Organic silicon modified epoxy resin and preparation method thereof

Abstract

The preparation method comprises the following steps: uniformly dispersing graphene oxide in a solvent, adding a sodium hydrogen sulfate solution, dispersing, adjusting the pH value to 9-11 by using an alkaline solution, adding meta-aluminate, dispersing, adding the sodium hydrogen sulfate solution again, dispersing, adjusting the pH value to 9-11 by using the alkaline solution, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, adding the sodium hydrogen sulfate solution, dispersing, after stirring for a period of time, standing, washing and drying to obtain a graphene oxide-aluminum oxide precursor; carrying out surface treatment on the graphene oxide-aluminum oxide precursor by using an organic silicon compound, and carrying out curing and drying to obtain an organic silicon-graphene oxide-aluminum oxide precursor; mixing the organic silicon-graphene oxide-aluminum oxide precursor with epoxy resin, heating to a molten state, and preserving heat in the molten state to obtain the modified epoxy resin doped with organic silicon-graphene oxide-aluminum oxide. The embodiment of the invention enhances the heat-conducting property and mechanical property of the modified epoxy resin.

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic packaging, and particularly relates to a silicone-modified epoxy resin and a preparation method thereof. Background Art

[0002] With the rapid development of fields such as artificial intelligence, 5G communication, and high performance computing (HPC), semiconductor packaging technology has been continuously evolving towards high density, miniaturization, and high reliability. Especially for the use in fields such as new energy vehicles and communications under extreme conditions, higher requirements are put forward for the wear resistance, corrosion resistance, and anti-pollution properties of plastic packaging materials, and for their ability to still maintain good performance under harsh environments such as high temperature, high pressure, strong acid, and strong base. Summary of the Invention

[0003] In order to solve the above problems existing in the prior art, the present invention provides a silicone-modified epoxy resin and a preparation method thereof. The technical problems to be solved by the present invention are achieved through the following technical solutions:

[0004] An embodiment of the present invention provides a preparation method of a silicone-modified epoxy resin, including the steps:

[0005] S1. Uniformly disperse graphene oxide in a solvent, add a sodium bisulfate solution for dispersion, then adjust the pH value to 9 - 11 with an alkaline solution, and then add a meta-aluminate for dispersion. After dispersion, add the sodium bisulfate solution again for dispersion and adjust the pH value to 9 - 11 with the alkaline solution. Stir for a period of time to make the meta-aluminate react ultrasonically with graphene oxide, and then let it stand, wash, and dry to obtain a graphene oxide-aluminum oxide precursor;

[0006] S2. Surface-treat the graphene oxide-aluminum oxide precursor with an organosilicon compound, and carry out curing and drying to obtain an organosilicon-graphene oxide-aluminum oxide precursor;

[0007] S3. Mix the organosilicon-graphene oxide-aluminum oxide precursor with an epoxy resin and heat it to a molten state, and keep it at the molten state to obtain a modified epoxy resin doped with organosilicon-graphene oxide-aluminum oxide, and the modified epoxy resin is used as a thermally conductive epoxy plastic packaging material for semiconductor structure packaging.

[0008] In an embodiment of the present invention, in step S1, the feeding mass ratio of the graphene oxide to the meta-aluminate is 1:50 - 1:150.

[0009] In one embodiment of the present invention, in step S1, the solvent includes one or more of water, ethanol, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethylene glycol, anhydrous acetonitrile, dichloromethane, and carbon tetrachloride;

[0010] the basic solution includes one or more of sodium hydroxide solution, ammonia water, and triethylamine;

[0011] the aluminate includes one or more of sodium aluminate and potassium aluminate;

[0012] the solvent for washing includes any one or more of methanol, ethanol, ethylene glycol, water, acetonitrile, and chloroform.

[0013] In one embodiment of the present invention, in step S1, the temperature of the ultrasonic reaction is 25 - 85 °C, and the time is 4 - 7 h.

[0014] In one embodiment of the present invention, in step S1, the drying temperature is 35 - 75 °C.

[0015] In one embodiment of the present invention, in step S2, the organosilicon compound includes one or more of sodium methyl silicate, tetramethylammonium silicate, and potassium methyl silicate.

[0016] In one embodiment of the present invention, in step S3, the structural formula of the epoxy resin is:

[0017]

[0018] In one embodiment of the present invention, in step S3, the mass percentage of the organosilicon-aluminum oxide-graphene oxide precursor is 15% - 30%, and the mass percentage of the epoxy resin is 70% - 85%.

[0019] In one embodiment of the present invention, in step S3, the temperature for heating to the molten state is 150 - 280 °C, and the holding time in the molten state is 2.5 - 6.0 h.

[0020] Another embodiment of the present invention provides an organosilicon-modified epoxy resin prepared by the preparation method as described in the above embodiment.

[0021] Compared with the prior art, the beneficial effects of the present invention:

[0022] 1. The present invention reacts graphene oxide with aluminates through ultrasonic reaction to obtain a graphene oxide-aluminum oxide precursor, and then modifies it with an organosilicon surfactant to obtain an organosilicon-graphene oxide-aluminum oxide precursor. Among them, aluminum oxide has good mechanical properties, graphene has good thermal conductivity, and organosilicon has good corrosion resistance and anti-pollution properties. The three have good interfacial compatibility, and the formed precursor has good thermal conductivity, corrosion resistance and anti-pollution properties. When doped with epoxy resin, the thermal conductivity of the modified epoxy resin is significantly enhanced, so that the modified epoxy resin can provide an additional heat dissipation path when applied to semiconductor structure encapsulation, meeting the requirements of electronic packaging for high thermal conductivity packaging materials. At the same time, the modified epoxy resin has good thermal properties and mechanical properties, which is conducive to the high integration, high density and green development of electronic packaging materials;

[0023] 2. The preparation method of the present invention is simple, the solvent is easy to obtain, the reaction temperature is relatively mild, the synthesis time is short, there are no by-products, and the post-treatment is simple. The obtained product has excellent thermal conductivity, is environmentally friendly and pollution-free, and conforms to the development direction of green chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a process schematic diagram of a preparation method of an organosilicon-modified epoxy resin provided by an embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] The following further describes the present invention in detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.

[0026] Please refer to Figure 1 , Figure 1 It is a process schematic diagram of a preparation method of an organosilicon-modified epoxy resin provided by an embodiment of the present invention. The preparation method includes the steps:

[0027] S1. Uniformly disperse graphene oxide in a solvent, add a sodium bisulfate solution for dispersion, then adjust the pH value to 9-11 with an alkaline solution, and then add aluminates for dispersion. After dispersion, add the sodium bisulfate solution again for dispersion and adjust the pH value to 9-11 with an alkaline solution. Stir for a period of time to make the aluminates react with graphene oxide through ultrasonic reaction, and then let it stand, wash and dry to obtain a graphene oxide-aluminum oxide precursor.

[0028] Specifically, uniformly disperse graphene oxide in a solvent. The solvents for dispersing graphene oxide include any one of water, ethanol, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethylene glycol, anhydrous acetonitrile, dichloromethane, carbon tetrachloride or a mixed solvent of any ratio thereof.

[0029] After the graphene oxide is dispersed, weak acids such as low-concentration dilute hydrochloric acid and sodium bicarbonate can be added to remove impurities on the surface of the graphene oxide; since the graphene oxide has been washed with alcohol, when adding acid, the strength of the acid should be controlled to remove slightly.

[0030] Then, add a sodium bisulfate solution for ultrasonic dispersion, and after dispersion, add an alkaline solution to adjust the pH value to 9-11. The alkaline solution can be one or more of sodium hydroxide solution, ammonia water, and triethylamine.

[0031] Next, add aluminates for ultrasonic dispersion. The feeding mass ratio of graphene oxide to the aluminates is 1:50-1:150. The aluminates include one or more of sodium aluminate and potassium aluminate. After the aluminates are dispersed, add the sodium bisulfate solution again, and after dispersion in the sodium bisulfate solution, adjust the pH value to 9-11 with an alkaline solution, and stir for a period of time to make the aluminates react ultrasonically with the graphene oxide. The temperature of the ultrasonic reaction is 25-85 °C, and the time is 4-7 h.

[0032] After that, let it stand, wash, and dry. The washing solvent includes any one of methanol, ethanol, ethylene glycol, water, acetonitrile, and chloroform or any mixture of them in any proportion. The drying temperature is 35-75 °C to obtain a graphene oxide-aluminum oxide precursor.

[0033] S2. Surface-treat the graphene oxide-aluminum oxide precursor with an organosilicon compound, and carry out curing and drying to obtain an organosilicon-graphene oxide-aluminum oxide precursor.

[0034] Specifically, wash the surface of the graphene oxide-aluminum oxide precursor obtained in step S1 with deionized water and then dry it. Add an organosilicon compound and stir to make the organosilicon compound cover the surface of the graphene oxide-aluminum oxide precursor through reaction to obtain a solid, and carry out curing and drying to obtain an organosilicon-graphene oxide-aluminum oxide precursor.

[0035] In the above steps, the organosilicon compound includes one or more of sodium methyl silicate, tetramethylammonium silicate, and potassium methyl silicate. The curing conditions are: curing with benzoyl peroxide (BPO) at 130-150 °C. For example, the curing temperature is 140 °C. The drying conditions are: drying in an oven at 200 °C for 8 h.

[0036] S3. Mix the organosilicon-graphene oxide-aluminum oxide precursor with epoxy resin and heat it up to the molten state, and keep it at the molten state to obtain a modified epoxy resin doped with organosilicon-graphene oxide-aluminum oxide. The modified epoxy resin is used as a thermally conductive epoxy encapsulation material for semiconductor structure encapsulation.

[0037] Specifically, the mass percentage of the silicone-aluminum oxide-graphene oxide precursor is 15% to 30%, and the mass percentage of the epoxy resin is 70% to 85%. The temperature for heating to the molten state is 150 to 280 °C, and the holding time in the molten state is 2.5 to 6.0 h. Among them, the structural formula of the epoxy resin is:

[0038]

[0039] This embodiment also provides a silicone-modified epoxy resin, which is a modified epoxy resin doped with silicone-graphene oxide-aluminum oxide and is prepared by the above preparation method.

[0040] For the convenience of understanding the present invention, the following examples are enumerated. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0041] Example 1

[0042] S1. Add 0.32 g of graphene oxide to a 500 ml glass bottle, add 200 ml of water, and disperse it by ultrasonic wave. After dispersion, add 25.30 g of sodium bisulfate solution, and after ultrasonic dispersion of the sodium bisulfate solution, add sodium hydroxide to adjust the pH to 11. Then, weigh 24.61 g of sodium aluminate and add it. After the sodium aluminate is dispersed, add 27.36 g of sodium bisulfate solution, and after ultrasonic dispersion, add sodium hydroxide to adjust the pH to 11. Stir at 55 °C for 6 h to make sodium aluminate react with graphene oxide. After the reaction is completed, let it stand to obtain a white precipitate. Finally, wash it with deionized water and absolute ethanol respectively, and dry it at 55 °C to obtain 20.15 g of graphene oxide-aluminum oxide precursor.

[0043] S2. Weigh 20.00 g of graphene oxide-aluminum oxide precursor, wash the surface with deionized water and then dry it. Add sodium methyl silicate and stir to obtain a solid. Cure it with benzoyl peroxide (BPO) at 140 °C, and then post-treat it by drying in an oven at 200 °C for 8 h to obtain a sodium methyl silicate-graphene oxide-aluminum oxide precursor.

[0044] S3. Weigh the sodium methyl silicate-graphene oxide-aluminum oxide precursor with a mass percentage of 20% and the epoxy resin with a mass percentage of 80%. Grind the weighed epoxy resin into a powder and mix it with the powdered sodium methyl silicate-graphene oxide-aluminum oxide precursor. Heat the mixed powder to 200 °C to make the mixed powder reach the molten state, hold it at the molten state for 2.5 h, and cool it down to obtain a modified epoxy resin doped with sodium methyl silicate-graphene oxide-aluminum oxide.

[0045] Example 2

[0046] S1. Add 0.25 g of graphene oxide to a 500 ml glass bottle, add 200 ml of water, and disperse it by ultrasonic wave. After dispersion, add 21.56 g of sodium bisulfate solution. After ultrasonic dispersion of the sodium bisulfate solution, add ammonia water to adjust the pH to 10. Then, weigh 18.42 g of potassium meta-aluminate and add it. After the potassium meta-aluminate is dispersed, add 24.87 g of sodium bisulfate solution. After ultrasonic dispersion, add ammonia water to adjust the pH to 10. Stir at 85 °C for 5 h and then let it stand to obtain a white precipitate. Finally, wash and dry it with deionized water and absolute ethanol respectively, and the drying temperature is 35 °C to obtain 18.52 g of graphene oxide-aluminum oxide precursor.

[0047] S2. Weigh 15.00 g of graphene oxide-aluminum oxide precursor, wash the surface with deionized water and then dry it. Add tetramethylammonium silicate and stir to obtain a solid. Cure it with benzoyl peroxide (BPO) at 140 °C, and then treat it by drying in an oven at 200 °C for 8 h to obtain a tetramethylammonium silicate-graphene oxide-aluminum oxide precursor.

[0048] S3. Weigh the tetramethylammonium silicate-graphene oxide-aluminum oxide precursor with a mass percentage of 18% and epoxy resin with a mass percentage of 72%. Grind the weighed epoxy resin into powder and mix it with the powdered tetramethylammonium silicate-graphene oxide-aluminum oxide. Heat the mixed powder to 200 °C to make the mixed powder reach the molten state, keep it at the molten state for 2.5 h, and cool it down to obtain a modified epoxy resin doped with tetramethylammonium silicate-graphene oxide-aluminum oxide.

[0049] Example 3

[0050] S1. Add 0.51 g of graphene oxide to a 500 ml glass bottle, add 350 ml of water, and disperse it by ultrasonic wave. After dispersion, add 32.75 g of sodium bisulfate solution. After ultrasonic dispersion of the sodium bicarbonate solution, add triethylamine to adjust the pH to 9. Weigh 40.25 g of potassium meta-aluminate. After dispersion, add 35.57 g of sodium bisulfate solution. After ultrasonic dispersion, add triethylamine to adjust the pH to 9. Stir at 25 °C for 7 h and then let it stand to obtain a white precipitate. Wash and dry it with deionized water and absolute ethanol respectively to obtain 35.82 g of graphene oxide-aluminum oxide precursor.

[0051] S2. Weigh 30.00 g of graphene oxide-aluminum oxide precursor, wash the surface with deionized water and then dry it. Add potassium methyl silicate and stir to obtain a solid. Cure it with benzoyl peroxide (BPO) at 140 °C, and then treat it by drying in an oven at 200 °C for 8 h to obtain a precursor of potassium methyl silicate-graphene oxide-aluminum oxide.

[0052] S3. Weigh the precursor potassium methyl silicate-graphene oxide-aluminum oxide with a mass percentage of 20% and epoxy resin with a mass percentage of 80%. Grind the weighed epoxy resin into powder and mix it with the powdered potassium methyl silicate-graphene oxide-aluminum oxide. Heat the mixed powder to 210 °C to make the mixed powder reach the molten state, keep it at the molten state for 2.5 h, and then cool it down to obtain the modified epoxy resin doped with potassium methyl silicate-graphene oxide-aluminum oxide.

[0053] Al2O3 is a compound with high hardness and can effectively improve the mechanical strength of epoxy resin. However, its specific surface area is large and there are micropores on the surface, which will further affect the wear resistance, corrosion resistance and anti-pollution properties of epoxy resin materials. Therefore, by preparing Al2O3 composite materials to improve the thermal conductivity, density and smoothness of its surface, the wear resistance, corrosion resistance and anti-pollution properties of epoxy resin can be further improved. In this example, graphene oxide and aluminate are subjected to ultrasonic reaction to obtain a graphene oxide-aluminum oxide precursor, and then modified with an organosilicon surfactant to obtain an organosilicon-graphene oxide-aluminum oxide precursor. Among them, alumina has good mechanical properties, graphene has good thermal conductivity, and organosilicon has good corrosion resistance and anti-pollution properties. The three have good interfacial compatibility, and the formed precursor has good thermal conductivity, corrosion resistance and anti-pollution properties. Doped with epoxy resin, it significantly enhances the thermal conductivity of the modified epoxy resin, enabling the modified epoxy resin to provide an additional heat dissipation path when applied to semiconductor structure encapsulation, meeting the requirements of electronic packaging for high-thermal-conductivity packaging materials. At the same time, the modified epoxy resin has good thermal properties and mechanical properties, which is conducive to the high-integration, high-density and green development of electronic packaging materials;

[0054] The preparation method of this example is simple, the solvent is easy to obtain, the reaction temperature is relatively mild, the synthesis time is short, there are no by-products, and the post-treatment is simple. The obtained product has excellent thermal conductivity, is environmentally friendly and pollution-free, and conforms to the development direction of green chemistry.

[0055] The above content is a further detailed description of the present invention in combination with specific preferred embodiments. It cannot be determined that the specific implementation of the present invention is only limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, without departing from the concept of the present invention, several simple deductions or substitutions can still be made, which should all be regarded as belonging to the protection scope of the present invention.

Claims

1. A preparation method of a silicone-modified epoxy resin, characterized in that, Including the steps: S1. Uniformly disperse graphene oxide in a solvent, add a sodium bisulfate solution for dispersion, then adjust the pH value to 9 - 11 with an alkaline solution, and then add a meta-aluminate for dispersion. After dispersion, add the sodium bisulfate solution again for dispersion and adjust the pH value to 9 - 11 with the alkaline solution. Stir for a period of time to enable the ultrasonic reaction of the meta-aluminate and graphene oxide. Then let it stand, wash, and dry to obtain a graphene oxide-aluminum oxide precursor; S2. Surface-treat the graphene oxide-aluminum oxide precursor with an organosilicon compound, and carry out curing and drying to obtain an organosilicon-graphene oxide-aluminum oxide precursor; S3. Mix the organosilicon-graphene oxide-aluminum oxide precursor with an epoxy resin and heat it to a molten state, and keep it at the molten state to obtain a modified epoxy resin doped with organosilicon-graphene oxide-aluminum oxide, and the modified epoxy resin is used as a thermally conductive epoxy encapsulation material for semiconductor structure encapsulation.

2. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S1, the feeding mass ratio of the graphene oxide to the meta-aluminate is 1:50 - 1:

150.

3. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S1, the solvent includes one or more of water, ethanol, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethylene glycol, anhydrous acetonitrile, dichloromethane, carbon tetrachloride; The alkaline solution includes one or more of sodium hydroxide solution, ammonia water, triethylamine; The meta-aluminate includes one or more of sodium meta-aluminate, potassium meta-aluminate; The solvent for washing includes any one or more of methanol, ethanol, ethylene glycol, water, acetonitrile, chloroform.

4. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S1, the temperature of the ultrasonic reaction is 25 - 85 °C, and the time is 4 - 7 h.

5. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S1, the temperature of drying is 35 - 75 °C.

6. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S2, the organosilicon compound includes one or more of sodium methyl silicate, tetramethylammonium silicate, potassium methyl silicate.

7. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S3, the structural formula of the epoxy resin is:

8. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S3, the mass percentage of the organosilicon-aluminum oxide-graphene oxide precursor is 15% - 30%, and the mass percentage of the epoxy resin is 70% - 85%.

9. The preparation method of the silicone-modified epoxy resin according to claim 1, characterized in that, In step S3, the temperature for heating to the molten state is 150 - 280 °C, and the time for keeping at the molten state is 2.5 - 6.0 h.

10. A silicone-modified epoxy resin, characterized in that, Prepared by the preparation method according to any one of claims 1 - 9.

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