CN112251178A - Electronic material with high thermal stability - Google Patents

Electronic material with high thermal stability Download PDF

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CN112251178A
CN112251178A CN202011136618.2A CN202011136618A CN112251178A CN 112251178 A CN112251178 A CN 112251178A CN 202011136618 A CN202011136618 A CN 202011136618A CN 112251178 A CN112251178 A CN 112251178A
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parts
mixing
temperature
epoxy resin
mass
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高路生
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/168—Zinc halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention discloses an electronic material with high thermal stability, and belongs to the field of electronic high polymer materials. According to the invention, firstly, nano silicon dioxide is subjected to polyacrylic acid chain extension and then is mixed with tetraethylenepentamine and polyethyleneimine to prepare aminated nano silicon dioxide, then, nano titanium dioxide is grafted with an epoxy group under the action of isocyanate, then, nano titanium dioxide grafted with the epoxy group is grafted with a hydroxyl-containing flexible chain segment under the action of alkaline amine to prepare modified nano titanium dioxide, and finally, epoxy resin, filler, diluent, aminated silicon dioxide, modified titanium dioxide, epoxidized soybean oil and a catalyst are mixed to prepare the electronic material with high thermal stability. The electronic material with high thermal stability prepared by the technical scheme of the invention has very good service performance under the high temperature condition.

Description

Electronic material with high thermal stability
Technical Field
The invention relates to the field of electronic high polymer materials, in particular to an electronic material with high thermal stability.
Background
The LED lamp is composed of five parts, namely a light-emitting chip, a wire, a support, a conducting layer, a packaging material and the like, wherein the packaging material is mainly used for protecting the chip part, the chip is prevented from being corroded by moisture or oxygen in the external environment, and the light-emitting efficiency of the LED is ensured. With the improvement of the LED industry and technology, the performance requirements for LED packaging materials are becoming more and more strict.
At present, LED packaging materials mainly comprise resins with high transparency, such as epoxy resin, organic silicon modified epoxy resin and the like, and because different packaging materials have different prices and functions, the application occasions and the output are different. Currently, the epoxy family still occupies the major market in the LED packaging industry.
When the epoxy resin is used as the LED packaging material, the epoxy resin has the unique advantages of low price, high bonding strength, good mechanical property, easily available raw materials and the like, however, when the LED is started to step into the era of power type LEDs, when the epoxy resin is used as the LED packaging material, the traditional epoxy resin packaging material has a series of defects and is gradually eliminated by the power type LEDs, and the following main points are shown:
(1) the problems of increased internal stress, reduced flexibility, increased brittleness and the like of the packaging material are caused by overlarge crosslinking density of the epoxy resin cured product, so that the packaging material is easy to crack, and a filament or a patch is easy to break after the packaging material is heated and expanded, thereby shortening the service life of the LED;
(2) aromatic rings in the epoxy resin are easily oxidized after being irradiated by long-time ultraviolet light to generate carbonyl chromophore, and finally the resin is yellowed, so that the service life of the LED is limited;
due to the defects of the traditional epoxy resin packaging material, various modification methods for improving the high temperature resistance of the epoxy resin packaging material appear in the market at present, but most of the existing modification methods aim at the modification of the epoxy resin, and the materials and the cost required by the modification are higher, so that the research and development of the novel LED packaging material with high thermal stability have very wide market prospect.
Disclosure of Invention
Aiming at the problems that the traditional LED epoxy packaging material has poor thermal stability under the use condition of a high-power LED, so that the epoxy packaging material has cracking and warping phenomena in the use process, thereby influencing the service life of the LED, the electronic material with high thermal stability and the preparation method thereof are provided.
In order to achieve the purpose, the invention provides the following technical scheme:
the electronic material with high thermal stability is characterized by mainly comprising the following raw material components in parts by weight: 50-80 parts of matrix resin, 5-15 parts of diluent, 12-20 parts of filler and 5-12 parts of curing agent, wherein the epoxy resin has good fluidity under the action of the diluent, so that the product has a good using effect, and under the action of the curing agent, the product has a good packaging effect.
The electronic material with high thermal stability is characterized by further comprising the following components in parts by weight: 15-20 parts of additive, after the additive is added into a product, a complex three-dimensional network which is alternately wound with epoxy resin can be formed in the product, so that the bonding force among molecules in the product is improved, the thermal stability of the product is improved, and meanwhile, the additive also contains nano titanium dioxide, so that the ultraviolet aging resistance of the product is improved.
Preferably, the matrix resin is any one of epoxy resin E-44 or epoxy resin E-51, the diluent is any one of diglycidyl ether, epoxypropane butyl ether or epoxypropane phenyl ether, the filler is any one or a mixture of aluminum powder, glass fiber and aluminum nitride powder, and the addition of the filler can ensure that the product has better thermal conductivity and the cracking resistance of the product is improved.
The curing agent is preferably aminated silicon dioxide, and the aminated silicon dioxide is prepared by chain extension of nano silicon dioxide by polyacrylic acid and mixing with tetraethylenepentamine and polyethyleneimine; the amine compound is grafted on the surface of the nano silicon dioxide, so that not only can the agglomeration of the nano silicon dioxide be reduced and the dispersibility of the nano silicon dioxide in a product be improved, but also the silicon dioxide grafted with the amine compound can be used as a curing agent of epoxy resin and the nano silicon dioxide is used as a connecting point, so that the product has better thermal stability and the anti-cracking performance is improved.
The modified titanium dioxide is prepared by grafting epoxy resin on nano titanium dioxide under the action of isocyanate and reacting under the action of alkaline amine, wherein the catalyst is any one of zinc chloride or magnesium chloride, and comprises 20-30 parts by weight of modified titanium dioxide, 2-6 parts by weight of catalyst and 8-12 parts by weight of epoxidized soybean oil; the addition of the modified titanium dioxide and the epoxidized soybean oil can enable the interior of the product to have a firmer cross-linked network, improve the thermal stability, and the addition of the catalyst is beneficial to the ring opening of the epoxidized soybean oil in the preparation process of the product, so that the reaction time is reduced.
As optimization, the electronic material with high thermal stability comprises the following components in parts by weight: 65 parts of base resin, 10 parts of diluent, 15 parts of filler, 8 parts of curing agent, 18 parts of additive, 24 parts of modified titanium dioxide, 5 parts of catalyst and 10 parts of epoxidized soybean oil.
As optimization, the preparation method of the electronic material with high thermal stability specifically comprises the following steps:
(1) mixing nano silicon dioxide and polyacrylic acid in N, N-dimethylformamide, adding 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide, stirring for reaction, filtering and drying;
(2) mixing the substance obtained in the step (1) and polyethyleneimine in N, N-dimethylformamide, adding tetraethylenepentamine, stirring for reaction, filtering, washing and drying;
(3) mixing nano titanium dioxide and diisocyanate in an anhydrous solvent, adding an epoxy resin solution, stirring for reaction, performing suction filtration, and drying;
(4) mixing the substance obtained in the step (3) with an anhydrous solvent, adding alkaline amine, stirring for reaction, performing suction filtration, washing and drying;
(5) mixing the substance obtained in the step (4) with the epoxidized soybean oil, adding a catalyst, and stirring and mixing;
(6) mixing epoxy resin and a diluent, adding a filler, stirring and mixing the substance obtained in the step (2) and the substance obtained in the step (5);
(7) and (4) performing index analysis on the product obtained in the step (6).
As optimization, the preparation method of the electronic material with high thermal stability specifically comprises the following steps:
(1) mixing nano silicon dioxide and polyacrylic acid according to a mass ratio of 1: 2, adding N, N-dimethylformamide with the mass of 150-300 times of that of the nano-silicon dioxide into the beaker, stirring and mixing for 50-80 min under the conditions that the temperature is 80-90 ℃ and the rotating speed is 300-360 r/min to obtain a nano-silicon dioxide mixed dispersion liquid, mixing the nano-silicon dioxide mixed dispersion liquid with 4-dimethylaminopyridine according to the mass ratio of 200: 1, adding N, N' -dicyclohexylcarbodiimide with the mass 10 times that of 4-dimethylaminopyridine, stirring and reacting for 12-13 h at the temperature of 120-130 ℃ and the rotating speed of 250-320 r/min, filtering and drying;
(2) mixing the substance obtained in the step (1) with polyethyleneimine according to a mass ratio of 5: mixing, adding tetraethylenepentamine accounting for 1-2 times of the mass of polyethyleneimine and N, N-dimethylformamide accounting for 40-60 times of the mass of polyethyleneimine, stirring and reacting for 20-30 h at the temperature of 60-70 ℃ and the rotating speed of 200-260 r/min, filtering, washing and drying;
(3) mixing nano silicon dioxide and diisocyanate according to a mass ratio of 1: 1, mixing, adding anhydrous acetone which is 10-30 times of the mass of the nano silicon dioxide and an epoxy resin solution which is 3-5 times of the mass of the nano silicon dioxide, stirring and reacting for 20-24 hours at the temperature of 100-150 ℃ and the rotating speed of 260-320 r/min in an inert gas atmosphere, filtering and drying;
(4) mixing the substance obtained in the step (3) with anhydrous acetone according to a mass ratio of 1: 80, adding ethanolamine which is 1-2 times of the mass of the substance obtained in the step (3), stirring and reacting for 1-4 hours at the temperature of 60-80 ℃ and the rotating speed of 300-320 r/min, and then performing suction filtration, washing and drying;
(5) mixing 20-30 parts of the substance obtained in the step (4) with 2-6 parts of a catalyst, adding 8-12 parts of epoxidized soybean oil, and stirring and mixing at the temperature of 30-50 ℃ and the rotating speed of 200-320 r/min;
(6) mixing 50-80 parts of epoxy resin and 5-15 parts of diluent, adding 12-20 parts of filler, and stirring and mixing 5-12 parts of the substance obtained in the step (2) and 15-20 parts of the substance obtained in the step (5) at the temperature of 40-80 ℃ and the rotating speed of 300-350 r/min;
(7) and (4) performing index analysis on the product obtained in the step (6).
Preferably, the diisocyanate in the step (3) is any one of toluene diisocyanate or isophorone diisocyanate.
Preferably, the epoxy resin solution in the step (3) is prepared by mixing epoxy resin E-44 and xylene according to a mass ratio of 1: 15 to obtain an epoxy resin solution.
Compared with the prior art, the invention has the beneficial effects that:
(1) the self-made curing agent is added in the preparation process of the electronic material with high thermal stability, the self-made curing agent is aminated nano silicon dioxide, firstly, the nano silicon dioxide can reduce the surface energy of the nano silicon dioxide after being aminated and modified, so that the self-aggregation phenomenon of the nano silicon dioxide is reduced, the nano silicon dioxide can be uniformly distributed in a product after being added into the product, so that the anti-cracking performance of the product is improved, secondly, the aminated and modified nano silicon dioxide has an amino compound on the surface, when the amino compound is added into the product, the epoxy resin can be promoted to be cured, the epoxy resin is cured by taking the nano silicon dioxide as a core, so that the product has higher internal binding force after being cured, the product has better thermal stability, and the anti-cracking performance is improved under the high-temperature condition;
(2) the invention adds the additive in the preparation process of the electronic material with high thermal stability, the additive contains modified nano titanium dioxide, catalyst and epoxidized soybean oil, on one hand, after the nano silicon dioxide is modified, the surface of the nano silicon dioxide can be grafted with a flexible chain segment containing hydroxyl, a rigid chain segment is embedded in the flexible chain segment, after the nano silicon dioxide is added into the product, the nano silicon dioxide can be wound with the molecular chain of matrix resin, so that the internal bonding force of the product is further improved, the thermal stability of the product is improved, and the crack resistance at high temperature is further improved, on the other hand, after the epoxidized soybean oil is added into the product, the epoxy soybean oil can perform ring-opening reaction under the action of the catalyst and react with primary amine contained on the surface of the self-made curing agent, so that the crosslinking density in the product is further improved, and the high thermal stability of the product is further improved, and after the epoxidized soybean oil reacts with the amino on the surface of the self-made curing agent, hydroxyl can be formed on the surface of the epoxidized soybean oil, so that the hydroxyl on the surface of the modified nano titanium dioxide generates hydrogen bond action, the cohesion of the product is improved, the thermal stability of the product is further improved, and the cracking resistance is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the method for testing each index of the electronic material with high thermal stability manufactured in the following examples is as follows:
high-temperature stability: the fracture strength of each example product and each comparative example product under the condition of 30 ℃ and the fracture strength of each example product after being treated for 12 hours under the condition of 200 ℃ are respectively measured, and the higher the fracture strength after being treated, the better the high-temperature stability system;
resistance to yellowing: after aging the example and comparative products under UV light at 80 ℃ for 12h, the yellowing of the surface of the products was observed.
Example 1:
an electronic material with high thermal stability mainly comprises the following components in parts by weight: 65 parts of epoxy resin E-44, 10 parts of diglycidyl ether, 15 parts of aluminum powder, 8 parts of a curing agent, 18 parts of an additive, 24 parts of modified titanium dioxide, 5 parts of zinc chloride and 10 parts of epoxidized soybean oil.
A preparation method of an electronic material with high thermal stability mainly comprises the following preparation steps:
(1) mixing nano silicon dioxide and polyacrylic acid according to a mass ratio of 1: 2, adding N, N-dimethylformamide 300 times of the mass of the nano-silica into the beaker, stirring and mixing for 80min at the temperature of 90 ℃ and the rotating speed of 360r/min to obtain nano-silica mixed dispersion, mixing the nano-silica mixed dispersion with 4-dimethylaminopyridine according to the mass ratio of 200: 1, adding N, N' -dicyclohexylcarbodiimide with the mass 10 times that of 4-dimethylaminopyridine, stirring and reacting for 13 hours at the temperature of 130 ℃ and the rotating speed of 320r/min, filtering, and drying at the temperature of 80 ℃;
(2) mixing the substance obtained in the step (1) with polyethyleneimine according to a mass ratio of 5: 1, mixing, adding tetraethylenepentamine with the mass of 1-2 times of that of polyethyleneimine and N, N-dimethylformamide with the mass of 40-60 times of that of polyethyleneimine, stirring and reacting for 30 hours at the temperature of 70 ℃ and the rotating speed of 260r/min, filtering to obtain a filter cake, washing the filter cake for 8 times by using absolute ethyl alcohol, and drying at the temperature of 70 ℃;
(3) mixing nano silicon dioxide and diisocyanate according to a mass ratio of 1: 1, mixing, adding anhydrous acetone accounting for 30 times of the mass of the nano silicon dioxide and epoxy resin solution accounting for 5 times of the mass of the nano silicon dioxide, stirring and reacting for 24 hours at the temperature of 150 ℃ and the rotating speed of 320r/min in the atmosphere of nitrogen gas, filtering, and drying at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) with anhydrous acetone according to a mass ratio of 1: 80, adding ethanolamine which is 2 times of the mass of the substance obtained in the step (3), stirring and reacting for 4 hours at the temperature of 80 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain filter residue, washing the filter residue with anhydrous propyl alcohol and anhydrous ethanol for 6 times respectively, and drying at the temperature of 70 ℃;
(5) mixing 24 parts of the substance obtained in the step (4) with 5 parts of a catalyst, adding 10 parts of epoxidized soybean oil, and stirring and mixing for 20-40 min at the temperature of 50 ℃ and the rotating speed of 320 r/min;
(6) mixing 65 parts of epoxy resin E-44 with 10 parts of diglycidyl ether, adding 15 parts of aluminum powder, 8 parts of the substance obtained in the step (2) and 18 parts of the substance obtained in the step (5), and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(7) and (4) performing index analysis on the product obtained in the step (6).
Preferably, the diisocyanate in the step (3) is any one of toluene diisocyanate or isophorone diisocyanate.
Preferably, the epoxy resin solution in the step (3) is prepared by mixing epoxy resin E-44 and xylene according to a mass ratio of 1: 15 to obtain an epoxy resin solution.
Example 2:
an electronic material with high thermal stability mainly comprises the following components in parts by weight: 65 parts of epoxy resin E-51, 10 parts of diglycidyl ether, 15 parts of aluminum powder, 8 parts of a curing agent, 18 parts of an additive, 24 parts of modified titanium dioxide, 5 parts of zinc chloride and 10 parts of epoxidized soybean oil.
A preparation method of an electronic material with high thermal stability mainly comprises the following preparation steps:
(1) mixing nano silicon dioxide and polyacrylic acid according to a mass ratio of 1: 2, adding N, N-dimethylformamide 300 times of the mass of the nano-silica into the beaker, stirring and mixing for 80min at the temperature of 90 ℃ and the rotating speed of 360r/min to obtain nano-silica mixed dispersion, mixing the nano-silica mixed dispersion with 4-dimethylaminopyridine according to the mass ratio of 200: 1, adding N, N' -dicyclohexylcarbodiimide with the mass 10 times that of 4-dimethylaminopyridine, stirring and reacting for 13 hours at the temperature of 130 ℃ and the rotating speed of 320r/min, filtering, and drying at the temperature of 80 ℃;
(2) mixing the substance obtained in the step (1) with polyethyleneimine according to a mass ratio of 5: 1, mixing, adding tetraethylenepentamine with the mass of 1-2 times of that of polyethyleneimine and N, N-dimethylformamide with the mass of 40-60 times of that of polyethyleneimine, stirring and reacting for 30 hours at the temperature of 70 ℃ and the rotating speed of 260r/min, filtering to obtain a filter cake, washing the filter cake for 8 times by using absolute ethyl alcohol, and drying at the temperature of 70 ℃;
(3) mixing nano silicon dioxide and diisocyanate according to a mass ratio of 1: 1, mixing, adding anhydrous acetone accounting for 30 times of the mass of the nano silicon dioxide and epoxy resin solution accounting for 5 times of the mass of the nano silicon dioxide, stirring and reacting for 24 hours at the temperature of 150 ℃ and the rotating speed of 320r/min in the atmosphere of nitrogen gas, filtering, and drying at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) with anhydrous acetone according to a mass ratio of 1: 80, adding ethanolamine which is 2 times of the mass of the substance obtained in the step (3), stirring and reacting for 4 hours at the temperature of 80 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain filter residue, washing the filter residue with anhydrous propyl alcohol and anhydrous ethanol for 6 times respectively, and drying at the temperature of 70 ℃;
(5) mixing 24 parts of the substance obtained in the step (4) with 5 parts of a catalyst, adding 10 parts of epoxidized soybean oil, and stirring and mixing for 20-40 min at the temperature of 50 ℃ and the rotating speed of 320 r/min;
(6) mixing 65 parts of epoxy resin E-51 and 10 parts of diglycidyl ether, adding 15 parts of aluminum powder, 8 parts of the substance obtained in the step (2) and 18 parts of the substance obtained in the step (5), and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(7) and (4) performing index analysis on the product obtained in the step (6).
Preferably, the diisocyanate in the step (3) is any one of toluene diisocyanate or isophorone diisocyanate.
Preferably, the epoxy resin solution in the step (3) is prepared by mixing epoxy resin E-44 and xylene according to a mass ratio of 1: 15 to obtain an epoxy resin solution.
Example 3:
an electronic material with high thermal stability mainly comprises the following components in parts by weight: 65 parts of epoxy resin E-44, 10 parts of diglycidyl ether, 15 parts of aluminum powder, 8 parts of tetraethylenepentamine, 18 parts of additive, 24 parts of modified titanium dioxide, 5 parts of zinc chloride and 10 parts of epoxidized soybean oil.
A preparation method of an electronic material with high thermal stability mainly comprises the following preparation steps:
(1) mixing nano silicon dioxide and diisocyanate according to a mass ratio of 1: 1, mixing, adding anhydrous acetone accounting for 30 times of the mass of the nano silicon dioxide and epoxy resin solution accounting for 5 times of the mass of the nano silicon dioxide, stirring and reacting for 24 hours at the temperature of 150 ℃ and the rotating speed of 320r/min in the atmosphere of nitrogen gas, filtering, and drying at the temperature of 80 ℃;
(2) mixing the substance obtained in the step (2) with anhydrous acetone according to a mass ratio of 1: 80, adding ethanolamine which is 2 times of the mass of the substance obtained in the step (2), stirring and reacting for 4 hours at the temperature of 80 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain filter residue, washing the filter residue with anhydrous propyl alcohol and anhydrous ethanol for 6 times respectively, and drying at the temperature of 70 ℃;
(3) mixing 24 parts of the substance obtained in the step (2) with 5 parts of a catalyst, adding 10 parts of epoxidized soybean oil, and stirring and mixing for 20-40 min at the temperature of 50 ℃ and the rotating speed of 320 r/min;
(4) mixing 65 parts of epoxy resin E-44 with 10 parts of diglycidyl ether, adding 15 parts of aluminum powder, 8 parts of tetraethylenepentamine and 18 parts of the substance obtained in the step (3), and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(5) and (4) performing index analysis on the product obtained in the step (4).
Preferably, the diisocyanate in the step (1) is any one of toluene diisocyanate or isophorone diisocyanate.
Preferably, the epoxy resin solution in the step (1) is prepared by mixing epoxy resin E-44 and xylene according to a mass ratio of 1: 15 to obtain an epoxy resin solution.
Example 4:
an electronic material with high thermal stability mainly comprises the following components in parts by weight: 65 parts of epoxy resin E-44, 10 parts of diglycidyl ether, 15 parts of aluminum powder, 8 parts of curing agent, 18 parts of additive, 24 parts of titanium dioxide, 5 parts of zinc chloride and 10 parts of epoxidized soybean oil.
A preparation method of an electronic material with high thermal stability mainly comprises the following preparation steps:
(1) mixing nano silicon dioxide and polyacrylic acid according to a mass ratio of 1: 2, adding N, N-dimethylformamide 300 times of the mass of the nano-silica into the beaker, stirring and mixing for 80min at the temperature of 90 ℃ and the rotating speed of 360r/min to obtain nano-silica mixed dispersion, mixing the nano-silica mixed dispersion with 4-dimethylaminopyridine according to the mass ratio of 200: 1, adding N, N' -dicyclohexylcarbodiimide with the mass 10 times that of 4-dimethylaminopyridine, stirring and reacting for 13 hours at the temperature of 130 ℃ and the rotating speed of 320r/min, filtering, and drying at the temperature of 80 ℃;
(2) mixing the substance obtained in the step (1) with polyethyleneimine according to a mass ratio of 5: 1, mixing, adding tetraethylenepentamine with the mass of 1-2 times of that of polyethyleneimine and N, N-dimethylformamide with the mass of 40-60 times of that of polyethyleneimine, stirring and reacting for 30 hours at the temperature of 70 ℃ and the rotating speed of 260r/min, filtering to obtain a filter cake, washing the filter cake for 8 times by using absolute ethyl alcohol, and drying at the temperature of 70 ℃;
(3) mixing 24 parts of nano titanium dioxide and 5 parts of catalyst, adding 10 parts of epoxidized soybean oil, and stirring and mixing for 20-40 min at the temperature of 50 ℃ and the rotating speed of 320 r/min;
(4) mixing 65 parts of epoxy resin E-44 with 10 parts of diglycidyl ether, adding 15 parts of aluminum powder, 8 parts of the substance obtained in the step (2) and 18 parts of the substance obtained in the step (3), and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(5) and (4) performing index analysis on the product obtained in the step (4).
Example 5:
an electronic material with high thermal stability mainly comprises the following components in parts by weight: 65 parts of epoxy resin E-44, 10 parts of diglycidyl ether, 15 parts of aluminum powder, 8 parts of a curing agent, 18 parts of an additive, 24 parts of modified titanium dioxide and 5 parts of zinc chloride.
A preparation method of an electronic material with high thermal stability mainly comprises the following preparation steps:
(1) mixing nano silicon dioxide and polyacrylic acid according to a mass ratio of 1: 2, adding N, N-dimethylformamide 300 times of the mass of the nano-silica into the beaker, stirring and mixing for 80min at the temperature of 90 ℃ and the rotating speed of 360r/min to obtain nano-silica mixed dispersion, mixing the nano-silica mixed dispersion with 4-dimethylaminopyridine according to the mass ratio of 200: 1, adding N, N' -dicyclohexylcarbodiimide with the mass 10 times that of 4-dimethylaminopyridine, stirring and reacting for 13 hours at the temperature of 130 ℃ and the rotating speed of 320r/min, filtering, and drying at the temperature of 80 ℃;
(2) mixing the substance obtained in the step (1) with polyethyleneimine according to a mass ratio of 5: 1, mixing, adding tetraethylenepentamine with the mass of 1-2 times of that of polyethyleneimine and N, N-dimethylformamide with the mass of 40-60 times of that of polyethyleneimine, stirring and reacting for 30 hours at the temperature of 70 ℃ and the rotating speed of 260r/min, filtering to obtain a filter cake, washing the filter cake for 8 times by using absolute ethyl alcohol, and drying at the temperature of 70 ℃;
(3) mixing nano silicon dioxide and diisocyanate according to a mass ratio of 1: 1, mixing, adding anhydrous acetone accounting for 30 times of the mass of the nano silicon dioxide and epoxy resin solution accounting for 5 times of the mass of the nano silicon dioxide, stirring and reacting for 24 hours at the temperature of 150 ℃ and the rotating speed of 320r/min in the atmosphere of nitrogen gas, filtering, and drying at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) with anhydrous acetone according to a mass ratio of 1: 80, adding ethanolamine which is 2 times of the mass of the substance obtained in the step (3), stirring and reacting for 4 hours at the temperature of 80 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain filter residue, washing the filter residue with anhydrous propyl alcohol and anhydrous ethanol for 6 times respectively, and drying at the temperature of 70 ℃;
(5) mixing 24 parts of the substance obtained in the step (4) with 5 parts of a catalyst, and stirring and mixing for 20-40 min at the temperature of 50 ℃ and the rotating speed of 320 r/min;
(6) mixing 65 parts of epoxy resin E-44 with 10 parts of diglycidyl ether, adding 15 parts of aluminum powder, 8 parts of the substance obtained in the step (2) and 18 parts of the substance obtained in the step (5), and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(7) and (4) performing index analysis on the product obtained in the step (6).
Preferably, the diisocyanate in the step (3) is any one of toluene diisocyanate or isophorone diisocyanate.
Preferably, the epoxy resin solution in the step (3) is prepared by mixing epoxy resin E-44 and xylene according to a mass ratio of 1: 15 to obtain an epoxy resin solution.
Comparative example:
an electronic material with high thermal stability mainly comprises the following components in parts by weight: 65 parts of epoxy resin E-44, 10 parts of diglycidyl ether, 15 parts of aluminum powder and 8 parts of tetraethylenepentamine.
A preparation method of an electronic material with high thermal stability mainly comprises the following preparation steps:
(1) mixing 65 parts of epoxy resin E-44 with 10 parts of diglycidyl ether, adding 15 parts of aluminum powder and 8 parts of tetraethylenepentamine, and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(2) and (3) performing index analysis on the product obtained in the step (1).
Effect example 1:
table 1 below shows the index analysis results of the preparation method of the electronic material having high thermal stability using examples 1 to 5 of the present invention and the comparative example.
TABLE 1
30 ℃ breaking strength/MPa Fracture Strength/MP after 200 ℃ treatmenta Yellowing resistance
Example 1 5.2 4.8 No yellowing phenomenon
Example 2 5.1 4.8 No yellowing phenomenon
Example 3 4.0 3.2 Small yellow spot
Example 4 3.8 3.0 Small yellow spot
Example 5 4.5 4.0 No yellowing phenomenon
Comparative example 2.8 1.8 Completely yellowing
As can be seen from table 1: compared with a comparative example, the product prepared by the invention has better thermal stability and still has better service performance after high-temperature treatment; the comparison of the example 1 and the example 2 shows that the results obtained by using two different epoxy resins in the invention are not very different, the comparison of the example 3 and the comparative example shows that the aminated nano-silica is added into the product, so that not only can the epoxy resin in the product be cured, but also the epoxy resin can be uniformly distributed in the product while being cured, so that the dispersibility of the nano-silica is improved, so that the thermal stability of the product is improved, the comparison of the example 4 and the comparative example shows that the yellowing resistance of the product can be improved to a certain extent by adding the modified nano-titania into the product, and the internal binding force of the product is further improved and the thermal stability of the product is further improved due to the existence of long carbon chains on the surface after the modified nano-titania is added into the product, and the comparison of the example 5 and the example 1 shows that, the proper amount of epoxidized soybean oil is added into the product, so that the internal binding force of the product can be improved, the stability of each molecule in the product is further improved, and the thermal stability of the product is further improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference thereto is therefore intended to be embraced therein.

Claims (1)

1. An electronic material having high thermal stability, characterized in that: the material mainly comprises the following raw material components in parts by weight: 65 parts of epoxy resin E-44, 10 parts of diglycidyl ether, 15 parts of aluminum powder, 8 parts of a curing agent, 18 parts of an additive, 24 parts of modified titanium dioxide, 5 parts of zinc chloride and 10 parts of epoxidized soybean oil;
the preparation method of the electronic material with high thermal stability comprises the following preparation steps:
(1) mixing nano silicon dioxide and polyacrylic acid according to a mass ratio of 1: 2, adding N, N-dimethylformamide 300 times of the mass of the nano-silica into the beaker, stirring and mixing for 80min at the temperature of 90 ℃ and the rotating speed of 360r/min to obtain nano-silica mixed dispersion, mixing the nano-silica mixed dispersion with 4-dimethylaminopyridine according to the mass ratio of 200: 1, adding N, N' -dicyclohexylcarbodiimide with the mass 10 times that of 4-dimethylaminopyridine, stirring and reacting for 13 hours at the temperature of 130 ℃ and the rotating speed of 320r/min, filtering, and drying at the temperature of 80 ℃;
(2) mixing the substance obtained in the step (1) with polyethyleneimine according to a mass ratio of 5: 1, mixing, adding tetraethylenepentamine with the mass of 1-2 times of that of polyethyleneimine and N, N-dimethylformamide with the mass of 40-60 times of that of polyethyleneimine, stirring and reacting for 30 hours at the temperature of 70 ℃ and the rotating speed of 260r/min, filtering to obtain a filter cake, washing the filter cake for 8 times by using absolute ethyl alcohol, and drying at the temperature of 70 ℃;
(3) mixing nano silicon dioxide and diisocyanate according to a mass ratio of 1: 1, mixing, adding anhydrous acetone accounting for 30 times of the mass of the nano silicon dioxide and epoxy resin solution accounting for 5 times of the mass of the nano silicon dioxide, stirring and reacting for 24 hours at the temperature of 150 ℃ and the rotating speed of 320r/min in the atmosphere of nitrogen gas, filtering, and drying at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) with anhydrous acetone according to a mass ratio of 1: 80, adding ethanolamine which is 2 times of the mass of the substance obtained in the step (3), stirring and reacting for 4 hours at the temperature of 80 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain filter residue, washing the filter residue with anhydrous propyl alcohol and anhydrous ethanol for 6 times respectively, and drying at the temperature of 70 ℃;
(5) mixing 24 parts of the substance obtained in the step (4) with 5 parts of a catalyst, adding 10 parts of epoxidized soybean oil, and stirring and mixing for 20-40 min at the temperature of 50 ℃ and the rotating speed of 320 r/min;
(6) mixing 65 parts of epoxy resin E-44 with 10 parts of diglycidyl ether, adding 15 parts of aluminum powder, 8 parts of the substance obtained in the step (2) and 18 parts of the substance obtained in the step (5), and stirring and mixing for 80min at the temperature of 60 ℃ and the rotating speed of 350 r/min;
(7) performing index analysis on the product obtained in the step (6);
the diisocyanate in the step (3) is any one of toluene diisocyanate or isophorone diisocyanate;
and (3) the epoxy resin solution is prepared by mixing epoxy resin E-44 and xylene according to a mass ratio of 1: 15 to obtain an epoxy resin solution.
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