Organosilicon-modified dual-network cross-linked epoxy resin as well as preparation method and application thereof

Abstract

The invention provides organic silicon modified dual-network cross-linked epoxy resin as well as a preparation method and application thereof, and belongs to the technical field of epoxy resin. The organic silicon modified dual-network cross-linked epoxy resin provided by the invention has an organic silicon modified epoxy group and maleimide group dual-cross-linked structure based on a naphthalene ring skeleton structure, and an organic silicon structural unit is introduced on the basis of an early-stage high-heat-resistance and high-toughness dual-cross-linked epoxy resin molecular structure; the heat resistance is further improved, the toughness is improved, the internal stress is reduced, meanwhile, the contradictory relationship among the heat resistance, the toughness and the viscosity of the epoxy resin is improved, and the high-heat-resistance and high-toughness polyfunctional epoxy resin is obtained so as to meet the application requirements of a new generation of semiconductor sealing materials. The organic silicon modified dual-network cross-linked epoxy resin provided by the invention has the characteristics of high heat resistance, high toughness and high glass-transition temperature of a cured product, and can improve the structural stability and service reliability of a packaged device when being used as a semiconductor packaging material.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resins, and in particular to an organosilicon-modified double-network cross-linked epoxy resin and a preparation method and application thereof. Background Art

[0002] In the past 20 years, silicon carbide (SiC) has attracted more and more attention as a wide bandgap power device. SiC has a larger bandgap width and high electron saturation velocity, and its devices have lower leakage current, higher operating temperature, lower on-resistance, higher switching frequency and better radiation resistance. However, these excellent characteristics of SiC devices can only be perfectly displayed through packaging and circuit systems to achieve efficient and reliable connection of power and signals. Among them, high-temperature packaging materials are the basis for ensuring the reliable operation of SiC devices at high temperatures. Therefore, research and development of packaging materials with high temperature resistance, high thermal conductivity, high voltage resistance and excellent dielectric properties is a major difficulty in device packaging design.

[0003] Epoxy resin has excellent heat resistance, chemical resistance, electrical insulation, sealing, excellent mechanical properties, small shrinkage, environmental friendliness and good processing operability. It is currently the most widely used type of packaging material. As advanced packaging develops towards high-density integration, high-power load and miniaturization, the packaging structure becomes more complex; correspondingly, more challenging packaging structures also put forward higher requirements for their corresponding materials. The maximum operating temperature of traditional epoxy resin-based packaging insulation materials is generally 175°C, which can no longer meet the requirements of SiC devices for higher temperatures (200-300°C), high voltage and high frequency. If rigid groups (biphenyl, naphthalene ring, etc.) are introduced into the molecular structure of epoxy resin or the cross-linking density is increased, the heat resistance of epoxy resin can be improved to a certain extent, but at the same time, the increase in molecular segment rigidity or cross-linking density leads to an increase in the viscosity of epoxy resin and a decrease in the toughness of the cured product, which in turn limits its application in the new generation of semiconductor packaging materials. Therefore, how to further improve the heat resistance level of epoxy resin while reducing viscosity and improving brittleness has become the key to improving the structural stability and service reliability of packaged devices. Summary of the invention

[0004] In view of this, the present invention aims to provide an organosilicon-modified double network cross-linked epoxy resin and a preparation method and application thereof. The organosilicon-modified double network cross-linked epoxy resin provided by the present invention has good heat resistance and toughness.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a silicone-modified double-network cross-linked epoxy resin having a structure shown in Formula 1:

[0007]

[0008] In formula 1, m:n=1 to 10:1.

[0009] Preferably, the epoxy equivalent of the organosilicon-modified double-network cross-linked epoxy resin is 300 to 400 g / mol.

[0010] The present invention provides a method for preparing the above-mentioned organosilicon-modified double-network cross-linked epoxy resin, comprising the following steps:

[0011] (1) mixing 5-amino-1-naphthol, maleic anhydride and a first organic solvent, and performing an amidation reaction to obtain 5-maleimido-1-naphthol;

[0012] (2) mixing the 5-maleimido-1-naphthol, hexaphenyl fused-ring hexasiloxane disilanol, a catalyst and a second organic solvent, and performing a hydroxyl dehydration condensation reaction to obtain organosilanol-modified 5-maleimido-1-naphthol;

[0013] (3) mixing 5-maleimido-1-naphthol, organosilanol-modified 5-maleimido-1-naphthol, paraformaldehyde and a third organic solvent to carry out a phenol-formaldehyde condensation reaction to obtain a phenol-formaldehyde condensation reaction product;

[0014] (4) mixing the phenolic condensation reaction product with epichlorohydrin, a cosolvent, a phase transfer catalyst, and sodium hydroxide to carry out an epoxy ring-opening-closing condensation reaction to obtain an organosilicon-modified double-network cross-linked epoxy resin.

[0015] Preferably, the catalyst in step (2) is dibutyltin dilaurate;

[0016] The polymerization degree of the paraformaldehyde in the step (3) is 8 to 10;

[0017] The phase transfer catalyst in step (4) is one or more of tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and ethyltriphenylammonium bromide.

[0018] Preferably, the cosolvent is isopropanol;

[0019] The first organic solvent and the third organic solvent are independently one or more of toluene, xylene and methyl isobutyl ketone;

[0020] The second organic solvent is one or more of cyclohexanone, butyl acetate, N,N-dimethylformamide and N,N-dimethylacetamide.

[0021] Preferably, in step (1), the mass ratio of 5-amino-1-naphthol to maleic anhydride is 1.2 to 1.6:1;

[0022] The ratio of the mass of the first organic solvent to the total mass of 5-amino-1-naphthol and maleic anhydride is 1.5 to 2:1;

[0023] The temperature of the amidation reaction is 70-160° C. and the time is 2-8 hours.

[0024] Preferably, in the step (2), the molar ratio of the hexaphenyl fused ring hexasiloxane disilanol to 5-maleimido-1-naphthol is 0.2 to 0.8:1;

[0025] The mass of the catalyst is 0.5-2% of the total mass of 5-maleimido-1-naphthol and hexaphenyl fused ring hexasiloxane disilanol;

[0026] The ratio of the mass of the second organic solvent to the total mass of 5-maleimido-1-naphthol and hexaphenyl fused-ring hexasiloxane disilanol is 5 to 10:1;

[0027] The temperature of the hydroxyl dehydration condensation reaction is 140-150° C. and the time is 2-4 hours.

[0028] Preferably, in the step (3), the molar ratio of the organosilanol-modified 5-maleimido-1-naphthol to 5-maleimido-1-naphthol is 0.2 to 1:1;

[0029] The mass of the polyformaldehyde is 10 to 50% of the total mass of the organosilanol-modified 5-maleimide-1-naphthol and 5-maleimide-1-naphthol;

[0030] The ratio of the mass of the third organic solvent to the total mass of 5-maleimido-1-naphthol, organosilanol-modified 5-maleimido-1-naphthol, and paraformaldehyde is 2 to 5:1;

[0031] The temperature of the phenol-formaldehyde condensation reaction is 100-120° C., and the time is 2-8 hours.

[0032] Preferably, in the step (4), the ratio of the mass of epichlorohydrin to the total mass of the organosilanol-modified 5-maleimido-1-naphthol and 5-maleimido-1-naphthol is 1 to 1.2:1;

[0033] The amount of the co-solvent is 0 to 30% of the total mass of the organosilanol-modified 5-maleimide-1-naphthol and 5-maleimide-1-naphthol;

[0034] The mass of the phase transfer catalyst is 1 to 5% of the total mass of the organosilanol-modified 5-maleimide-1-naphthol, 5-maleimide-1-naphthol and paraformaldehyde;

[0035] The mass of the sodium hydroxide is 5 to 15% of the total mass of the organosilanol-modified 5-maleimido-1-naphthol, 5-maleimido-1-naphthol and paraformaldehyde;

[0036] The temperature of the epoxy ring-opening-closing condensation reaction is 45-125° C. and the time is 3-9 hours.

[0037] The present invention provides the use of the organosilicon-modified double-network cross-linked epoxy resin as a semiconductor packaging material.

[0038] After adopting the above technical solution, the beneficial effects of the present invention are as follows:

[0039] The present invention provides a silicone-modified double network cross-linked epoxy resin having a structure shown in Formula 1, wherein m:n=1 to 10:1. The silicone-modified double network cross-linked epoxy resin provided by the present invention is a silicone-modified double cross-linked structure of epoxy and maleimide groups based on a naphthalene ring skeleton structure. On the basis of the molecular structure of the previous high heat-resistant and tough double cross-linked epoxy resin, the silicone structural unit is introduced to further improve the heat resistance, improve the toughness, and reduce the internal stress. At the same time, the contradictory relationship between the heat resistance, toughness and viscosity of the epoxy resin is improved, and a high heat-resistant and tough multifunctional epoxy resin is obtained to meet the application requirements of a new generation of semiconductor sealing materials. The silicone-modified double network cross-linked epoxy resin provided by the present invention has the characteristics of high heat resistance, high toughness, and high glass transition temperature of the cured product. When used as a semiconductor packaging material, it can improve the structural stability and service reliability of the packaging device.

[0040] The present invention provides a method for preparing the organosilicon-modified double-network cross-linked epoxy resin. The method is simple to operate, low in cost, and easy to realize industrialized mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a synthetic route for silicone-modified double-network cross-linked epoxy resin. DETAILED DESCRIPTION

[0042] The present invention provides a silicone-modified double-network cross-linked epoxy resin having a structure shown in Formula 1:

[0043]

[0044] In Formula 1, m:n=1 to 10:1, preferably 2 to 8:1, and more preferably 4 to 6:1.

[0045] In the present invention, the epoxy equivalent of the organosilicon-modified double-network cross-linked epoxy resin is preferably 300 to 400 g / mol, more preferably 350 g / mol.

[0046] The present invention provides a method for preparing the above-mentioned organosilicon-modified double-network cross-linked epoxy resin, comprising the following steps:

[0047] (1) mixing 5-amino-1-naphthol, maleic anhydride and a first organic solvent, and performing an amidation reaction to obtain 5-maleimido-1-naphthol;

[0048] (2) mixing the 5-maleimido-1-naphthol, hexaphenyl fused-ring hexasiloxane disilanol, a catalyst and a second organic solvent, and performing a hydroxyl dehydration condensation reaction to obtain organosilanol-modified 5-maleimido-1-naphthol;

[0049] (3) mixing 5-maleimido-1-naphthol, organosilanol-modified 5-maleimido-1-naphthol, paraformaldehyde and a third organic solvent to carry out a phenol-formaldehyde condensation reaction to obtain a phenol-formaldehyde condensation reaction product;

[0050] (4) mixing the phenolic condensation reaction product with epichlorohydrin, a cosolvent, a phase transfer catalyst, and sodium hydroxide to carry out an epoxy ring-opening-closing condensation reaction to obtain an organosilicon-modified double-network cross-linked epoxy resin.

[0051] The present invention mixes 5-amino-1-naphthol, maleic anhydride and a first organic solvent, and performs an amidation reaction to obtain 5-maleimide-1-naphthol. In the present invention, the first solvent is preferably one or more of toluene, xylene and methyl isobutyl ketone.

[0052] In the present invention, the mass ratio of 5-amino-1-naphthol to maleic anhydride is preferably 1.2-1.6:1, more preferably 1.3-1.5:1; the ratio of the mass of the first organic solvent to the total mass of 5-amino-1-naphthol and maleic anhydride is 1.5-2:1, more preferably 1.6-1.8:1.

[0053] In the present invention, the mixing and amidation reaction are preferably carried out in a reactor equipped with nitrogen protection and a condensation device, and the mixing is preferably carried out by stirring.

[0054] In the present invention, the temperature of the amidation reaction is preferably 70 to 160° C., more preferably 100 to 130° C., and the time is preferably 2 to 8 hours, more preferably 4 to 6 hours.

[0055] After the amidation reaction, the present invention preferably performs reduced pressure distillation on the amidation reaction product to remove the organic solvent.

[0056] The present invention mixes the 5-maleimido-1-naphthol, hexaphenyl fused-ring hexasiloxane disilanol, a catalyst and a second organic solvent, and performs a hydroxyl dehydration condensation reaction to obtain organosilanol-modified 5-maleimido-1-naphthol. In the present invention, the catalyst is preferably dibutyltin dilaurate, and the second organic solvent is preferably one or more of cyclohexanone, butyl acetate, N,N-dimethylformamide and N,N-dimethylacetamide.

[0057] In the present invention, the structural formula of the hexaphenyl fused ring hexasiloxane disilanol is shown in Formula 2:

[0058]

[0059] In the present invention, the source of the hexaphenyl-fused-ring hexasiloxane disilanol is commercially available. As a specific embodiment of the present invention, the hexaphenyl-fused-ring hexasiloxane disilanol is purchased from Xiameter Dow Corning, model number RSN-8016.

[0060] In the present invention, the molar ratio of the hexaphenyl fused-ring hexasiloxane disilanol to 5-maleimido-1-naphthol is preferably 0.2 to 0.8:1, and more preferably 0.4 to 0.6:1.

[0061] In the present invention, the mass of the catalyst is preferably 0.5-2% of the total mass of 5-maleimido-1-naphthol and hexaphenyl fused-ring hexasiloxane disilanol, and more preferably 1-1.5%.

[0062] In the present invention, the ratio of the mass of the second organic solvent to the total mass of 5-maleimido-1-naphthol and hexaphenyl-fused-ring hexasiloxane disilanol is preferably 5 to 10:1, more preferably 6 to 8:1.

[0063] In the present invention, the mixing and hydroxyl dehydration condensation reaction are preferably carried out in a reactor equipped with nitrogen protection and a condensation device, and the mixing is preferably carried out by stirring.

[0064] In the present invention, the temperature of the hydroxyl dehydration condensation reaction is preferably 140-150° C., more preferably 145° C., and the time is preferably 2-4 h, more preferably 3 h.

[0065] In the present invention, after the hydroxyl dehydration condensation reaction, the present invention preferably performs reduced pressure distillation on the obtained hydroxyl dehydration condensation reaction product to remove the organic solvent.

[0066] The present invention mixes 5-maleimide-1-naphthol, organosilanol-modified 5-maleimide-1-naphthol, polyformaldehyde and a third organic solvent, and performs a phenol-formaldehyde condensation reaction to obtain a phenol-formaldehyde condensation reaction product. In the present invention, the third organic solvent is preferably one or more of toluene, xylene and methyl isobutyl ketone. In the present invention, the polymerization degree of the polyformaldehyde is preferably 8 to 10.

[0067] In the present invention, the molar ratio of the organosilanol-modified 5-maleimido-1-naphthol to 5-maleimido-1-naphthol is preferably 0.2 to 1:1, and more preferably 0.5 to 0.8:1.

[0068] In the present invention, the mass of the paraformaldehyde is preferably 10 to 50% of the total mass of the organosilanol-modified 5-maleimido-1-naphthol and 5-maleimido-1-naphthol, and more preferably 20 to 40%.

[0069] In the present invention, the ratio of the mass of the third organic solvent to the total mass of 5-maleimido-1-naphthol, organosilanol-modified 5-maleimido-1-naphthol and paraformaldehyde is preferably 2-5:1, more preferably 3-4:1.

[0070] In the present invention, the mixing and phenolic condensation reaction are preferably carried out in a reactor equipped with nitrogen protection and a condensation device, and the mixing is preferably carried out by stirring.

[0071] In the present invention, the temperature of the phenol-formaldehyde condensation reaction is preferably 100-120° C., more preferably 110° C., and the time is preferably 2-8 h, more preferably 4-6 h.

[0072] In the present invention, after the phenol-formaldehyde condensation reaction, the present invention preferably cools the obtained phenol-formaldehyde condensation reaction product.

[0073] The present invention mixes the phenolic condensation reaction product with epichlorohydrin, a cosolvent, a phase transfer catalyst, and sodium hydroxide to carry out an epoxy ring-opening-closing condensation reaction to obtain an organosilicon-modified double network cross-linked epoxy resin. In the present invention, the phase transfer catalyst is preferably one or more of tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, and ethyltriphenylammonium bromide; and the cosolvent is preferably isopropyl alcohol.

[0074] In the present invention, the ratio of epichlorohydrin to the total mass of organosilanol-modified 5-maleimido-1-naphthol and 5-maleimido-1-naphthol is preferably 1 to 1.2:1, more preferably 1.1:1.

[0075] In the present invention, the amount of the co-solvent is preferably 0 to 30% of the total mass of the organosilanol-modified 5-maleimido-1-naphthol and 5-maleimido-1-naphthol, and more preferably 10 to 20%.

[0076] In the present invention, the mass of the phase transfer catalyst is preferably 1 to 5% of the total mass of the organosilanol-modified 5-maleimido-1-naphthol, 5-maleimido-1-naphthol and paraformaldehyde, and more preferably 2 to 4%;

[0077] In the present invention, the mass of the sodium hydroxide is preferably 5 to 15% of the total mass of the organosilanol-modified 5-maleimido-1-naphthol, 5-maleimido-1-naphthol and paraformaldehyde, and more preferably 8 to 10%;

[0078] In the present invention, the temperature of the epoxy ring-opening-closing condensation reaction is preferably 45 to 125° C., more preferably 60 to 100° C., and the time is 3 to 9 hours, more preferably 5 to 7 hours.

[0079] In the present invention, after the epoxy ring-opening-ring-closing condensation reaction, the present invention preferably cools the obtained epoxy ring-opening-ring-closing condensation reaction product to room temperature, filters it, and washes the obtained filtrate with water and performs reduced pressure distillation.

[0080] In the present invention, it is preferred to remove the generated sodium chloride by filtration, and to remove the unreacted epichlorohydrin and the organic solvent by distillation under reduced pressure.

[0081] In the present invention, the synthesis route of the organosilicon-modified double network cross-linked epoxy resin is as follows: Figure 1 shown.

[0082] The present invention provides the use of the organosilicon-modified double-network cross-linked epoxy resin as a semiconductor packaging material.

[0083] The organosilicon-modified double-network cross-linked epoxy resin provided by the present invention and its preparation method and application are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0084] Example 1

[0085] The preparation method of organosilicon-modified double network cross-linked epoxy resin comprises the following steps:

[0086] Take 15 g of 5-amino-1-naphthol and 10 g of maleic anhydride, add them into a reactor with nitrogen protection and condensation device, add 45 g of toluene to dissolve, mix evenly at 70°C, react for 2 hours, and after the reaction is completed, remove the solvent and unreacted raw materials by reduced pressure distillation to obtain 5-maleimido-1-naphthol.

[0087] Take 23.9 g of the above-prepared 5-maleimido-1-naphthol, 18 g of hexaphenyl fused-ring hexasiloxane disilanol, and 0.45 g of dibutyltin dilaurate, add them into a reactor with nitrogen protection and a condensing device, add 250 g of cyclohexanone to dissolve, react at 140° C. for 2 hours, and after the reaction is completed, remove the solvent by reduced pressure distillation to obtain organosilanol-modified 5-maleimido-1-naphthol.

[0088] Take 23.9g of the prepared 5-maleimide-1-naphthol, 31.47g of organosilanol-modified 5-maleimide-1-naphthol, and 11g of paraformaldehyde (degree of polymerization 8), add them into a reactor with nitrogen protection and a condensing device, add 150g of toluene to dissolve, react at 100°C for 2 hours, cool and add 60.9g of epichlorohydrin, 3.5g of isopropanol and 1.73g of tetrabutylammonium bromide, mix well to form a transparent solution, then slowly add 8g of sodium hydroxide, react at 45°C for 3 hours, cool to room temperature after the reaction is completed, remove the generated sodium chloride, wash with water and distill under reduced pressure to remove unreacted epichlorohydrin and solvent, and obtain an organosilicon-modified double network cross-linked epoxy resin, and its epoxy equivalent is 335g / mol when tested by hydrochloric acid acetone method.

[0089] Example 2

[0090] The preparation method of organosilicon-modified double network cross-linked epoxy resin comprises the following steps:

[0091] A certain amount of 5-amino-1-naphthol 13g and maleic anhydride 10g were added to a reactor equipped with nitrogen protection and a condensing device, 40g of toluene was added to dissolve, mixed evenly at 100°C, reacted for 5 hours, and after the reaction was completed, the solvent and unreacted raw materials were removed by reduced pressure distillation to obtain 5-maleimido-1-naphthol;

[0092] Take 23.9g of the above-prepared 5-maleimide-1-naphthol, 41.4g of hexaphenyl fused ring hexasiloxane disilanol, and 0.65g of dibutyltin dilaurate, add them into a reactor with nitrogen protection and condensation device, add 500g of N,N-dimethylformamide to dissolve, and react at 130°C for 4 hours. After the reaction is completed, remove the solvent by vacuum distillation to obtain organosilanol-modified 5-maleimide-1-naphthol;

[0093] Take 23.9g of the prepared 5-maleimide-1-naphthol, 51.45g of organosilanol-modified 5-maleimide-1-naphthol, and 22.6g of paraformaldehyde (degree of polymerization 10), add them to a reactor with nitrogen protection and a condensing device, add 300g of toluene to dissolve, react at 120°C for 6 hours, cool and add 83g of epichlorohydrin, 10g of isopropanol and 3.5g of tetrabutylammonium bromide, mix well to form a transparent solution, then slowly add 7.5g of sodium hydroxide, react at 100°C for 9 hours, cool to room temperature after the reaction is completed, remove the generated sodium chloride, wash with water and distill under reduced pressure to remove unreacted epichlorohydrin and solvent, and obtain an organosilicon-modified double network cross-linked epoxy resin, and its epoxy equivalent is 346g / mol when tested by hydrochloric acid acetone method.

[0094] Example 3

[0095] The preparation method of organosilicon-modified double network cross-linked epoxy resin comprises the following steps:

[0096] Take a certain amount of 5-amino-1-naphthol 14g and maleic anhydride 9.8g, add them into a reactor equipped with nitrogen protection and a condensing device, add 40g of toluene to dissolve, mix evenly at 160°C, react for 8 hours, and after the reaction is completed, remove the solvent and unreacted raw materials by reduced pressure distillation to obtain 5-maleimido-1-naphthol;

[0097] 23.9 g of the 5-maleimido-1-naphthol prepared above, 49.86 g of hexaphenyl fused-ring hexasiloxane disilanol, and 1.2 g of dibutyltin dilaurate were added into a reactor equipped with nitrogen protection and a condensing device, 400 g of cyclohexanone was added to dissolve, and the mixture was reacted at 150° C. for 2 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain organosilanol-modified 5-maleimido-1-naphthol;

[0098] Take 23.9g of the prepared 5-maleimide-1-naphthol, 83.92g of organosilanol-modified 5-maleimide-1-naphthol, and 32.3g of paraformaldehyde (degree of polymerization 9), add them to a reactor with nitrogen protection and a condensing device, add 420g of toluene to dissolve, react at 120°C for 8 hours, cool and add 115g of epichlorohydrin, 60g of isopropanol and 4.2g of tetrabutylammonium bromide, mix them evenly into a transparent solution, then slowly add 15g of sodium hydroxide, react at 125°C for 9 hours, cool to room temperature after the reaction is completed, remove the generated sodium chloride, wash with water and distill under reduced pressure to remove unreacted epichlorohydrin and solvent, and obtain an organosilicon-modified double network cross-linked epoxy resin, and its epoxy equivalent is 360g / mol when tested by hydrochloric acid acetone method.

[0099] Performance Testing

[0100] Heat resistance: The test was conducted using a TA-Q500 thermogravimetric analyzer from TA Instruments, USA. 15-25 mg of sample was taken and the temperature was raised from 40°C to 800°C at a rate of 10°C / min in a N2 atmosphere.

[0101] Glass transition temperature: Dynamic thermomechanical analysis was used to determine the variation of loss factor (tanδ) with temperature in the temperature range of 30 to 350°C in a liquid nitrogen atmosphere and film stretching mode. The heating rate was 5°C / min and the test frequency was 10 Hz, so as to determine the glass transition temperature of the resin composition after curing. The sample size was 42 mm×8 mm×0.3 mm.

[0102] Mechanical properties test: With reference to the standard GB / T 2567-2021, the tensile properties are measured on a universal material testing machine, the elongation rate is 2mm / min, 5 splines are taken from each group for parallel testing, the dumbbell-shaped spline test section has a cross-sectional size of 10mm×4mm, a parallel section length of 60mm, and a total length of 200mm. The three-point bending performance is also measured on a universal material testing machine, with a moving rate of 2mm / min, a spline size of 4mm×15mm×90mm, and 5 splines are taken from each group for parallel experiments. The impact strength is tested using a simply supported beam impact toughness test, with 5 splines with and without notches for parallel experiments, with a spline size of 15mm×10mm×120mm, the pendulum is released steadily, and the work consumed and the form of failure of the breaking specimen are read.

[0103] 100 g of each of the organosilicon-modified double network cross-linked epoxy resins prepared in Examples 1 to 3 was mixed with 23 g of 4,4-diaminophenylsulfone (DDS) curing agent and dissolved in a mixed solvent of 250 mL of acetone and 250 mL of N,N-dimethylformamide. After the dissolution was completed, the solvent was removed by reduced pressure distillation to obtain 123 g of a mixture of the resin and the curing agent. The mixture was cured at 120° C. for 1 h, 180° C. for 1.5 h, and 220° C. for 3 h to obtain an organosilicon-modified double network cross-linked epoxy resin cured product.

[0104] The properties of the organosilicon-modified double-network cross-linked epoxy resin cured products obtained in Examples 1 to 3 are shown in Table 1.

[0105] Table 1 Performance of silicone modified double network cross-linked epoxy resin cured products of Examples 1 to 3

[0106] Example 1 Example 2 Example 3 <![CDATA[Initial thermal decomposition temperature (T 5％ °C)]]> 428 425 430 Glass transition temperature (Tg℃) 278 275 283 Toughness (impact strength) (MPa) 23.7 24.8 22.4 Tensile strength(MPa) 34.5 32.2 35.2 Tensile modulus(GPa) 3.02 2.96 3.08 Bending strength(MPa) 55.3 53.4 55.4 Flexural modulus(GPa) 3.18 3.03 3.19

[0107] It can be seen from Table 1 that the organosilicon-modified double-network cross-linked epoxy resin provided by the present invention has good heat resistance, strength and toughness.

[0108] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A silicone-modified double-network cross-linked epoxy resin having a structure shown in Formula 1: In formula 1, m:n=1 to 10:

1.

2. The organosilicon-modified double network cross-linked epoxy resin according to claim 1, characterized in that: The epoxy equivalent of the organosilicon-modified double-network cross-linked epoxy resin is 300 to 400 g / mol.

3. The method for preparing the organosilicon-modified double-network cross-linked epoxy resin according to claim 1 or 2, comprising the following steps: (1) mixing 5-amino-1-naphthol, maleic anhydride and a first organic solvent, and performing an amidation reaction to obtain 5-maleimido-1-naphthol; (2) mixing the 5-maleimido-1-naphthol, hexaphenyl fused-ring hexasiloxane disilanol, a catalyst and a second organic solvent, and performing a hydroxyl dehydration condensation reaction to obtain organosilanol-modified 5-maleimido-1-naphthol; (3) mixing 5-maleimido-1-naphthol, organosilanol-modified 5-maleimido-1-naphthol, paraformaldehyde and a third organic solvent to carry out a phenol-formaldehyde condensation reaction to obtain a phenol-formaldehyde condensation reaction product; (4) mixing the phenolic condensation reaction product with epichlorohydrin, a cosolvent, a phase transfer catalyst, and sodium hydroxide to carry out an epoxy ring-opening-closing condensation reaction to obtain an organosilicon-modified double-network cross-linked epoxy resin.

4. The preparation method according to claim 3, characterized in that: The catalyst in step (2) is dibutyltin dilaurate; The polymerization degree of the paraformaldehyde in the step (3) is 8 to 10; The phase transfer catalyst in step (4) is one or more of tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and ethyltriphenylammonium bromide.

5. The preparation method according to claim 3, characterized in that: The cosolvent is isopropanol; The first organic solvent and the third organic solvent are independently one or more of toluene, xylene and methyl isobutyl ketone; The second organic solvent is one or more of cyclohexanone, butyl acetate, N,N-dimethylformamide and N,N-dimethylacetamide.

6. The preparation method according to claim 3, characterized in that: In the step (1), the mass ratio of 5-amino-1-naphthol to maleic anhydride is 1.2 to 1.6:1; The ratio of the mass of the first organic solvent to the total mass of 5-amino-1-naphthol and maleic anhydride is 1.5 to 2:1; The temperature of the amidation reaction is 70-160° C. and the time is 2-8 hours.

7. The preparation method according to claim 3, characterized in that: In the step (2), the molar ratio of the hexaphenyl fused ring hexasiloxane disilanol to 5-maleimido-1-naphthol is 0.2 to 0.8:1; The mass of the catalyst is 0.5-2% of the total mass of 5-maleimido-1-naphthol and hexaphenyl fused ring hexasiloxane disilanol; The ratio of the mass of the second organic solvent to the total mass of 5-maleimido-1-naphthol and hexaphenyl fused-ring hexasiloxane disilanol is 5 to 10:1; The temperature of the hydroxyl dehydration condensation reaction is 140-150° C. and the time is 2-4 hours.

8. The preparation method according to claim 3, characterized in that: In the step (3), the molar ratio of the organosilanol-modified 5-maleimido-1-naphthol to 5-maleimido-1-naphthol is 0.2 to 1:1; The mass of the polyformaldehyde is 10 to 50% of the total mass of the organosilanol-modified 5-maleimide-1-naphthol and 5-maleimide-1-naphthol; The ratio of the mass of the third organic solvent to the total mass of 5-maleimido-1-naphthol, organosilanol-modified 5-maleimido-1-naphthol, and paraformaldehyde is 2 to 5:1; The temperature of the phenol-formaldehyde condensation reaction is 100-120° C., and the time is 2-8 hours.

9. The preparation method according to claim 3, characterized in that: In the step (4), the ratio of the mass of epichlorohydrin to the total mass of the organosilanol-modified 5-maleimido-1-naphthol and 5-maleimido-1-naphthol is 1 to 1.2:1; The amount of the co-solvent is 0 to 30% of the total mass of the organosilanol-modified 5-maleimide-1-naphthol and 5-maleimide-1-naphthol; The mass of the phase transfer catalyst is 1 to 5% of the total mass of the organosilanol-modified 5-maleimide-1-naphthol, 5-maleimide-1-naphthol and paraformaldehyde; The mass of the sodium hydroxide is 5 to 15% of the total mass of the organosilanol-modified 5-maleimido-1-naphthol, 5-maleimido-1-naphthol and paraformaldehyde; The temperature of the epoxy ring-opening-closing condensation reaction is 45-125° C. and the time is 3-9 hours.

10. Use of the organosilicon-modified double network cross-linked epoxy resin according to claim 1 or 2 or the organosilicon-modified double network cross-linked epoxy resin prepared by the preparation method according to any one of claims 3 to 9 as a semiconductor packaging material.

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