CN114539809A - Surface-modified silicon micropowder and preparation method thereof - Google Patents
Surface-modified silicon micropowder and preparation method thereof Download PDFInfo
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Abstract
The invention provides a surface modified silicon micropowder and a preparation method thereof, belonging to the field of electronic packaging materials, wherein the preparation method comprises the steps of taking natural quartz sand with the purity of more than 99.7 percent as a raw material, sequentially carrying out melting, crushing, grinding and grading, and then carrying out surface modification on the surface of the graded silicon micropowder.
Description
Technical Field
The invention relates to the field of electronic packaging materials, in particular to surface-modified silicon micropowder and a preparation method thereof.
Background
The spherical silicon micropowder is an amorphous quartz powder material with spherical particles and the main component of silicon dioxide, is white powder, and has wide development prospect due to high purity, fine particles, excellent dielectric property, low thermal expansion coefficient, high thermal conductivity and other superior properties; the spherical silicon micropowder is mainly applied to copper clad laminates and epoxy plastic packaging material fillers in large-scale integrated circuit packaging, and also has application in high and new technical fields of aviation, aerospace, coatings, catalysts, medicines, special ceramics, daily cosmetics and the like.
At present, more than 95 percent of electronic elements and integrated circuits are packaged by adopting epoxy resin composite materials, wherein the used matrix resin is mainly o-cresol formaldehyde epoxy resin, and the used filler is mainly silicon powder, and the content of the filler is 70-90 percent. With the development of ultra-large scale, high density, high power, high precision, and multi-function integrated circuits and the rapid development of electronic packaging technology, the development of Epoxy Molding Compound (EMC) is developing towards high purity, high reliability, high thermal conductivity, high temperature soldering resistance, high moisture resistance, high bonding strength, low stress, low expansion, low water absorption, low viscosity, low environmental pollution, and easy processing. The key technology for preparing the high-performance EMC is to improve the filling amount of the silicon micro powder, but the content and the surface structure form of the silicon micro powder greatly influence the flowability of the epoxy molding compound and the packaging effect of the integrated circuit, and the major defects brought by increasing the filling amount of the silicon micro powder are that the flowability of the EMC is greatly reduced and the packaging and forming process is not facilitated.
Disclosure of Invention
In order to solve the problems, the invention provides surface-modified silicon micropowder and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of surface modified silicon micropowder comprises the following steps:
(1) selecting natural quartz sand with the purity of more than 99.7 percent as a raw material, firstly washing with water to remove dust and impurities on the surface, then soaking in an acid solution overnight, then washing with deionized water to be neutral, and drying for later use;
(2) transferring the quartz sand prepared in the step (1) into a high-temperature furnace for melting treatment, cooling to room temperature to obtain a high-purity quartz fused body, transferring the quartz fused body into a ball mill, adding a ball milling medium for ball milling, and grading by a grading machine after ball milling to respectively obtain first silicon micro powder with the median particle size of 13-15 mu m and second silicon micro powder with the median particle size of 8-10 mu m for later use;
(3) adding the second silicon micropowder into an air flow mill for air flow crushing, and separating in a classification area to obtain third silicon micropowder with the median particle size of 2.5-3.5 mu m;
(4) the first silicon micro powder and the third silicon micro powder are mixed according to the weight ratio of (6-7): 2 to obtain graded micro powder;
(5) heating the graded micro powder to 90-120 ℃, adding 1-4% of surface modification solution according to the mass ratio, preserving heat, fully stirring and mixing for 0.5-2h, removing a heat source, and continuing stirring until cooling to obtain the surface modified silicon micro powder.
Preferably, the selected particle size of the natural quartz sand is 0.1-3 mm.
Preferably, the melting temperature of the melting treatment in the step (2) is 1850 ℃, and the melting time is 12-14 h.
Preferably, the ball milling medium is mixed by weight ratio of 1: (2-3): (1.5-2) alumina grinding balls with diameters of 3cm, 4cm and 5cm respectively, and performing ball milling for 25-35 min.
Preferably, the surface modification solution comprises the following components in parts by weight: 12-25 parts of silane coupling agent, 5-9 parts of polyether modified polysiloxane, 6-12 parts of polydimethylsiloxane, 10-15 parts of weak polar solvent and 1-3 parts of deionized water.
Preferably, the silane coupling agent is methyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane or N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane.
Preferably, the weakly polar solvent is toluene, xylene, gasoline or petroleum ether.
Preferably, the grading micropowder in the step (4) further comprises the following processing steps:
s1, weighing 3-aminopropyltriethoxysilane, dissolving the 3-aminopropyltriethoxysilane in absolute ethanol to obtain a solution with the concentration of 1-3 wt.%, adding 1% deionized water by volume, mixing and stirring uniformly, adding the graded micropowder, stirring at a low speed for reaction overnight, filtering, washing with absolute ethanol, and drying for later use;
s2, dispersing the graded micro powder prepared in S1 in toluene or xylene, adding 3-bromo-2-bromomethylpropionic acid, introducing nitrogen for degassing, adding pentamethyldiethylenetriamine, introducing nitrogen for degassing again, stirring at room temperature for reaction for 8-12h, filtering, washing and dispersing in dimethylformamide after the reaction is finished, adding sodium azide, heating to 90-110 ℃, keeping the temperature and stirring for reaction for 24-30h, cooling to room temperature after the reaction is finished, filtering, washing and dispersing in dimethylformamide again, adding propiolic acid and 4-dimethylaminopyridine as a catalyst under the condition of an ice water bath, stirring and mixing until the temperature of the system is stable, dropwise adding N, N-diisopropylcarbodiimide while stirring, stirring and reacting the reaction system under the condition of the ice water bath for 8-12h after the dropwise adding is finished, after the reaction is finished, returning to room temperature, adding the aminated cage-like silsesquioxane, continuously stirring for reaction for 1-3h, filtering, washing and drying to obtain first modified graded micro powder;
wherein the mass ratio of the graded micro powder to the 3-bromo-2-bromomethylpropionic acid to the pentamethyldiethylenetriamine is 100: (3-5): (2.6-3.2); the mass ratio of the graded micro powder to the sodium azide, the propiolic acid, the 4-dimethylaminopyridine, the N, N-diisopropylcarbodiimide and the amination polyhedral oligomeric silsesquioxane is 100: (2.6-3.6): (1-1.2): (0.1-0.14): (2.3-2.5);
s3, transferring the first modified graded micro powder into a high-temperature furnace for high-temperature heat treatment, and cooling to room temperature to obtain second modified graded micro powder; the treatment temperature of the high-temperature heat treatment is 800-1200 ℃, and the treatment time is 1-6 h.
Preferably, the second modified graded micro powder further comprises the following processing steps:
s1, weighing the coupling agent, dissolving the coupling agent in the solvent, adding malonic acid, mixing and stirring uniformly, standing overnight, adding an ammonia solution, stirring for reaction for 5-6h, and continuing to stand for 1-2 days; preparing a dispersion solution after ultrasonic dispersion;
wherein the coupling agent is methyltrimethoxysilane or methyltriethoxysilane, and the solvent is methanol or ethanol; the molar ratio of the solvent to the coupling agent is (30-35): 1, the molar ratio of the coupling agent to the malonic acid to the ammonia water is 1: (0.01-0.02): (0.8-1);
s2, adding the second modified graded micro powder into the dispersion solution, stirring and mixing for 1-2min, filtering, drying at 60-80 ℃, spreading and transferring into a vacuum drying oven, covering with a polydimethylsiloxane film, heating to 180-200 ℃ in a nitrogen atmosphere, and preserving heat for 1-3h to obtain third modified graded micro powder.
Another object of the present invention is to provide a surface-modified fine silica powder prepared by the foregoing preparation method.
The invention has the beneficial effects that:
the invention is based on the prior art, obtains the silicon micropowder with narrow particle size distribution by particle size classification, and leads the contact among the silicon micropowder particles to mainly occur between large particles and the small particles to mainly fill in gaps among the large particles by the specific proportion grading of the large particle size (13-15 mu m) and the small particle size (2.5-3.5 mu m), thereby improving the fluidity among the silicon micropowder, and simultaneously further improving the dispersibility of the silicon micropowder in the resin melt by surface modification treatment, thereby improving the fluidity of the resin melt and simplifying the packaging process; specifically, the surface of the silicon micropowder is modified by taking a silane coupling agent as a surface active agent, polyether modified polysiloxane as a dispersing agent and polydimethylsiloxane as a lubricating agent so as to further improve the surface inertia of the silicon micropowder.
Further, in the aspect of sphericity of the silicon micropowder, as the shape obtained by grinding the raw materials is mostly in a random rhombohedral shape, the sphericity is generally not high, and the improvement effect on the fluidity of a resin melt is limited.
In order to further improve the surface modification effect, the invention also soaks a layer of silica gel layer on the surface of the silicon micropowder on the basis of stabilizing the silicon micropowder at high temperature, the silica gel layer is converted into an aerogel layer after heat treatment, and then polydimethylsiloxane is surface-modified under the vapor deposition condition, so that the liquid holding content of the surface modification solution on the surface of the microsphere can be improved, and the surface lubricating property can be improved.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of surface modified silicon micropowder comprises the following steps:
(1) selecting natural quartz sand with the purity of more than 99.7 percent as a raw material, wherein the selected particle size of the natural quartz sand is 0.1-3mm, firstly washing with water to remove dust and impurities on the surface, then soaking in an acid solution overnight, then washing with deionized water to be neutral, and drying for later use;
(2) transferring the quartz sand prepared in the step (1) into a high-temperature furnace for melting treatment, wherein the melting temperature is 1850 ℃, the melting time is 12-14h, obtaining a high-purity quartz fused mass after the temperature is reduced to room temperature, transferring the quartz fused mass into a ball mill, and adding a ball milling medium for ball milling, wherein the weight ratio of the ball milling medium to the ball milling medium is 1: 2.5: 1.5 of alumina grinding balls with the diameters of 3cm, 4cm and 5cm respectively, wherein the ball milling time is 30min, and the first silicon micro powder with the median particle size of 13-15 mu m and the second silicon micro powder with the median particle size of 8-10 mu m are obtained respectively after ball milling and grading by a grading machine for later use;
(3) adding the second silicon micropowder into an air flow mill for air flow crushing, and separating in a classification area to obtain third silicon micropowder with the median particle size of 2.5-3.5 mu m;
(4) and (3) mixing the first silicon micro powder and the third silicon micro powder according to the weight ratio of 3.25: 1 to obtain graded micro powder;
(5) heating the graded micro powder to 100 ℃, adding 2% of surface modification solution according to the mass ratio, preserving heat, fully stirring and mixing for 1.5h, removing a heat source, and continuing stirring until cooling to obtain the surface modified silicon micro powder;
the surface modification solution comprises the following components in parts by weight: 15 parts of vinyl triethoxysilane, 7 parts of polyether modified polysiloxane, 9 parts of polydimethylsiloxane, 12 parts of toluene and 1.5 parts of deionized water.
Example 2
A preparation method of surface modified silicon micropowder comprises the following steps:
(1) selecting natural quartz sand with the purity of more than 99.7 percent as a raw material, wherein the selected particle size of the natural quartz sand is 0.1-3mm, firstly washing with water to remove dust and impurities on the surface, then soaking in an acid solution overnight, then washing with deionized water to be neutral, and drying for later use;
(2) transferring the quartz sand prepared in the step (1) into a high-temperature furnace for melting treatment, wherein the melting temperature is 1850 ℃, the melting time is 12-14h, obtaining a high-purity quartz fused mass after the temperature is reduced to room temperature, transferring the quartz fused mass into a ball mill, and adding a ball milling medium for ball milling, wherein the weight ratio of the ball milling medium to the ball milling medium is 1: 2.5: 1.5 of alumina grinding balls with the diameters of 3cm, 4cm and 5cm respectively, wherein the ball milling time is 30min, and the first silicon micro powder with the median particle size of 13-15 mu m and the second silicon micro powder with the median particle size of 8-10 mu m are obtained respectively after ball milling and grading by a grading machine for later use;
(3) adding the second silicon micropowder into an air flow mill for air flow crushing, and separating in a classification area to obtain third silicon micropowder with the median particle size of 2.5-3.5 mu m;
(4-1) mixing the first silicon micro powder and the third silicon micro powder according to a weight ratio of 3.25: 1 to obtain graded micro powder;
(4-2) weighing 3-aminopropyltriethoxysilane, dissolving the 3-aminopropyltriethoxysilane in absolute ethanol to obtain a solution with the concentration of 1.5 wt.%, adding 1% deionized water, mixing and stirring uniformly, adding the graded micropowder, stirring at a low speed for reaction overnight, filtering, washing with absolute ethanol, and drying for later use;
(4-3) dispersing the graded micro powder prepared in the step (4-2) in toluene or xylene, adding 3-bromo-2-bromomethylpropionic acid, introducing nitrogen for degassing, adding pentamethyldiethylenetriamine, introducing nitrogen for degassing again, stirring at room temperature for 8-12h, filtering, washing and dispersing in dimethylformamide after the reaction is finished, adding sodium azide, heating to 90-110 ℃, keeping the temperature and stirring for reaction for 24-30h, cooling to room temperature after the reaction is finished, filtering, washing and dispersing in dimethylformamide again, adding propiolic acid under the condition of an ice water bath, adding 4-dimethylaminopyridine as a catalyst, stirring and mixing until the system temperature is stable, stirring while dropwise adding N, N-diisopropylcarbodiimide, stirring and reacting the reaction system under the condition of the dropwise adding in the ice water bath for 8-12h, after the reaction is finished, returning to room temperature, adding the aminated cage-like silsesquioxane, continuously stirring for reaction for 1-3h, filtering, washing and drying to obtain first modified graded micro powder;
wherein the mass ratio of the graded micro powder to the 3-bromo-2-bromomethylpropionic acid to the pentamethyldiethylenetriamine is 100: 3.8: 2.9; the mass ratio of the graded micro powder to the sodium azide, the propiolic acid, the 4-dimethylaminopyridine, the N, N-diisopropylcarbodiimide and the amination polyhedral oligomeric silsesquioxane is 100: 3.2: 1.1: 0.12: 2.3;
(4-4) transferring the first modified graded micro powder into a high-temperature furnace for high-temperature heat treatment, and cooling to room temperature to obtain second modified graded micro powder; the treatment temperature of the high-temperature heat treatment is 1000 ℃, and the treatment time is 4 hours;
(5) heating the second modified graded micro powder to 100 ℃, adding 2% of surface modification solution according to the mass ratio, preserving heat, fully stirring and mixing for 1.5h, removing a heat source, and continuing stirring until cooling to obtain the surface modified silicon micro powder;
the surface modification solution comprises the following components in parts by weight: 15 parts of vinyl triethoxysilane, 7 parts of polyether modified polysiloxane, 9 parts of polydimethylsiloxane, 12 parts of toluene and 1.5 parts of deionized water.
Example 3
A method for preparing surface-modified silica micropowder, which is the same as example 2 except that the second modified graded micropowder further comprises the following processing steps:
s1, weighing methyltriethoxysilane, dissolving the methyltriethoxysilane in absolute ethyl alcohol, adding malonic acid, mixing and stirring uniformly, standing overnight, adding an ammonia solution, stirring for reacting for 5-6h, and continuing to stand for 1-2 days; preparing a dispersion solution after ultrasonic dispersion;
wherein the molar ratio of the solvent to the coupling agent is 32: 1, the molar ratio of the coupling agent to the malonic acid to the ammonia water is 1: 0.01: 0.82;
s2, adding the second modified graded micro powder into the dispersion solution, stirring and mixing for 1-2min, filtering, drying at 60-80 ℃, spreading and transferring into a vacuum drying oven, covering with a polydimethylsiloxane film, heating to 180-200 ℃ in a nitrogen atmosphere, and preserving heat for 1-3 h.
Comparative example 1
In the same way as in example 1, the graded micro powder is prepared from the first silicon micro powder and the third silicon micro powder according to the weight ratio of 2: 1, and mixing the components in a ratio of 1.
Comparative example 2
Example 1 grading of micropowder as described in step (4).
The silica powder described in comparative examples and examples 1-3 and comparative examples 1-2 were used in the same formulation system for underfill performance testing with the following results:
finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of surface modified silica micropowder is characterized by comprising the following steps:
(1) selecting natural quartz sand with the purity of more than 99.7 percent as a raw material, firstly washing with water to remove dust and impurities on the surface, then soaking in an acid solution overnight, then washing with deionized water to be neutral, and drying for later use;
(2) transferring the quartz sand prepared in the step (1) into a high-temperature furnace for melting treatment, cooling to room temperature to obtain a high-purity quartz fused body, transferring the quartz fused body into a ball mill, adding a ball milling medium for ball milling, and grading by a grading machine after ball milling to respectively obtain first silicon micro powder with the median particle size of 13-15 mu m and second silicon micro powder with the median particle size of 8-10 mu m for later use;
(3) adding the second silicon micropowder into an air flow mill for air flow crushing, and separating in a classification area to obtain third silicon micropowder with the median particle size of 2.5-3.5 mu m;
(4) the first silicon micro powder and the third silicon micro powder are mixed according to the weight ratio of (6-7): 2, obtaining graded micro powder;
(5) heating the graded micro powder to 90-120 ℃, adding 1-4% of surface modification solution according to the mass ratio, preserving heat, fully stirring and mixing for 0.5-2h, removing a heat source, and continuously stirring until cooling to obtain the surface modified silicon micro powder.
2. The method for preparing surface-modified silica micropowder according to claim 1, wherein the natural silica sand has a selected particle size of 0.1 to 3 mm.
3. A method for preparing surface modified silica micropowder according to claim 1, wherein the melting temperature of the melting treatment in the step (2) is 1850 ℃ and the melting time is 12-14 h.
4. The method for preparing surface-modified silica micropowder according to claim 1, wherein the ball milling medium is a mixture of a ball milling medium and a silica micropowder, wherein the weight ratio of the ball milling medium is 1: (2-3): (1.5-2) alumina grinding balls with diameters of 3cm, 4cm and 5cm respectively, and performing ball milling for 25-35 min.
5. A method for preparing surface modified silica micropowder according to claim 1, characterized in that the surface modification solution comprises the following components in parts by weight: 12-25 parts of silane coupling agent, 5-9 parts of polyether modified polysiloxane, 6-12 parts of polydimethylsiloxane, 10-15 parts of weak polar solvent and 1-3 parts of deionized water.
6. A method for preparing surface-modified fine silica powder according to claim 5, wherein the silane coupling agent is methyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, γ - (2, 3-glycidoxy) propyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane or N- (β -aminoethyl) - γ -aminopropyltriethoxysilane.
7. A method for preparing surface-modified fine silica powder according to claim 5, wherein the solvent with low polarity is toluene, xylene, gasoline or petroleum ether.
8. A method for preparing surface modified silica micropowder according to claim 1, wherein the grading micropowder of step (4) further comprises the following processing steps:
s1, weighing 3-aminopropyltriethoxysilane, dissolving the 3-aminopropyltriethoxysilane in absolute ethanol to obtain a solution with the concentration of 1-3 wt.%, adding 1% deionized water by volume, mixing and stirring uniformly, adding the graded micropowder, stirring at a low speed for reaction overnight, filtering, washing with absolute ethanol, and drying for later use;
s2, dispersing the graded micro powder prepared in S1 in toluene or xylene, adding 3-bromo-2-bromomethylpropionic acid, introducing nitrogen for degassing, adding pentamethyldiethylenetriamine, introducing nitrogen for degassing again, stirring at room temperature for reaction for 8-12h, filtering, washing and dispersing in dimethylformamide after the reaction is finished, adding sodium azide, heating to 90-110 ℃, keeping the temperature and stirring for reaction for 24-30h, cooling to room temperature after the reaction is finished, filtering, washing and dispersing in dimethylformamide again, adding propiolic acid and 4-dimethylaminopyridine as a catalyst under the condition of an ice water bath, stirring and mixing until the temperature of the system is stable, dropwise adding N, N-diisopropylcarbodiimide while stirring, stirring and reacting the reaction system under the condition of the ice water bath for 8-12h after the dropwise adding is finished, after the reaction is finished, returning to room temperature, adding the aminated cage-like silsesquioxane, continuously stirring for reaction for 1-3h, filtering, washing and drying to obtain first modified graded micro powder;
wherein the mass ratio of the graded micro powder to the 3-bromo-2-bromomethylpropionic acid to the pentamethyldiethylenetriamine is 100: (3-5): (2.6-3.2); the mass ratio of the graded micro powder to the sodium azide, the propiolic acid, the 4-dimethylaminopyridine, the N, N-diisopropylcarbodiimide and the amination polyhedral oligomeric silsesquioxane is 100: (2.6-3.6): (1-1.2): (0.1-0.14): (2.3-2.5);
s3, transferring the first modified graded micro powder into a high-temperature furnace for high-temperature heat treatment, and cooling to room temperature to obtain second modified graded micro powder; the treatment temperature of the high-temperature heat treatment is 800-1200 ℃, and the treatment time is 1-6 h.
9. A method for preparing surface modified silica micropowder according to claim 8, wherein the second modified graded micropowder further comprises the following processing steps:
s1, weighing the coupling agent, dissolving the coupling agent in the solvent, adding malonic acid, mixing and stirring uniformly, standing overnight, adding an ammonia solution, stirring for reaction for 5-6h, and continuing to stand for 1-2 days; preparing a dispersion solution after ultrasonic dispersion;
wherein the coupling agent is methyltrimethoxysilane or methyltriethoxysilane, and the solvent is methanol or ethanol; the molar ratio of the solvent to the coupling agent is (30-35): 1, the molar ratio of the coupling agent to the malonic acid to the ammonia water is 1: (0.01-0.02): (0.8-1);
s2, adding the second modified graded micro powder into the dispersion solution, stirring and mixing for 1-2min, filtering, drying at 60-80 ℃, spreading and transferring into a vacuum drying oven, covering with a polydimethylsiloxane film, heating to 180-200 ℃ in a nitrogen atmosphere, and preserving heat for 1-3h to obtain third modified graded micro powder.
10. The surface-modified fine silica powder produced by the production method according to any one of claims 1 to 9.
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| CN115974085A (en) * | 2022-02-14 | 2023-04-18 | 连云港威晟硅材料有限公司 | Surface-modified silicon micropowder and preparation method thereof |
| CN116285474A (en) * | 2023-03-29 | 2023-06-23 | 安徽中科思沃生物科技有限公司 | Aldehyde-free putty and preparation method thereof |
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| CN117326563B (en) * | 2023-09-28 | 2024-03-22 | 吉安豫顺新材料有限公司 | Preparation method and system of low-impurity silicon micro powder for vehicle-mounted copper-clad plate |
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