A curable resin composition and its preparation method and application

Abstract

The present invention discloses a curable resin composition and a preparation method and application thereof, wherein the curable resin composition comprises component A and component B; component A comprises: base glue, vinyl-terminated polysiloxane, pigment, platinum catalyst, and silane coupling agent of formula I; component B comprises: base glue, vinyl-terminated polysiloxane, terminal hydrogen-containing polysiloxane, side hydrogen-containing polysiloxane, and inhibitor; wherein the base glue comprises: vinyl-terminated polysiloxane, silane coupling agent of formula I, silane coupling agent of formula II, and thermally conductive filler. The present invention uses vinyl-terminated polysiloxane, terminal hydrogen-containing polysiloxane, side hydrogen-containing polysiloxane, and is matched with thermally conductive filler and methoxy-containing silane coupling agents of formula I and formula II to prepare a high thermally conductive silicone potting glue, which has good thermal conductivity, flame retardancy of V0, excellent leveling performance, good anti-settling performance, low working temperature rise of the potted inverter, no aging cracking of the colloid, small hardness change, and no damage to the magnetic core inductor device.

Description

Technical Field

[0001] The present invention relates to the technical field of silicone rubber, and in particular to a curable resin composition and a preparation method and application thereof. Background Art

[0002] In recent years, the new energy industry has been developing rapidly, and the photovoltaic industry has been particularly favored by the market. As one of the key equipment for photovoltaic power generation and electricity consumption, the performance of photovoltaic inverters affects the conversion efficiency and safety of the entire power generation system. The current market generally uses thermal conductive silicone materials to pot the inverter. With the innovation of technology, the power of the inverter is increasing and the volume is decreasing. It is bound to have higher requirements for the temperature resistance, thermal conductivity, fluidity and operating reliability of thermal conductive potting glue under harsh conditions.

[0003] According to the actual working conditions and requirements of the core inductor of the photovoltaic inverter, the thermal conductive potting glue used for the core inductor needs to have high thermal conductivity, excellent fluidity, moderate viscosity, low operating temperature rise, and the ability to withstand low temperature (-40°C) and high temperature (150°C) conditions for a long time without cracking the colloid, and will not damage the core device of the inverter due to excessive internal stress. The related art discloses that the glue obtained by using spherical thermal conductive fillers and adding carbon black has excellent fluidity and anti-sedimentation properties. However, it only uses spherical alumina as a filler, the material cost is high, and the thermal conductivity of the potting glue obtained is about 1.5W / mK. There are also related technologies reporting a silicone potting glue, the filler treatment agent is a silane with 12 to 20 carbons, and the tackifier is a silane coupling agent with epoxy and vinyl groups, but the silane structure of the filler, the thermal conductivity, fluidity and aging performance of the potting glue are unknown. Summary of the invention

[0004] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the object of the present invention is to provide a curable resin composition and a preparation method and application thereof.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A curable resin composition, comprising component A and component B;

[0007] The component A comprises: base glue, vinyl-terminated polysiloxane, pigment, platinum catalyst, and silane coupling agent of formula I;

[0008] The B component includes: base glue, vinyl-terminated polysiloxane, hydrogen-terminated polysiloxane, side hydrogen-containing polysiloxane, and inhibitor;

[0009] Wherein, the base glue comprises: vinyl-terminated polysiloxane, a silane coupling agent of formula I, a silane coupling agent of formula II, and a thermally conductive filler;

[0010]

[0011] Among them, R 1 , R 2 Each independently selected from C 1 ~C 4 Alkyl; x is selected from any integer from 4 to 15; m is selected from any integer from 1 to 5; n is selected from any integer from 50 to 400.

[0012] In some embodiments of the present invention, the curable resin composition includes component A and component B in a mass ratio of 1:1.

[0013] In some embodiments of the present invention, the base glue comprises, by weight: 20 to 30 parts of vinyl-terminated polysiloxane, 3 to 10 parts of silane coupling agent of formula I, 0.1 to 5 parts of silane coupling agent of formula II, and 500 to 550 parts of thermal conductive filler.

[0014] In some embodiments of the present invention, the base glue comprises, by weight: 22 to 30 parts of vinyl-terminated polysiloxane, 3.5 to 8 parts of silane coupling agent of formula I, 0.5 to 4 parts of silane coupling agent of formula II, and 500 to 550 parts of thermal conductive filler.

[0015] In some embodiments of the present invention, the component A includes, by weight: 500-550 parts of base glue, 20-30 parts of terminal vinyl polysiloxane, 0.1-1 part of pigment, 0.1-2 parts of platinum catalyst, and 1-10 parts of formula I silane coupling agent.

[0016] In some embodiments of the present invention, the component A includes, by weight: 526-534 parts of base glue, 20-30 parts of terminal vinyl polysiloxane, 0.5-1 part of pigment, 0.5-2 parts of platinum catalyst, and 5-10 parts of formula I silane coupling agent.

[0017] In some embodiments of the present invention, the component B includes, by weight: 500-550 parts of base gum, 1-15 parts of terminal vinyl polysiloxane, 10-30 parts of terminal hydrogen-containing polysiloxane, 1-10 parts of side hydrogen-containing polysiloxane, and 0.1-1 part of inhibitor.

[0018] In some embodiments of the present invention, the B component includes, by weight: 500 parts of base gum, 3-10 parts of terminal vinyl polysiloxane, 12-26 parts of terminal hydrogen-containing polysiloxane, 2-8 parts of side hydrogen-containing polysiloxane, and 0.1-1 part of inhibitor.

[0019] In some embodiments of the present invention, the viscosity of the vinyl-terminated polysiloxane is 100-600 mPa.s, and the volatile matter is ≤0.8%; preferably, the viscosity of the vinyl-terminated polysiloxane is 100-450 mPa.s, and the volatile matter is ≤0.8%.

[0020] In some embodiments of the present invention, the viscosity of the hydrogen-terminated polysiloxane is 20-80 mPa.s, the hydrogen content is 0.1-0.5%, and the volatile matter is ≤3%; preferably, the viscosity of the hydrogen-terminated polysiloxane is 20-45 mPa.s, the hydrogen content is 0.1-0.4%, and the volatile matter is ≤3%.

[0021] In some embodiments of the present invention, the viscosity of the side hydrogen-containing polysiloxane is 20-65 mPa.s, the hydrogen content is 0.08-0.3%, and the volatile matter is ≤2%; preferably, the viscosity of the side hydrogen-containing polysiloxane is 20-45 mPa.s, the hydrogen content is 0.08-0.3%, and the volatile matter is ≤2%.

[0022] In some embodiments of the present invention, the thermally conductive filler includes at least one of spherical alumina, quasi-spherical alumina, zinc oxide or aluminum nitride; preferably, the thermally conductive filler includes at least two of spherical alumina, quasi-spherical alumina, zinc oxide or aluminum nitride; preferably, the particle size of the thermally conductive filler is 1 μm to 50 μm; preferably, the particle size of the thermally conductive filler is 1 μm to 40 μm; preferably, the thermally conductive filler includes 1 μm to 5 μm quasi-spherical alumina, 3 μm to 10 μm quasi-spherical alumina, 10 μm to 30 μm spherical alumina, 30 μm to 50 μm spherical alumina; preferably, the thermally conductive filler includes a mass ratio of (1 to 3): (0.5-2): (1-3): (3-8) of 1μm-5μm quasi-spherical alumina, 3μm-10μm quasi-spherical alumina, 10μm-30μm spherical alumina, 30μm-50μm spherical alumina; preferably, the thermally conductive filler comprises 2μm quasi-spherical alumina, 5μm quasi-spherical alumina, 20μm spherical alumina, 40μm spherical alumina in a mass ratio of (1-3): 1: (1-3): (3-8); preferably, the thermally conductive filler comprises 2μm quasi-spherical alumina, 5μm quasi-spherical alumina, 20μm spherical alumina, 40μm spherical alumina in a mass ratio of 2:1:2:5. In the present invention, multiple materials including spherical alumina, quasi-spherical alumina, zinc oxide and aluminum nitride are compounded and used, which can significantly improve the sedimentation performance of the potting compound, form a more excellent heat conduction channel, and improve the thermal conductivity of the potting compound.

[0023] In some embodiments of the present invention, the catalyst includes at least one of a platinum (zero valent)-divinyltetramethyldisiloxane complex, a cyclopentadienyl platinum complex, and a triazene platinum complex; preferably, the platinum content of the platinum (zero valent)-divinyltetramethyldisiloxane complex is 1000 to 6500 ppm; preferably, the platinum content of the platinum (zero valent)-divinyltetramethyldisiloxane complex is 2000 to 6500 ppm.

[0024] In some embodiments of the present invention, the inhibitor includes at least one of acetylene cyclohexanol, methyl butynol, tetramethyl divinyl disiloxane, and trimethyl-dodecyl alcohol; preferably, the inhibitor includes any one of acetylene cyclohexanol, methyl butynol, and trimethyl-dodecyl alcohol. The use of the inhibitor in the present invention can control the reaction speed of the organic silicon potting glue during curing, and has excellent operability during potting.

[0025] According to a second aspect of the present invention, a method for preparing the curable resin composition is provided, comprising the following steps:

[0026] S1: preparing a base adhesive: heating the vinyl-terminated polysiloxane, the silane coupling agent of formula I, the silane coupling agent of formula II, and the thermal conductive filler, and stirring to obtain the base adhesive;

[0027] S2: Preparation of component A: Adding vinyl-terminated polysiloxane, pigment, and silane coupling agent of formula I to the base rubber prepared in S1, adding platinum catalyst after dispersion and stirring, and dispersing and stirring to obtain the component A;

[0028] S3: Preparation of component B: Add terminal vinyl polysiloxane, terminal hydrogen-containing polysiloxane and side hydrogen-containing polysiloxane to the base rubber prepared in S1, disperse and stir, then add inhibitor, disperse and stir to obtain the component B.

[0029] In some embodiments of the present invention, the method for preparing the curable resin composition comprises the following steps:

[0030] S1: preparing a base rubber: heating the vinyl-terminated polysiloxane, the silane coupling agent of formula I, the silane coupling agent of formula II, and the thermal conductive filler to 80°C to 100°C and stirring at normal pressure for 0.5h to 1h, raising the temperature to 120°C to 150°C, stirring at a pressure of -0.095MPa for 1h to 2h to obtain the base rubber;

[0031] S2: Preparation of component A: Add terminal vinyl polysiloxane, pigment, and silane coupling agent of formula I to the base rubber prepared in S1, disperse at 800 rpm to 1000 rpm, stir at 20 rpm to 30 rpm for 20 min to 30 min, then add platinum catalyst, disperse at 800 rpm to 1200 rpm, stir at 20 rpm to 30 rpm for 10 min to 15 min to obtain component A;

[0032] S3: Preparation of component B: Add terminal vinyl polysiloxane, terminal hydrogen polysiloxane and side hydrogen polysiloxane to the base rubber prepared in S1, disperse at 800rpm-1200rpm, stir at 20rpm-30rpm for 20min-30min, then add inhibitor, disperse at 800rpm-1200rpm, stir at 20rpm-30rpm for 10min-15min to obtain the component B.

[0033] According to a third aspect of the present invention, a silicone potting compound is provided, comprising the curable resin composition.

[0034] According to a fourth aspect of the present invention, a use of the curable resin composition and / or the organosilicon potting compound in potting electronic devices is proposed.

[0035] In some embodiments of the present invention, the electronic device includes any one of a photovoltaic inverter, an LED driving power supply, and a network transformer.

[0036] The beneficial effects of the present invention are:

[0037] (1) In the present invention, the combination of the silane coupling agent of formula I and the silane coupling agent of formula II can be used to modify the base rubber powder. In the components A and B, the use of the silane coupling agent is optimized, the aging hardness of the rubber block increases less, and the mechanical properties are improved.

[0038] (2) In the present invention, terminal vinyl polysiloxane, terminal hydrogen polysiloxane, and side hydrogen polysiloxane are used in combination with thermal conductive fillers and methoxy silane coupling agents of formula I and formula II to prepare a high thermal conductive silicone potting compound, which has a thermal conductivity of 1.9 to 2.5 W / mK, a flame retardancy of V0, excellent leveling performance, good anti-settling performance, and a low operating temperature rise of the potted inverter. The colloid has no aging cracking and a small change in hardness under long-term low temperature (-40°C) and high temperature (150°C), and has no damage to the magnetic core inductor device, and the inverter operates normally.

[0039] (3) The curable resin composition of the present invention has excellent flow properties and is easy to construct and operate. It has high thermal conductivity and meets the thermal management requirements of heat dissipation of various high-power inverters, controllers and power supplies. In addition, under high and low temperature environments, the colloid itself has excellent mechanical properties and small hardness changes. The colloid does not crack or damage the device, ensuring the stable operation of various electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 It is the infrared spectrum of the silane coupling agent of formula I of the present invention.

[0041] Figure 2 It is the infrared spectrum of the silane coupling agent of formula II of the present invention. DETAILED DESCRIPTION

[0042] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0043] In the following examples or comparative examples, the raw materials are:

[0044] The preparation method of silane coupling agent is:

[0045] Preparation of formula I silane coupling agent: Weigh 80-300 parts by weight of end-hydrogenated polysiloxane S-83 (Zhejiang Runhe Silicone New Materials Co., Ltd.) in a three-necked flask and heat it to 60-80°C. Take 0.01-0.1 parts by weight of platinum catalyst (platinum-divinyltetramethyldisiloxane complex) and 0.2-1.5 parts by weight of vinyltrimethoxysilane and add them to a constant pressure dropping funnel and mix them evenly. Control the flow rate to 1 drop per second and add them dropwise into the three-necked flask and stir to react. After the addition is complete, continue the reaction for 2-5 hours. Control the temperature at 60-80°C, then add 1-5 parts by weight of 1-octene and stir to react for 2-5 hours. After the reaction is completed, heat it to 170-180°C and vacuum it for 4-6 hours to remove low boiling points.

[0046] Preparation of silane coupling agent of formula II: weigh 50-120 parts by mass of tetramethyldisiloxane in a three-necked flask, heat and stir to 45-60°C under nitrogen, take 45-100 parts by mass of vinyltrimethoxysilane and 0.01-0.1 parts by mass of platinum catalyst (platinum-divinyltetramethyldisiloxane complex) and add them to a constant pressure dropping funnel and mix them evenly, control the flow rate to 1 drop per second and add them dropwise into the three-necked flask, stir and react. After the addition is completed, continue the reaction for 1-3 hours, and control the temperature at 45-60°C. After the reaction is completed, heat to 85-90°C and vacuum for 3-5 hours to remove low boiling points to obtain an intermediate.

[0047] Weigh 150-350 parts by weight of vinyl-terminated polysiloxane (viscosity 500mPa.s) (Zhejiang Runhe Silicone New Materials Co., Ltd.) in a three-necked flask and heat it to 60-80°C. Take 0.01-0.1 parts by weight of platinum catalyst (platinum-divinyltetramethyldisiloxane complex) and 20-50 parts by weight of the intermediate in the previous step and add them to a constant pressure dropping funnel and mix evenly. Control the flow rate to 1 drop per second and add it dropwise into the three-necked flask and stir to react. After the addition is complete, control the temperature at 60-80°C and continue the reaction for 2-5 hours. After the reaction is completed, heat it to 160-170°C and vacuum it for 4-6 hours to remove low-boiling substances.

[0048] The infrared spectra of the silane coupling agent of formula I and the silane coupling agent of formula II are as follows: Figure 1-2 shown.

[0049] It can be seen that the characteristic peaks of the reaction functional groups before and after synthesis are characterized by infrared FTIR. In the infrared spectrum, 2200-2100 cm -1 The peak at is the characteristic absorption peak of the Si-H bond. Comparing before and after the reaction, it can be seen that the characteristic absorption peak at this location completely disappears, indicating that the reaction groups of Si-H react completely to generate the target product.

[0050] Vinyl-terminated polysiloxane, 100# vinyl polysiloxane and 350# polysiloxane from Jiangxi Lanxing Xinghuo Silicone Co., Ltd.;

[0051] Hydrogenated polysiloxane, from Ambiya Specialty Silicone Co., Ltd. XL 1B;

[0052] Hydrogen-terminated polysiloxanes, RH-H45 and RH-H6 from Zhejiang Runhe Silicone New Materials Co., Ltd.;

[0053] Thermal conductive filler: 2 μm quasi-spherical alumina, 5 μm quasi-spherical alumina, 20 μm spherical alumina, and 40 μm spherical alumina are mixed in a mass ratio of 2:1:2:5.

[0054] Example 1

[0055] This embodiment prepares a kind of organic silicon potting glue, and the specific process is as follows:

[0056] S1: Preparation of base glue: Mix 22 parts of vinyl-terminated polysiloxane, 5 parts of silane coupling agent of formula I, 1 part of silane coupling agent of formula II and 500 parts of thermal conductive filler according to weight ratio, heat to 100°C, disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain base glue, and cool for use.

[0057] S2: Preparation of component A: According to weight ratio, add 22 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of silane coupling agent of formula I to 528 parts of base rubber, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 1 part of platinum catalyst, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component A.

[0058] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 15 parts of terminal hydrogen polysiloxane and 5 parts of side hydrogen polysiloxane to 528 parts of base glue, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 0.5 parts of inhibitor, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component B.

[0059] Mix component A and component B in a mass ratio of 1:1, pour into the inverter core inductor for potting, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0060] Mix component A and component B in a mass ratio of 1:1, vacuum degassing, put them into a mold to prepare rubber strips and rubber blocks, heat them at 80°C for 30 minutes to completely cure, and place them in an oven under specified conditions for corresponding performance tests.

[0061] Example 2

[0062] This embodiment prepares a kind of organic silicon potting glue, and the specific process is as follows:

[0063] S1: Preparation of base glue: Mix 22 parts of vinyl-terminated polysiloxane, 10 parts of silane coupling agent of formula I, 1 part of silane coupling agent of formula II and 500 parts of thermal conductive filler according to weight ratio, heat to 100°C, disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain base glue, and cool for use.

[0064] S2: Preparation of component A: According to weight ratio, add 22 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of silane coupling agent of formula I to 533 parts of base rubber, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 1 part of platinum catalyst, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component A.

[0065] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 15 parts of terminal hydrogen polysiloxane and 5 parts of side hydrogen polysiloxane to 533 parts of base glue, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 0.5 parts of inhibitor, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component B.

[0066] Mix component A and component B in a mass ratio of 1:1, pour into the inverter core inductor for potting, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0067] Mix component A and component B in a mass ratio of 1:1, vacuum degassing, put them into a mold to prepare rubber strips and rubber blocks, heat them at 80°C for 30 minutes to completely cure, and place them in an oven under specified conditions for corresponding performance tests.

[0068] Example 3

[0069] This embodiment prepares a kind of organic silicon potting glue, and the specific process is as follows:

[0070] S1: Preparation of base glue: Mix 22 parts of vinyl-terminated polysiloxane, 5 parts of silane coupling agent of formula I, 2 parts of silane coupling agent of formula II and 500 parts of thermal conductive filler according to weight ratio, heat to 100°C, disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain base glue, and cool for use.

[0071] S2: Preparation of component A: According to weight ratio, add 22 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of silane coupling agent of formula I to 529 parts of base rubber, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 1 part of platinum catalyst, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component A.

[0072] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 15 parts of terminal hydrogen-containing polysiloxane and 5 parts of side hydrogen-containing polysiloxane to 529 parts of base glue, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 0.5 parts of inhibitor, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component B.

[0073] Mix component A and component B in a mass ratio of 1:1, pour into the inverter core inductor for potting, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0074] Mix component A and component B in a mass ratio of 1:1, vacuum degassing, put them into a mold to prepare rubber strips and rubber blocks, heat them at 80°C for 30 minutes to completely cure, and place them in an oven under specified conditions for corresponding performance tests.

[0075] Example 4

[0076] This embodiment prepares a kind of organic silicon potting glue, and the specific process is as follows:

[0077] S1: Preparation of base glue: Mix 22 parts of vinyl-terminated polysiloxane, 5 parts of silane coupling agent of formula I, 1 part of silane coupling agent of formula II and 500 parts of thermal conductive filler according to weight ratio, heat to 100°C, disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain base glue, and cool for use.

[0078] S2: Preparation of component A: According to weight ratio, add 26 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of silane coupling agent of formula I to 528 parts of base rubber, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 1 part of platinum catalyst, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component A.

[0079] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 17 parts of terminal hydrogen polysiloxane and 7 parts of side hydrogen polysiloxane to 528 parts of base rubber, disperse at 1000 rpm / second, stir at 25 rpm / second for 30 minutes, then add 0.5 parts of inhibitor, evacuate at 1000 rpm / second, stir at 25 rpm / second, and stir for 15 minutes to obtain component B.

[0080] Mix component A and component B in a mass ratio of 1:1, pour into the inverter core inductor for potting, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0081] Example 5

[0082] This embodiment prepares a kind of organic silicon potting glue, and the specific process is as follows:

[0083] S1: Preparation of base glue: Mix 22 parts of vinyl-terminated polysiloxane, 5 parts of silane coupling agent of formula I, 1 part of silane coupling agent of formula II and 500 parts of thermal conductive filler according to weight ratio, heat to 100°C, disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain base glue, and cool for use.

[0084] S2: Preparation of component A: According to weight ratio, add 30 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of silane coupling agent of formula I to 528 parts of base rubber, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 1 part of platinum catalyst, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component A.

[0085] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 20 parts of terminal hydrogen polysiloxane and 7 parts of side hydrogen polysiloxane to 528 parts of base glue, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 0.5 parts of inhibitor, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component B.

[0086] S4: Mix component A and component B in a mass ratio of 1:1. After application, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0087] Comparative Example 1

[0088] This comparative example prepared a silicone potting adhesive, and the specific process was as follows:

[0089] S1: Preparation of base glue: Mix 22 parts of terminal vinyl polysiloxane, 6 parts of methyltrimethoxysilane (Shanghai Aladdin Biochemical Technology Co., Ltd.) and 500 parts of thermal conductive filler according to the weight ratio, heat to 100°C and disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain the base glue, and cool for use.

[0090] S2: Preparation of component A: According to weight ratio, add 26 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of silane coupling agent of formula II to 528 parts of base rubber, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 1 part of platinum catalyst, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component A.

[0091] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 17 parts of terminal hydrogen polysiloxane and 7 parts of side hydrogen polysiloxane to 528 parts of base glue, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 0.5 parts of inhibitor, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component B.

[0092] Mix component A and component B in a mass ratio of 1:1, pour into the inverter core inductor for potting, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0093] Mix component A and component B in a mass ratio of 1:1, vacuum degassing, put them into a mold to prepare rubber strips and rubber blocks, heat them at 80°C for 30 minutes to completely cure, and place them in an oven under specified conditions for corresponding performance tests.

[0094] Comparative Example 2

[0095] This comparative example prepared a silicone potting adhesive, and the specific process was as follows:

[0096] S1: Preparation of base glue: Mix 22 parts of vinyl-terminated polysiloxane, 5 parts of silane coupling agent of formula I, 1 part of silane coupling agent of formula II and 500 parts of thermal conductive filler according to weight ratio, heat to 100°C, disperse and stir at normal pressure for 0.5h, then heat to 150°C, evacuate to above -0.095MPa, disperse and stir for 1h to obtain base glue, and cool for use.

[0097] S2: Preparation of component A: According to weight ratio, add 26 parts of terminal vinyl polysiloxane, 0.5 parts of black pigment and 5 parts of methyl polysiloxane (viscosity 50mPa.s) to 528 parts of base rubber, set the dispersion speed to 1000rpm and the revolution speed to 25rpm, stir thoroughly for 30min, then add 1 part of platinum catalyst, set the dispersion speed to 1000rpm and the revolution speed to 25rpm, vacuum and stir thoroughly for 15min to obtain component A.

[0098] S3: Preparation of component B: According to weight ratio, add 3 parts of terminal vinyl polysiloxane, 17 parts of terminal hydrogen polysiloxane and 7 parts of side hydrogen polysiloxane to 528 parts of base glue, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, stir thoroughly for 30 minutes, then add 0.5 parts of inhibitor, set the dispersion speed to 1000 rpm and the revolution speed to 25 rpm, vacuum and stir thoroughly for 15 minutes to obtain component B.

[0099] Mix component A and component B in a mass ratio of 1:1, pour into the inverter core inductor for potting, vacuum degassing, heat at 80°C for 30 minutes to completely cure, and place in an oven under specified conditions for corresponding performance tests.

[0100] Mix component A and component B in a mass ratio of 1:1, vacuum degassing, put them into a mold to prepare rubber strips and rubber blocks, heat them at 80°C for 30 minutes to completely cure, and place them in an oven under specified conditions for corresponding performance tests.

[0101] Test example

[0102] This test example tests the performance of the silicone potting adhesives prepared in the examples and comparative examples, and the specific process is as follows:

[0103] The specific testing methods of the products are as follows:

[0104] Viscosity: Tested according to the method specified in GB / T 2794 using a Brookfield viscometer with rotor No. 5 and 20 rpm;

[0105] Hardness: Tested using a Shore A hardness tester according to the method specified in GB / T 531.1;

[0106] Thermal conductivity: Tested using Hot Disk according to the method specified in ISO 22007-2;

[0107] Leveling value: Weigh 10g of glue and place it upside down on the PCB board. Test the diameter of the circle formed by the glue for 5 minutes.

[0108] Tensile strength and elongation at break: tested using a universal tensile testing machine according to the method specified in GB / T 528;

[0109] Flame retardant grade: According to the method specified in GB / T 2408, the sample is 3.0±0.05mm, and the vertical burning method is used for testing;

[0110] Thermal expansion coefficient: Tested using TMA according to the method specified in ISO 11359-2;

[0111] The results are shown in Table 1:

[0112] Table 1

[0113]

[0114] As can be seen from Table 1, in Examples 1 to 5, a base glue is prepared by using a combination of silane coupling agent I and silane coupling agent II, and then a two-component potting glue of components A and B is prepared by using the base glue. The thermal conductivity of the prepared thermal conductive potting glue is 1.9-2.5 W / mK, the viscosity range is 6000-12000 mPa.s, the leveling value is 5.6-8 cm, and the hardness increase of the glue block after aging at 150°C for 1000 hours is controlled to be 8-15 HA. Comparison between Example 1 and Comparative Example 1 shows that when preparing a potting compound with the same thermal conductivity of about 2.5 W / mK, the viscosity of the potting compound obtained by treating the small molecule methyltrimethoxysilane in Comparative Example 1 is 14500 mPa.s, and the leveling value is only 4.8 cm. After being used in the inverter core inductor device and aged at 150°C for 1000 h, the colloid cracks. The viscosity of the potting compound prepared in Example 1 is 12150 mPa.s, and the leveling value is 5.6 cm, and the colloid did not crack after being used in the inverter core inductor device and aged at 150°C for 1000h. By comparing Example 5 with Comparative Example 2, it can be seen that when preparing a potting compound with a lower thermal conductivity of about 2W / mK, the potting compound obtained by treating Comparative Example 2 with small molecule methyltrimethoxysilane has a viscosity of 10500mPa.s and a leveling value of only 5.6cm. After being used in the inverter core inductor device and aged at 150°C for 1000h, the colloid cracked.

[0115] According to the data of the examples and comparative examples, a high thermal conductivity silicone potting glue is prepared by using terminal vinyl polysiloxane, terminal hydrogen polysiloxane, side hydrogen polysiloxane, thermal conductive filler and formula I, formula II methoxy silane coupling agent, and the thermal conductivity is 1.9-2.5W / mK, with excellent flow properties and easy construction operation. The potted inverter has a low working temperature rise, and under long-term high temperature (150°C), the colloid itself has excellent mechanical properties, the colloid has no aging cracking, the hardness changes little, the colloid does not crack and damage the device, and the stable operation of various electronic devices is guaranteed.

[0116] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A curable resin composition, characterized in that: It includes component A and component B; The component A comprises: 500-550 parts of base rubber, 20-30 parts of vinyl-terminated polysiloxane, 0.1-1 parts of pigment, 0.1-2 parts of platinum catalyst, and 1-10 parts of formula I silane coupling agent; The B component comprises: 500-550 parts of base glue, 1-15 parts of terminal vinyl polysiloxane, 10-30 parts of terminal hydrogen-containing polysiloxane, 1-10 parts of side hydrogen-containing polysiloxane, and 0.1-1 parts of inhibitor; The base glue comprises: 20-30 parts of vinyl-terminated polysiloxane, 3-10 parts of formula I silane coupling agent, 0.1-5 parts of formula II silane coupling agent, and 500-550 parts of thermal conductive filler; ； ； Wherein, R1 and R2 are independently selected from C1~C4 alkyl; x is selected from any integer from 4 to 15; m is selected from any integer from 1 to 5; and n is selected from any integer from 50 to 400.

2. The curable resin composition according to claim 1, characterized in that: In parts by weight, the base glue comprises: 22-30 parts of vinyl-terminated polysiloxane, 3.5-8 parts of formula I silane coupling agent, 0.5-4 parts of formula II silane coupling agent, and 500-550 parts of thermal conductive filler.

3. The curable resin composition according to claim 1, characterized in that: In parts by weight, the component A includes: 526-534 parts of base glue, 20-30 parts of vinyl-terminated polysiloxane, 0.5-1 parts of pigment, 0.5-2 parts of platinum catalyst, and 5-10 parts of formula I silane coupling agent.

4. The curable resin composition according to claim 1, characterized in that: In parts by weight, the component B comprises: 500 parts of base glue, 3-10 parts of terminal vinyl polysiloxane, 12-26 parts of terminal hydrogen-containing polysiloxane, 2-8 parts of side hydrogen-containing polysiloxane, and 0.1-1 part of inhibitor.

5. The curable resin composition according to claim 1, characterized in that: The viscosity of the vinyl-terminated polysiloxane is 100-600 mPa.s, and the volatile matter is ≤0.8%.

6. The curable resin composition according to claim 1, characterized in that: The hydrogen-terminated polysiloxane has a viscosity of 20-80 mPa.s, a hydrogen content of 0.1-0.5%, and a volatile content of ≤3%.

7. The curable resin composition according to claim 1, characterized in that: The thermally conductive filler includes at least one of spherical aluminum oxide, quasi-spherical aluminum oxide, zinc oxide or aluminum nitride.

8. A method for preparing a curable resin composition according to any one of claims 1 to 7, comprising the following steps: S1: preparing a base adhesive: heating the vinyl-terminated polysiloxane, the silane coupling agent of formula I, the silane coupling agent of formula II, and the thermal conductive filler, and stirring to obtain the base adhesive; S2: Preparation of component A: Adding vinyl-terminated polysiloxane, pigment, and silane coupling agent of formula I to the base rubber prepared in S1, adding platinum catalyst after dispersion and stirring, and dispersing and stirring to obtain the component A; S3: Preparation of component B: Add terminal vinyl polysiloxane, terminal hydrogen-containing polysiloxane and side hydrogen-containing polysiloxane to the base rubber prepared in S1, disperse and stir, then add inhibitor, disperse and stir to obtain the component B.

9. An organosilicon potting compound comprising the curable resin composition according to any one of claims 1 to 7.

10. Use of the curable resin composition according to any one of claims 1 to 7 and / or the silicone potting adhesive according to claim 9 in potting electronic devices.

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