CN116120520A - Epoxy resin monomer and preparation method and application thereof - Google Patents
Epoxy resin monomer and preparation method and application thereof Download PDFInfo
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- CN116120520A CN116120520A CN202211709604.4A CN202211709604A CN116120520A CN 116120520 A CN116120520 A CN 116120520A CN 202211709604 A CN202211709604 A CN 202211709604A CN 116120520 A CN116120520 A CN 116120520A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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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
- 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
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Abstract
The invention relates to an epoxy resin monomer, a preparation method and application thereof. The preparation method comprises the following steps: synthesizing hydroquinone with a plurality of fluorocarbon bonds; mixing hydroquinone with a plurality of fluorocarbon bonds with epichlorohydrin and tetrabutylammonium bromide, and stirring and reacting for 5.5-6.5 h at the temperature of 90+/-2 ℃; removing excess epichlorohydrin to obtain a first reaction mixture; adding toluene and sodium hydroxide solution into the first reaction mixture, and stirring and reacting for 2.5-3.5 hours at 90+/-2 ℃ to obtain a second reaction mixture; and washing the second reaction mixture to neutrality, and vacuum drying to obtain the epoxy resin monomer. The technical problem solved by the invention is how to provide an epoxy resin monomer which can improve the heat conductivity of the electronic packaging adhesive and can not reduce the mechanical property, the insulating property, the weather resistance and the like of the electronic packaging adhesive when being applied to the electronic packaging adhesive, so that the epoxy resin monomer is more practical.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to an epoxy resin monomer and a preparation method and application thereof.
Background
The core of contemporary electronic products is the electronic components therein, which are generally encapsulated with electronic encapsulation materials in order to protect the electronic components. With the miniaturization, miniaturization and densification of electronic components, the working heat generation amount thereof is also increasing. Therefore, the electronic packaging adhesive used for protecting the electronic element has high impact resistance, good waterproof property and insulating property, and certain heat conductivity, so that a heat dissipation effect is provided for the electronic element, and damage caused by excessive accumulated heat is prevented.
Single-performance electronic packaging materials are currently on the market, but the number of electronic packaging materials with multiple performances is smaller. Epoxy resin generally has higher mechanical strength and good insulativity, and can well protect an integrated circuit from being damaged by short circuit and collision; meanwhile, most of epoxy resin is a thermosetting material, has low viscosity and good fluidity at normal temperature, and the curing temperature is more than 200 ℃, so that the epoxy resin can be easily molded on the surface of an integrated circuit, and can be cured and shaped at the temperature without damaging the integrated circuit. Therefore, epoxy resins have been one of the materials of priority in the selection of electronic packaging materials. However, epoxy is not a good heat conducting material. In fact, since epoxy resin has only molecular covalent bonds after curing, heat can only be transferred slowly by means of molecular vibration (also called phonon transfer) in epoxy resin, and the efficiency of such transfer is extremely low. In most cases, the epoxy resin cannot be used as a heat conducting material, but can play a good role in heat preservation. Epoxy resins are more prone to secondary thermal damage to electronic components than other materials.
Although it has been reported in the literature that the addition of a heat conductive filler to an epoxy resin material can improve this problem, the mechanical strength, water resistance and insulation properties of the epoxy resin are greatly reduced with the addition of the heat conductive filler.
Disclosure of Invention
The invention mainly aims to provide an epoxy resin monomer, a preparation method and application thereof, and aims to provide an epoxy resin monomer which can improve the heat conductivity of electronic packaging glue when applied to the electronic packaging glue, enable electronic components to quickly dissipate heat when in operation, prevent the electronic components from being possibly damaged by factors such as water vapor, current and collision, and the like, has good comprehensive performance and low cost, and is more suitable for practical use.
The aim and the technical problems of the invention are realized by adopting the following technical proposal. The preparation method of the epoxy resin monomer provided by the invention comprises the following steps:
1) Synthesizing hydroquinone with a plurality of fluorocarbon bonds;
2) Mixing hydroquinone with a plurality of fluorocarbon bonds with epichlorohydrin and tetrabutylammonium bromide, and stirring and reacting for 5.5-6.5 h at the temperature of 90+/-2 ℃; removing excess epichlorohydrin to obtain a first reaction mixture;
3) Adding toluene and sodium hydroxide solution into the first reaction mixture, and stirring and reacting for 2.5-3.5 hours at 90+/-2 ℃ to obtain a second reaction mixture;
4) And washing the second reaction mixture to neutrality, and vacuum drying to obtain the epoxy resin monomer.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, in the foregoing preparation method, the structural formula of the hydroquinone with plural fluorocarbon bonds is shown in formula 2:
preferably, in the preparation method, in the step 2), the feeding mass ratio of hydroquinone with plural fluorocarbon bonds to epichlorohydrin to tetrabutylammonium bromide is 30-32: 90-100: 1.
preferably, the preparation method of the foregoing, wherein the preparation of hydroquinone having a plurality of fluorocarbon bonds in step 1) includes the steps of:
1a) Mixing 2-methyl-4-heptafluoroisopropyl aniline and deionized water, placing in an ice-water bath, dropwise adding concentrated hydrochloric acid and sodium nitrite solution into the mixture, stirring the mixture for 1h, and filtering the mixture to obtain a diazotization reagent;
1b) Mixing 1, 4-p-benzoquinone and sodium bicarbonate, placing in an ice-water bath, dropwise adding the diazotizing agent into the mixture, stirring, controlling the temperature of the reaction solution to be less than or equal to 10 ℃, and stirring and reacting for 2.5-3.5 h at 8-10 ℃; standing the reaction solution for 2.5-3.5 h, filtering, flushing the solid component with deionized water, and vacuum drying to obtain p-benzoquinone with a plurality of fluorocarbon bonds;
1c) Mixing the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and deionized water, heating to 90+/-2 ℃ under the stirring condition, dropwise adding concentrated hydrochloric acid, and refluxing for 1.5-2.5 hours;
1d) Filtering the reactant solution, taking filtrate for cooling, and obtaining the crystal of hydroquinone with a plurality of fluorocarbon bonds.
Preferably, in the preparation method, the mass ratio of the 2-methyl-4-heptafluoroisopropyl aniline to the deionized water to the concentrated hydrochloric acid to the sodium nitrite is 2.6-2.8: 6.8 to 7:5.3 to 5.5:1, a step of; the weight percentage of the 1, 4-p-benzoquinone is 7.7-7.9% of the total amount of the 2-methyl-4-heptafluoroisopropylaniline, deionized water, concentrated hydrochloric acid and sodium nitrite, and the weight percentage of the sodium bicarbonate is 8.6-8.8% of the total amount of the 2-methyl-4-heptafluoroisopropylaniline, deionized water, concentrated hydrochloric acid and sodium nitrite.
Preferably, in the foregoing preparation method, in the step 1 c), the feeding mass ratio of the p-benzoquinone with plural fluorocarbon bonds to the zinc powder to the deionized water is 1:0.8 to 0.9:6.5 to 7.0; the concentrated hydrochloric acid accounts for 50-60% of the total amount of the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and deionized water.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the epoxy resin monomer provided by the invention, a molecular unit of the epoxy resin monomer comprises a plurality of benzene ring structures and a plurality of fluorocarbon bond structures; the complex benzene ring structure is two adjacent benzene rings; the complex fluorocarbon bond structure is-C 3 H 7 。
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the aforementioned epoxy resin monomer is prepared according to the aforementioned method for preparing an epoxy resin monomer.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. The epoxy resin-based electronic packaging adhesive provided by the invention comprises the epoxy resin monomer.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the preparation method of the epoxy resin-based electronic packaging adhesive, the epoxy resin monomer is mixed with 2-methylimidazole and hexagonal boron nitride nano powder according to the mass ratio of 100:1:25, then the mixture is mixed with thionyl chloride and chloroform, and finally the epoxy resin-based electronic packaging adhesive is obtained by diluting with chloroform.
By means of the technical scheme, the epoxy resin monomer and the preparation method and application thereof provided by the invention have at least the following advantages:
the invention provides an epoxy resin monomer and a preparation method and application thereof, wherein the epoxy resin monomer is prepared by reacting 2-methyl-4-heptafluoroisopropylaniline with sodium nitrite under the condition of concentrated hydrochloric acid to obtain a diazotization reagent; then dripping a diazotizing reagent into the 1, 4-p-benzoquinone under the action of sodium bicarbonate solution to modify the benzoquinone so as to obtain p-benzoquinone with a plurality of fluorocarbon bonds; the plural fluorocarbon bonds (-C) can be obtained by the above process 3 H 7 ) The structure and plural benzene ring structures (two adjacent benzene rings, biphenyl) are introduced into p-benzoquinone; then, the p-benzoquinone with complex fluorocarbon bonds is taken as a raw material, and zinc powder is taken as a reduction materialReducing the p-benzoquinone with a plurality of fluorocarbon bonds into hydroquinone with a plurality of fluorocarbon bonds under the condition of concentrated hydrochloric acid; finally, under the catalysis of tetrabutylammonium bromide, removing hydrogen chloride from the phenolic hydroxyl group of the hydroquinone with a plurality of fluorocarbon bonds and chlorine atoms in epoxy chloropropane to obtain an epoxy resin monomer; in the above-mentioned reduction reaction and grafting reaction, the complex fluorocarbon bond (-C) contained in the p-benzoquinone material having complex fluorocarbon bonds 3 H 7 ) The structure and the plural benzene ring structures (two adjacent benzene rings and biphenyl) are not changed and are completely introduced into the epoxy resin monomer, so that the epoxy resin monomer prepared by the technical scheme of the invention not only contains the plural benzene ring structures with good heat resistance, namely the biphenyl structure, but also contains more fluorocarbon bond structures. On one hand, a biphenyl structure is constructed in the epoxy resin, and the performance of a plurality of benzene ring structures is more outstanding because the benzene ring has a compact molecular structure and higher electron density; the modified epoxy resin is introduced into the epoxy resin to modify the epoxy resin, so that the strength, the temperature resistance and other performances of the epoxy resin can be better improved; moreover, the biphenyl structure can provide more and stronger three-dimensional crosslinking structures, so that higher durability can be provided for external impact and internal heating; on the other hand, a side chain containing a plurality of fluorocarbon bonds is introduced on the biphenyl structure of the epoxy resin, so that the fluorine content in the epoxy resin can be effectively improved; the fluorocarbon bond has stronger electronegativity due to the introduction of the fluorocarbon bond, so that the water resistance and the insulativity of the epoxy resin are greatly improved; that is, the molecular density of the fluorocarbon bond is also higher, and the structural strength of the three-dimensional network structure of the cured product is enhanced, so that the impact resistance of the epoxy resin is improved well, and the electronic packaging adhesive taking the epoxy resin as a main component can effectively resist various external injuries such as water vapor, electric arc, impact and the like for electronic elements. From the above, the technical proposal of the invention introduces a plurality of heat-resistant benzene ring structures and a plurality of fluorocarbon bond structures into the molecular chain of the epoxy resin, and under the combined action of the two structures, the molecular density of the macromolecule in the epoxy resin can be improved, and the production of the cured epoxy resin is enhancedThe three-dimensional network structure of the material has the structural strength, so that the electronic packaging adhesive prepared from the material has better impact resistance, water resistance and insulativity, and can allow the addition of the heat conducting filler without excessively affecting the due weather resistance; practical tests show that the electronic packaging adhesive taking the modified epoxy resin as the main component has the heat conductivity coefficient reaching 2.0-2.2W/m < 2 > K, the water contact angle being more than 90 degrees and the dielectric constant being less than 4.0; furthermore, the electronic packaging adhesive taking the modified epoxy resin monomer as a main component has the impact strength basically equivalent to that of the common epoxy resin electronic packaging adhesive, and the test data of the electronic packaging adhesive are equivalent to 97% -101% of the prior art, which shows that the electronic packaging adhesive has improved heat conductivity and does not seriously reduce the weather resistance of various protection electronic elements.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the following is a detailed description of a specific implementation, structure, characteristics and effects of an epoxy resin monomer, a preparation method and application thereof according to the invention in combination with a preferred embodiment.
The invention provides a preparation method of an epoxy resin monomer, which comprises the following steps:
firstly, self-preparing a p-benzoquinone containing a plurality of benzene ring structures and a plurality of fluorocarbon bonds. The method comprises the following specific steps:
firstly, preparing a diazotizing agent by taking 2-methyl-4-heptafluoroisopropyl aniline, deionized water, concentrated hydrochloric acid and sodium nitrite as raw materials; wherein, 2-methyl-4-heptafluoroisopropyl aniline and sodium nitrite are reactants, and concentrated hydrochloric acid provides a concentrated acid environment for the reaction so as to facilitate the diazotization reaction to be better carried out; preferably, the feeding mass ratio of the 2-methyl-4-heptafluoroisopropyl aniline, deionized water, concentrated hydrochloric acid and sodium nitrite is 2.6-2.8: 6.8 to 7:5.3 to 5.5:1, a step of; firstly, mixing 2-methyl-4-heptafluoroisopropyl aniline and deionized water, placing the mixture in an ice-water bath with the temperature less than or equal to 5 ℃, and dropwise adding concentrated hydrochloric acid into the mixture to adjust the PH value of the mixture to 3 so as to control the reaction progress and the form of reaction products; then dropwise adding sodium nitrite solution into the mixture for reaction; preferably, the mass concentration of the sodium nitrite solution is 25-30%; stirring and reacting for 1h, and filtering to obtain the diazotizing reagent of the 2-methyl-4-heptafluoroisopropylaniline.
The 2-methyl-4-heptafluoroisopropyl aniline used in the step can be purchased in the market and can also be synthesized by a laboratory; the method comprises the following specific steps: sequentially adding m-trifluoromethyl benzene, zinc powder and a proper amount of ethanol into an autoclave, fully mixing, and introducing hydrogen to keep the pressure in the autoclave at about 0.1MPa for 24 hours; reducing to normal pressure, and replacing the gas atmosphere with nitrogen; heating to 120 ℃, reacting for 2 hours, and then reducing the temperature in the kettle to below 40 ℃; filtering the reaction solution to remove zinc powder, distilling at normal pressure to remove ethanol, performing reduced pressure distillation, and collecting 60 ℃ fractions under the vacuum degree of 460Pa to obtain colorless and transparent meta-trichloromethylaniline; preferably, the hydrogen pressurization and reduction reaction are performed in two steps.
Secondly, preparing p-benzoquinone with complex fluorocarbon bonds by taking 1, 4-p-benzoquinone, sodium bicarbonate and the diazotizing agent as raw materials; mixing 1, 4-p-benzoquinone with sodium bicarbonate, placing in an ice-water bath at the temperature of less than or equal to 5 ℃, dripping a heavy nitriding reagent into the 1, 4-p-benzoquinone under the action of sodium bicarbonate solution for modification, dripping the reagent while stirring, and controlling the temperature of the reaction solution at the whole process to be less than or equal to 10 ℃ to obtain a bright yellow mixture; the dropping speed is slow to be added, and the dropping speed is controlled to be 2-5 ml/min; preferably, the addition amount of the 1, 4-p-benzoquinone is 7.7-7.9% of the total amount of the 2-methyl-4-heptafluoroisopropyl aniline, deionized water, concentrated hydrochloric acid and sodium nitrite; preferably, the addition amount of the sodium bicarbonate is 8.6-8.8% of the total amount of the 2-methyl-4-heptafluoroisopropyl aniline, deionized water, concentrated hydrochloric acid and sodium nitrite; stirring the mixture at 8-10 ℃ for 2.5-3.5 h; after the reaction is finished, standing the reaction solution for 2.5 to 3.5 hours, and filtering to obtain a crude product, namely a solid component; washing the solid component with deionized water for a plurality of times, such as five times, and taking out the product; placing the mixture in a vacuum oven, and drying the mixture at 45-55 ℃ to obtain yellow p-benzoquinone product with complex fluorocarbon bonds; the structural formula of the p-benzoquinone product with complex fluorocarbon bonds is shown in the following formula 1:
secondly, preparing hydroquinone with a plurality of fluorocarbon bonds by taking the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and concentrated hydrochloric acid as raw materials; wherein zinc powder is used as a reducing agent, and the p-benzoquinone with a plurality of fluorocarbon bonds is reduced into hydroquinone with a plurality of fluorocarbon bonds under the condition of concentrated hydrochloric acid, and the structural formula of a p-benzoquinone product with a plurality of fluorocarbon bonds is shown as the following formula 2:
mixing the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and deionized water, heating to 90+/-2 ℃ under the stirring condition, then dropwise adding concentrated hydrochloric acid, and refluxing for 1.5-2.5 hours after bubbles disappear; preferably, the feeding mass ratio of the p-benzoquinone with a plurality of fluorocarbon bonds to zinc powder to deionized water is 1:0.8 to 0.9:6.5 to 7.0; preferably, the amount of the concentrated hydrochloric acid is 50-60% of the total amount of the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and deionized water in percentage by mass. Filtering the reaction mixture while it is hot; cooling the filtrate to obtain the hydroquinone crystal with plural fluorocarbon bonds.
Finally, hydroquinone with a plurality of fluorocarbon bonds, epichlorohydrin, tetrabutylammonium bromide, toluene and sodium hydroxide solution are used as raw materials to prepare epoxy resin monomers; before adding epichlorohydrin and tetrabutylammonium bromide into the hydroquinone with a plurality of fluorocarbon bonds, carrying out vacuum drying treatment on the hydroquinone at 110 ℃ to ensure the effect of subsequent grafting reaction; mixing hydroquinone with a plurality of fluorocarbon bonds with epichlorohydrin and tetrabutylammonium bromide, and stirring and reacting for 5.5-6.5 h at the temperature of 90+/-2 ℃; removing excess epichlorohydrin to obtain a first reaction mixture; tetrabutylammonium bromide is used as a catalyst, and under the catalysis of the tetrabutylammonium bromide, the phenolic hydroxyl group of the hydroquinone with a plurality of fluorocarbon bonds and chlorine atoms in the epichlorohydrin are subjected to hydrogen chloride removal to obtain an epoxy resin monomer; preferably, the charging mass ratio of hydroquinone with a plurality of fluorocarbon bonds to epichlorohydrin to tetrabutylammonium bromide is 30-32: 90-100: 1, a step of; after the reaction is finished, toluene and sodium hydroxide solution are added into the first reaction mixture for extraction, and the mixture is stirred and reacted for 2.5 to 3.5 hours at the temperature of 90+/-2 ℃ to obtain a second reaction mixture; washing the second reaction mixture to neutrality, and vacuum drying to obtain brown liquid, namely the epoxy resin monomer; the structural formula of the epoxy resin monomer is shown in the following formula 3:
the invention also provides an epoxy resin monomer, wherein the molecular unit of the epoxy resin monomer comprises a plurality of benzene ring structures and a plurality of fluorocarbon bond structures; the complex benzene ring structure is two adjacent benzene rings; the complex fluorocarbon bond structure is-C 3 H 7 。
Preferably, the epoxy resin monomer is prepared according to the aforementioned method for preparing an epoxy resin monomer.
The invention also provides an epoxy resin-based electronic packaging adhesive, which mainly comprises the epoxy resin monomer. The epoxy resin monomer prepared by the invention is used by blending with the heat-conducting filler, so that the heat-conducting property is improved, and meanwhile, the performances of impact resistance, water resistance, insulation and the like of the epoxy resin monomer can be kept without serious reduction.
The invention also provides a preparation method of the epoxy resin-based electronic packaging adhesive, which comprises the steps of firstly mixing the epoxy resin monomer with 2-methylimidazole and hexagonal boron nitride nano powder according to the mass ratio of 100:1:25, and then mixing the mixture with thionyl chloride and chloroform; preferably, the mixing ratio of the mixture to thionyl chloride and chloroform is 2.4-2.5:2.9-3.0:1.0; finally, the mixture is diluted by chloroform until the mass solid content is 15-20%, and the epoxy resin-based electronic packaging adhesive can be obtained.
The invention will be further described with reference to specific examples, which are not to be construed as limiting the scope of the invention, but rather as falling within the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will now occur to those skilled in the art in light of the foregoing disclosure.
Unless otherwise indicated, materials, reagents, and the like referred to below are commercially available products well known to those skilled in the art; unless otherwise indicated, the methods are all methods well known in the art. Unless otherwise defined, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1:
70mL of 2-methyl-4-heptafluoroisopropylaniline and 250mL of deionized water were added to a three-necked flask. The three-necked flask was placed in an ice-water bath at a temperature of 5 ℃. 168mL of concentrated hydrochloric acid was then added dropwise to the three-necked flask. 36.25g of sodium nitrite was prepared as a 27.7wt% solution, and the solution was added dropwise to the mixture in the three-necked flask through a dropping funnel, stirred for 1 hour, and then filtered to obtain a diazotizing agent.
Taking a beaker, adding a small amount of water, mixing 45g of 1, 4-p-benzoquinone and 50g of sodium bicarbonate in the beaker, slowly dripping the diazotizing agent prepared in the embodiment into the mixture by using a dropping funnel in an ice-water bath at the temperature of 5 ℃, controlling the dripping speed to be 3.5ml/min, and dripping while stirring, and controlling the temperature to be lower than 10 ℃ to obtain the mixture; stirring the mixture at 8-10 ℃ for 3 hours, standing for 3 hours at room temperature, filtering the mixture to obtain a crude product, and flushing the crude product with deionized water for five times. The product was taken out and placed in a vacuum oven and dried at 50 ℃. The p-benzoquinone product can be obtained.
30g of synthesized p-benzoquinone and 25g of zinc powder and 200mL of deionized water are mixed. The mixture was heated to 90℃with stirring, then 120mL of concentrated hydrochloric acid was added dropwise, and after the addition was completed, the mixture was refluxed for 2 hours after the bubbles disappeared. The mixture was filtered while hot. After cooling the filtrate, the hydroquinone product can be obtained.
25g of hydroquinone, 65mL of epichlorohydrin, and 0.8g of tetrabutylammonium bromide were mixed together. In a three-necked flask, stirring was carried out at 90℃for 6 hours. After the reaction, the mixture was cooled to room temperature, distilled under reduced pressure, and excess epichlorohydrin was removed. Subsequently, 45mL of toluene and 30mL of 30wt% sodium hydroxide solution were added, and the mixture was heated to 90℃for 3 hours. Then, the mixture was washed with deionized water to neutrality. The product was vacuum dried at 60℃for 12 hours to obtain an epoxy resin monomer.
Taking 100g of epoxy resin monomer, mixing 1g of 2-methylimidazole and 25g of hexagonal boron nitride nano powder, mixing the mixture with 92mL of thionyl chloride and 35mL of chloroform, and diluting the mixture with chloroform until the mass solid content is 20% to obtain the epoxy resin-based electronic packaging adhesive.
The electronic packaging adhesive prepared in the embodiment is cured at 200 ℃ under high temperature, and the thermal conductivity coefficient of the cured product is measured to be 2.1W/m < 2 > K, the bending strength is 115Mpa, the water contact angle is 98 degrees, and the dielectric constant is 4.4.
Example 2:
70mL of 2-methyl-4-heptafluoroisopropylaniline and 240mL of deionized water were added to a three-necked flask. The three-necked flask was placed in an ice-water bath at a temperature of 5 ℃. 165mL of concentrated hydrochloric acid was then added dropwise to the three-necked flask. Then, 35g of sodium nitrite was prepared into a 27.7wt% solution, which was added dropwise to the mixture in the three-necked flask via a dropping funnel, stirred for 1 hour, and then filtered to obtain a diazotizing agent.
Taking a beaker, adding a small amount of water, mixing 44g of 1, 4-p-benzoquinone and 49g of sodium bicarbonate in the beaker, slowly dripping the diazotizing agent prepared in the embodiment into the mixture by using a dropping funnel in an ice-water bath at the temperature of 5 ℃, controlling the dripping speed to be 3.5ml/min, and dripping while stirring, and controlling the temperature to be lower than 10 ℃ to obtain the mixture; stirring the mixture at 8-10 ℃ for 3 hours, standing for 3 hours at room temperature, filtering the mixture to obtain a crude product, and flushing the crude product with deionized water for five times. The product was taken out and placed in a vacuum oven and dried at 50 ℃. The p-benzoquinone product can be obtained.
30g of synthesized p-benzoquinone and 25g of zinc powder and 200mL of deionized water are mixed. The mixture was heated to 90℃with stirring, then 120mL of concentrated hydrochloric acid was added dropwise, and after the addition was completed, the mixture was refluxed for 2 hours after the bubbles disappeared. The mixture was filtered while hot. After cooling the filtrate, the hydroquinone product can be obtained.
25g of hydroquinone, 68mL of epichlorohydrin, and 0.8g of tetrabutylammonium bromide were mixed together. In a three-necked flask, stirring was carried out at 90℃for 6 hours. After the reaction, the mixture was cooled to room temperature, distilled under reduced pressure, and excess epichlorohydrin was removed. Subsequently, 45mL of toluene and 30mL of 30wt% sodium hydroxide solution were added, and the mixture was heated to 90℃for 3 hours. Then, the mixture was washed with deionized water to neutrality. The product was vacuum dried at 60℃for 12 hours to obtain an epoxy resin monomer.
Taking 100g of epoxy resin monomer, mixing 1g of 2-methylimidazole and 25g of hexagonal boron nitride nano powder, mixing the mixture with 92mL of thionyl chloride and 35mL of chloroform, and diluting the mixture with chloroform until the mass solid content is 20% to obtain the epoxy resin-based electronic packaging adhesive.
The electronic packaging adhesive prepared in the embodiment is cured at a high temperature of 200 ℃, and the thermal conductivity coefficient of the cured product is measured to be 2.2W/m < 2 > K, the bending strength is 120Mpa, the water contact angle is 92 degrees, and the dielectric constant is 4.3.
The technical features of the claims and/or the description of the present invention may be combined in a manner not limited to the combination of the claims by the relation of reference. The technical scheme obtained by combining the technical features in the claims and/or the specification is also the protection scope of the invention.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the epoxy resin monomer is characterized by comprising the following steps:
1) Synthesizing hydroquinone with a plurality of fluorocarbon bonds;
2) Mixing hydroquinone with a plurality of fluorocarbon bonds with epichlorohydrin and tetrabutylammonium bromide, and stirring and reacting for 5.5-6.5 h at the temperature of 90+/-2 ℃; removing excess epichlorohydrin to obtain a first reaction mixture;
3) Adding toluene and sodium hydroxide solution into the first reaction mixture, and stirring and reacting for 2.5-3.5 hours at 90+/-2 ℃ to obtain a second reaction mixture;
4) And washing the second reaction mixture to neutrality, and vacuum drying to obtain the epoxy resin monomer.
2. The preparation method according to claim 1, wherein the hydroquinone having a plurality of fluorocarbon bonds has a structural formula shown in formula 2:
3. the preparation method according to claim 1, wherein the mass ratio of hydroquinone with plural fluorocarbon bonds to epichlorohydrin to tetrabutylammonium bromide in the step 2) is 30-32: 90-100: 1.
4. the method according to claim 1, wherein the preparation of hydroquinone having a plurality of fluorocarbon bonds in step 1) comprises the steps of:
1a) Mixing 2-methyl-4-heptafluoroisopropyl aniline and deionized water, placing in an ice-water bath, dropwise adding concentrated hydrochloric acid and sodium nitrite solution into the mixture, stirring the mixture for 1h, and filtering the mixture to obtain a diazotization reagent;
1b) Mixing 1, 4-p-benzoquinone and sodium bicarbonate, placing in an ice-water bath, dropwise adding the diazotizing agent into the mixture, stirring, controlling the temperature of the reaction solution to be less than or equal to 10 ℃, and stirring and reacting for 2.5-3.5 h at 8-10 ℃; standing the reaction solution for 2.5-3.5 h, filtering, flushing the solid component with deionized water, and vacuum drying to obtain p-benzoquinone with a plurality of fluorocarbon bonds;
1c) Mixing the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and deionized water, heating to 90+/-2 ℃ under the stirring condition, dropwise adding concentrated hydrochloric acid, and refluxing for 1.5-2.5 hours;
1d) Filtering the reactant solution, taking filtrate for cooling, and obtaining the crystal of hydroquinone with a plurality of fluorocarbon bonds.
5. The preparation method of claim 4, wherein the mass ratio of the 2-methyl-4-heptafluoroisopropylaniline to the deionized water to the concentrated hydrochloric acid to the sodium nitrite is 2.6-2.8: 6.8 to 7:5.3 to 5.5:1, a step of; the weight percentage of the 1, 4-p-benzoquinone is 7.7-7.9% of the total amount of the 2-methyl-4-heptafluoroisopropylaniline, deionized water, concentrated hydrochloric acid and sodium nitrite, and the weight percentage of the sodium bicarbonate is 8.6-8.8% of the total amount of the 2-methyl-4-heptafluoroisopropylaniline, deionized water, concentrated hydrochloric acid and sodium nitrite.
6. The preparation method of claim 4, wherein the mass ratio of the p-benzoquinone with plural fluorocarbon bonds to the zinc powder to the deionized water in the step 1 c) is 1:0.8 to 0.9:6.5 to 7.0; the concentrated hydrochloric acid accounts for 50-60% of the total amount of the p-benzoquinone with a plurality of fluorocarbon bonds, zinc powder and deionized water.
7. An epoxy resin monomer is characterized in that the molecular unit of the epoxy resin monomer comprises a plurality of benzene ring structures and a plurality of fluorocarbon bond structures; the complex benzene ring structure is two adjacent benzene rings; the complex fluorocarbon bond structure is-C 3 H 7 。
8. The epoxy resin monomer according to claim 7, which is prepared according to the preparation method of the epoxy resin monomer according to any one of claims 1 to 6.
9. An epoxy resin-based electronic packaging adhesive, which is characterized by comprising the epoxy resin monomer according to claim 7 or 8.
10. The preparation method of the epoxy resin-based electronic packaging adhesive is characterized in that the epoxy resin monomer according to claim 7 or 8 is mixed with 2-methylimidazole and hexagonal boron nitride nano powder according to the mass ratio of 100:1:25, then the mixture is mixed with thionyl chloride and chloroform, and finally the epoxy resin-based electronic packaging adhesive is obtained by diluting with chloroform.
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| CN202211709604.4A CN116120520A (en) | 2022-12-29 | 2022-12-29 | Epoxy resin monomer and preparation method and application thereof |
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