2 with 5% acetic acid, and the temperature is raised to 130°C for stirring reaction for 6h. After the reaction is completed, the pH is adjusted to 7.0 with 5% sodium hydroxide, 100 parts by weight of deionized water is used for washing and stirring for 10 min, and then the layers are separated after standing. The upper water layer is sucked off, and the lower resin is left. After repeated washing for 3 times, the reinforced electronic-grade phenolic resin is prepared by vacuum dehydration at a temperature of 145°C and a pressure of -0.08 MPa.

[0136] 60 parts by weight of phenolic resin, 5.5 parts by weight of modified polyether amine prepared in Preparation Example 5, and 4.5 parts by weight of modified silica prepared in Preparation Example 11 are dispersed in 50 parts by weight of xylene, and then 0.2 parts by weight of azobisisobutyronitrile is added. After stirring and mixing for 130 min, the temperature is raised to 120°C for stirring reaction for 12h in a nitrogen protection environment. After the reaction is completed, the residual solvent is removed by distillation under reduced pressure to obtain the reinforced electronic-grade phenolic resin.

[0137] Test Example 1: Physical and chemical index detection

[0138] The enhanced electronic grade phenolic resin prepared from Examples 1-5 and Comparative Examples 1-7 was subjected to physical and chemical detection, the content of free phenol in the enhanced electronic grade phenolic resin was determined by gas chromatography according to GB / T 30773-2014, and the softening point was tested by the method in GB / T 4507-1999, and the detection results are shown in Table 1.

[0139] Table 1. Physical and chemical indexes

[0140]

[0141] From the detection results in Table 1, it can be seen that the enhanced electronic grade phenolic resin prepared from Examples 1-5 has good performance, while the performance of the enhanced electronic grade phenolic resin prepared from Comparative Examples 1-7 is decreased. In the present application, the modified nano-silicon dioxide enhances the dispersibility and compatibility in the phenolic resin matrix, which may reduce the deterioration of dielectric properties caused by agglomeration or interface defects; the polyetheramine segment in the modified polyetheramine has lower polarity, which may also improve the overall insulation performance; the high cross-linked dense network formed by the phenolic resin matrix, modified silicon dioxide and modified polyetheramine, together with the insulation barrier and interface strengthening provided by the silicon dioxide, makes the enhanced electronic grade phenolic resin have good insulation performance.

[0142] Test Example 2: Performance test

[0143] The tensile strength of the enhanced electronic grade phenolic resin prepared from Examples 1-5 and Comparative Examples 1-7 was detected by the method in GB / T 1040.1-2018, the high temperature resistance of the enhanced electronic grade phenolic resin prepared from Examples 1-5 and Comparative Examples 1-7 was detected by using a thermal gravimetric analyzer, and the UL-94 of Examples 1-5 and Comparative Examples 1-7 was evaluated by using a vertical combustion tester to detect the flame retardant performance, and the detection results are shown in Table 2.

[0144] Table 2. Performance test

[0145]

[0146] It can be seen from the test results in Table 2 that the enhanced electronic-grade phenolic resin prepared in Examples 1-5 has good tensile properties, high-temperature resistance and flame retardant properties, while the enhanced electronic-grade phenolic resin prepared in Comparative Examples 1-7 has a decline in performance compared with Examples 1-5. The acrylate groups at the ends of the modified polyether amine and the modified silica react with the mercapto phenolic resin, greatly increasing the density of the crosslinked network, which helps to enhance the heat resistance and tensile properties of the enhanced electronic-grade phenolic resin; the modified silica and the modified polyether amine achieve a balance between rigidity and toughness, improving the tensile properties of the enhanced electronic-grade phenolic resin; the modified silica can delay heat transfer as a physical thermal barrier, and the stable segment of the modified polyether amine and the high crosslinked network formed synergistically improve the heat resistance of the enhanced electronic-grade phenolic resin; the enhanced electronic-grade phenolic resin combines multiple flame-retardant elements such as phosphorus, nitrogen, sulfur and silicon, and synergistically improves the flame-retardant properties of the enhanced electronic-grade phenolic resin through multiple mechanisms such as condensed phase and gas phase flame retardation.

[0147] The above-described examples have described the technical solutions and beneficial effects of the present application in detail, and it should be understood that the above-described examples are only specific embodiments of the present application and are not intended to limit the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A method for producing a reinforced electronic grade phenol formaldehyde resin having heat resistance, characterized by, The preparation method comprises the following steps: phenol and formaldehyde are mixed in a weight ratio of 2.55-2.85:10, then acetic acid is used to adjust the pH, and then the mixture is heated to 95-130 DEG C and reacted for 3-4 h, then 3-mercaptopropyl (dimethoxy) silane is added, and the mixture is heated to 150-160 DEG C and reacted for 1-2 h to obtain the mercaptophenolic aldehyde resin; the mercaptophenolic aldehyde resin, the modified polyether amine, the modified silicon dioxide and azobisisobutyronitrile are reacted in a weight ratio of 40-60:4.5-5.5:2.5-4.5:0.07-0.2 at 90-120 DEG C for 8-12 h to obtain the enhanced electronic-grade phenolic aldehyde resin; The preparation method of the modified polyether amine comprises the following steps: phosphorus oxychloride and hydroxyethyl acrylate are reacted in a weight ratio of 1.5-2.1:1.3-1.9 to obtain an intermediate; the intermediate, polyether amine D230, 4-dimethylaminopyridine and triethylamine are reacted in a weight ratio of 1.4-1.9:0.5-0.7:0.08-0.1:0.5-1.5 to obtain the modified polyether amine; The preparation method of the modified silicon dioxide comprises the following steps: gamma-glycidoxypropyltrimethoxysilane, p-aminobenzenesulfonic acid and triethylamine are reacted in a weight ratio of 2.2-2.8:1.2-1.5:0.002-0.008 to obtain an intermediate A; the intermediate A, benzyl chloride and potassium carbonate are reacted in a weight ratio of 3-4:1.2-1.7:0.9-1.2 to obtain an intermediate B; the intermediate B, methacryloyl chloride and triethylamine are reacted in a weight ratio of 4-5:0.9-1.2:1.2-1.5 to obtain an intermediate C; nano-silicon dioxide and the intermediate C are reacted in a weight ratio of 10-15:2-5 to obtain the modified silicon dioxide.

2. The method for preparing a heat-resistant reinforced electronic-grade phenolic resin as described in claim 1, characterized in that, The reaction conditions of the gamma-glycidoxypropyltrimethoxysilane and the p-aminobenzenesulfonic acid comprise a reaction temperature of 80-100 DEG C and a reaction time of 4-6 h.

3. The method for preparing a heat-resistant reinforced electronic-grade phenolic resin as described in claim 1, characterized in that, The reaction conditions of the intermediate A, the benzyl chloride and the potassium carbonate comprise a reaction temperature of 70-90 DEG C and a reaction time of 8-12 h.

4. The method for preparing a heat-resistant reinforced electronic-grade phenolic resin as described in claim 1, characterized in that, The reaction conditions of the intermediate B, the methacryloyl chloride and the triethylamine comprise a reaction temperature of 40-60 DEG C and a reaction time of 5-7 h.

5. The method for preparing a heat-resistant reinforced electronic-grade phenolic resin as described in claim 1, characterized in that, The acetic acid is an acetic acid solution with a mass fraction of 5%.

6. The method for preparing a heat-resistant reinforced electronic-grade phenolic resin as described in claim 1, characterized in that, The pH value of the acetic acid is 1-2.

7. The method for preparing a heat-resistant reinforced electronic-grade phenolic resin as described in claim 1, characterized in that, The amount of the 3-mercaptopropyl (dimethoxy) silane is 10% of the total weight of the phenol and the formaldehyde.

8. A reinforced electronic grade phenol formaldehyde resin having heat resistance, characterized by, The enhanced electronic-grade phenolic aldehyde resin with heat resistance is prepared by the preparation method of any one of claims 1-7.

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