MS resin-epoxy resin two-component hybrid glue and preparation method thereof

Abstract

The invention relates to the technical field of adhesives, in particular to MS resin-epoxy resin two-component hybrid glue and a preparation method thereof.The MS resin-epoxy resin two-component hybrid glue comprises a component A and a component B. The component A comprises silane modified polyether resin, polysiloxane-polyether epoxy block copolymer, a silane coupling agent, an antioxidant, an epoxy resin curing accelerator, first filler and a first catalyst; the component B comprises epoxy resin, a silane coupling agent, a plasticizer, a silane modified polyether resin curing accelerator, a second filler and a second catalyst; and the silane coupling agent is a compound of KH-560 and KH-792. According to the MS resin-epoxy resin two-component hybrid glue, the polysiloxane-polyether epoxy block copolymer is added, and the bifunctional silane coupling agent is adopted, so that the compatibility of the MS resin-epoxy resin two-component hybrid glue is improved, effective chemical crosslinking is formed between the MS resin component and the epoxy resin component, and the performance of the two-component hybrid glue is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and particularly relates to an MS resin-epoxy resin two-component hybrid adhesive and a preparation method thereof. Background Art

[0002] The power battery module provides the power source for new energy vehicles. In actual use, the outer shell frame of the power battery module needs to be sealed to ensure safety. Currently, most of them ensure the sealing performance through the combined action of adhesive bonding and welding. And the adhesive mainly uses polyurethane structural adhesive. However, the existing polyurethane structural adhesives have the disadvantages of low high-temperature strength and poor low-temperature toughness, and it is difficult to meet the requirements of current power batteries.

[0003] Therefore, people have studied other types of adhesives and found that the two-component hybrid adhesive of MS resin and epoxy resin has better strength and toughness retention in high-temperature and low-temperature environments than polyurethane structural adhesives. It has both the toughness of MS resin and the high strength of epoxy, and can meet the requirements of current power batteries. However, the MS resin-epoxy resin hybrid adhesive is formed by the separate curing of two independent components. The MS resin and the silane-modified resin are respectively present in different components and are cured with different curing agents. No effective chemical bond is formed between the two components. Therefore, after being exposed to harsh environments such as high temperature and high humidity, adhesive failure will occur, which limits the application fields of the two-component hybrid adhesive of MS resin and epoxy resin.

[0004] Therefore, how to improve the compatibility of the MS resin-epoxy resin hybrid adhesive system and achieve a stable cross-linked network is of great significance for its stability in the application environment of power batteries.

[0005] The information disclosed in this background art section is only intended to deepen the understanding of the overall background art of the present invention, and should not be regarded as an admission or any form of suggestion that this information constitutes the prior art known to those skilled in the art. Summary of the Invention

[0006] The purpose of the present invention is to provide an MS resin-epoxy resin two-component hybrid adhesive. By adding a polysiloxane-polyether epoxy block copolymer, the compatibility of the MS resin-epoxy resin two-component is improved, and an effective chemical cross-linking is formed between the MS resin component and the epoxy resin component, thereby enhancing the performance of the two-component hybrid adhesive.

[0007] The technical solution adopted by the present invention to solve the above problems is as follows:

[0008] An MS resin-epoxy resin two-component hybrid adhesive, comprising component A and component B;

[0009] Component A includes silane-modified polyether resin (MS resin), polysiloxane-polyether epoxy block copolymer, silane coupling agent, antioxidant, epoxy resin curing accelerator, first filler, and first catalyst;

[0010] Component B includes epoxy resin, silane coupling agent, plasticizer, silane-modified polyether resin curing accelerator, second filler, and second catalyst;

[0011] The polysiloxane-polyether epoxy block copolymer is a block copolymer formed by coupling a hydroxyl-terminated polysiloxane segment and an epoxy-terminated polyether segment through a diisocyanate. It bridges the siloxane segment and the polyether epoxy segment through chemical bonds, inhibits phase separation, and forms a homogeneous interpenetrating network. Through the structural design of the block copolymer and the compounding of a two-component silane coupling agent, the present invention systematically solves the key technical bottlenecks such as phase separation, weak interfacial adhesion, and poor curing synergy of MS / epoxy hybrid adhesives, achieving a breakthrough in high-performance and high-reliability adhesives, and is applicable to high-end fields such as automobiles, electronics, and aerospace.

[0012] Preferably, the polysiloxane-polyether epoxy block copolymer is prepared by the following preparation method:

[0013] S1 React a cyclic siloxane monomer with a capping agent under the action of a catalyst to generate a hydroxyl-terminated polysiloxane segment;

[0014] Preferably, the cyclic siloxane monomer is octamethylcyclotetrasiloxane (D4), the capping agent is hexamethyldisiloxane (MM), the catalyst is concentrated sulfuric acid, the molar ratio of the cyclic siloxane monomer to the capping agent is 1:0.02 - 0.05, and the mass percentage of the catalyst in the system is 0.5 - 1%. Under the catalysis of concentrated sulfuric acid, octamethylcyclotetrasiloxane (D4) undergoes ring-opening polymerization to form a linear polysiloxane chain. Hexamethyldisiloxane (MM) serves as a capping agent to provide methyl termination sites, and at the same time, trace water in the system participates in the reaction to generate hydroxyl termination. The length of the PDMS segment is precisely regulated by the molar ratio of hexamethyldisiloxane (MM) to octamethylcyclotetrasiloxane (D4) to avoid mechanical property fluctuations caused by over-crosslinking or too short chain segments.

[0015] S2 React polyethylene glycol diglycidyl ether with epichlorohydrin to generate an epoxy-terminated polyether segment;

[0016] Preferably, it further includes a catalyst and an initiator. The catalyst is DMP-30, and the initiator is ethylenediamine. The molar ratio of polyethylene glycol diglycidyl ether, epichlorohydrin, and the initiator is 1:2.2-2.5:0.05-0.1, and the mass percentage of the catalyst in the system is 0.1-0.5%. In the present invention, ethylenediamine preferentially initiates the ring-opening polymerization of the epoxy groups of PEG-DGE to form an active secondary amine intermediate, driving chain growth, avoiding random polymerization caused by directly using ECH, and ensuring a linear structure. Subsequently, excessive epichlorohydrin (ECH) performs epoxy capping on the terminal hydroxyl groups of PEG to ensure complete chain termination and avoid interfering with subsequent coupling reactions with PDMS-OH.

[0017] S3 Dissolve the hydroxyl-terminated polysiloxane chain segment in step S1 and the epoxy-terminated polyether chain segment in step S2 in an organic solvent, add diisocyanate and a catalyst, and under nitrogen protection, purify after the reaction to obtain a polysiloxane-polyether epoxy block copolymer.

[0018] Preferably, the diisocyanate is hexamethylene diisocyanate (HDI), the catalyst is dibutyltin dilaurate, the organic solvent is toluene, and the molar ratio of the hydroxyl-terminated polysiloxane chain segment, the epoxy-terminated polyether chain segment, and the diisocyanate is 1:1:2.0:2.2. The mass percentage of the catalyst is 0.05-0.1%, and the dosage of the organic solvent is 2-3 times the total mass of the reactants. During the reaction process, the -NCO group of hexamethylene diisocyanate (HDI) directly reacts with the hydroxyl group of PDMS-OH to form a urethane bond, and at the same time, it undergoes secondary cross-linking with the secondary hydroxyl group generated by the ring-opening of PEG-EPOXY to construct a three-dimensional interpenetrating network. The urethane bond acts as a "molecular bridge" to connect the siloxane and polyether chain segments, reducing the interfacial energy between the two phases.

[0019] Further preferably, the preparation method of the polysiloxane-polyether epoxy block copolymer includes:

[0020] S1 Synthesize a hydroxyl-terminated polysiloxane chain segment

[0021] Under nitrogen protection, octamethylcyclotetrasiloxane (D4), hexamethyldisiloxane (MM), and the catalyst concentrated sulfuric acid are heated and stirred to react at 80-100°C for 4-6 hours. After the reaction, it is neutralized with sodium bicarbonate, filtered to remove sulfate precipitates, and then distilled under reduced pressure to remove unreacted monomers to obtain hydroxyl-terminated polydimethylsiloxane PDMS-OH;

[0022] S2 Synthesize an epoxy-terminated polyether chain segment

[0023] Dissolve polyethylene glycol diglycidyl ether in tetrahydrofuran (THF), add a catalyst (DMP-30), under nitrogen protection, dropwise add the initiator ethylenediamine, stir and react at 60 - 80 °C for 3 - 5 h, then add an excessive amount of epichlorohydrin for end-capping. After the reaction, an epoxy group-terminated polyether segment PEG-EPOXY is obtained. Add methanol for precipitation, filter, and then dry in vacuum;

[0024] S3 Synthesize polysiloxane-polyether epoxy block copolymer

[0025] Dissolve hydroxyl-terminated polydimethylsiloxane PDMS-OH and epoxy group-terminated polyether segment PEG-EPOXY in toluene, add diisocyanate and the catalyst dibutyltin dilaurate, under nitrogen protection, react at 70 - 90 °C for 6 - 8 h, then add methanol to terminate the reaction. After precipitation, dissolve with tetrahydrofuran (THF), and then dialyze to remove small molecule by-products, and dry in vacuum to obtain the final block copolymer PDMS-PEG-EPOXY.

[0026] Preferably, the silane coupling agents in component A and component B are a complex of silane coupling agents with different functional groups. The silane coupling agent in component A contains an epoxy group, and the silane coupling agent in component B contains an amino group. The silane coupling agent in component A is used to enhance the interfacial bonding between the silicone resin and the inorganic filler, and the silane coupling agent in component B is used to improve the adhesion between the epoxy resin and the organic substrate. The epoxy group-containing silane coupling agent in component A only participates in the moisture condensation curing of the silicone, without interfering with the epoxy curing of component B; and there is no amino interference, avoiding pre-gelation of the silicone resin and improving the storage stability. In the amino group-containing silane coupling agent in component B, the amino group is both a coupling agent and a latent curing agent, promoting the cross-linking of the epoxy resin and matching the curing rate of the silane; avoiding the competitive reaction of the epoxy silane in component A in component B, resulting in incomplete epoxy curing.

[0027] Preferably, the silane coupling agent in component A is KH-560. The epoxy group of KH-560 reacts with the Si-OH of the silicone resin to form a stable Si-O-C bond, enhancing the resin-filler binding force; after the methoxy group is hydrolyzed, it condenses with the hydroxyl groups on the surface of the inorganic filler to improve the dispersibility.

[0028] Preferably, the silane coupling agent in component B is KH-792. The amino group of KH-792 undergoes a ring-opening reaction with the epoxy group of the epoxy resin and directly participates in the cross-linking network; the ethoxy group condenses with the hydroxyl groups on the surface of the filler to enhance the interfacial adhesion.

[0029] Preferably, the first filler is at least one of a reinforcing filler, a flame retardant filler, and a thermal conductive filler, and the second filler is at least one of a reinforcing filler, a flame retardant filler, and a thermal conductive filler. The present invention allows the A component (siloxane system) and the B component (epoxy system) to independently select the filler type according to their respective requirements, and the two-phase fillers are coupled through a block copolymer interface to form a continuous functional network.

[0030] Preferably, the reinforcing filler includes one or a mixture of nano calcium carbonate and nano silicon oxide to improve the tensile / shear strength and inhibit crack propagation. The flame retardant filler includes one or more of aluminum hydroxide (ATH), zinc borate, and phosphorus-nitrogen based flame retardants to improve the UL94 rating through endothermic / gas-phase flame retardancy. The thermal conductive filler includes one or more of boron nitride, alumina, and graphene to enhance heat conduction and avoid local overheating.

[0031] Preferably, the reinforcing filler is nano calcium carbonate. Through the "rigid particle toughening" mechanism, nano calcium carbonate forms stress concentration points after being dispersed in epoxy resin, induces crazes and shear bands, and absorbs impact energy; at the same time, it improves flexibility through interface slippage in MS resin, achieving the synergistic improvement of strength and toughness.

[0032] Preferably, the epoxy resin curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol, and the curing accelerator for the silane-modified polyether resin is water. As an efficient tertiary amine catalyst, the catalytic mechanism of 2,4,6-tris(dimethylaminomethyl)phenol is to promote the ring-opening polymerization reaction of epoxy groups, shorten the curing time, show excellent synergistic effects with KH-792 in the B component, and at the same time does not interfere with the moisture curing process of the A component siloxane, ensuring the synchronous crosslinking of the two-component system.

[0033] Water is used as the curing accelerator for the silane-modified polyether resin. Water molecules play a dual role in the curing process: on the one hand, they generate active silanol groups by hydrolyzing the methoxy groups of silanes, and then condense to form a stable Si-O-Si three-dimensional network; on the other hand, they can pre-activate the hydroxyl groups on the surface of inorganic fillers, significantly improving the bonding efficiency between the fillers and KH-560.

[0034] Preferably, the antioxidant is at least one of BASF antioxidant 1010 and antioxidant 2246. The pentaerythritol ester structure of antioxidant 1010 enables it to be evenly dispersed in both the non-polar siloxane phase and the polar epoxy phase, avoiding the problems of easy migration and blooming of traditional antioxidants. The molecular weight of antioxidant 2246 is moderate, which can not only ensure its solubility in the resin but also prevent volatilization loss due to too small a molecular weight. These two hindered phenolic antioxidants provide comprehensive antioxidant protection for the material through synergistic effects.

[0035] Preferably, the first catalyst is a chelated tin catalyst and the second catalyst is a tertiary amine catalyst. Compared with traditional organotin catalysts, chelated tin compounds have significantly reduced ecotoxicity, and the molecular structure design of tertiary amine catalysts makes them non-volatile and non-migrating at room temperature. In addition, chelated tin catalysts are basically inactive to epoxy systems, and tertiary amine catalysts do not interfere with siloxane curing. This selectivity avoids curing defects caused by competitive reactions.

[0036] Preferably, the plasticizer is diisononyl hexahydrophthalate. Diisononyl hexahydrophthalate has moderate polarity and can form a homogeneous system with both MS resin and epoxy resin, avoiding phase separation or interface weakening caused by plasticizer seepage. The cyclohexane structure in the molecule provides a rigid barrier, which can reduce the migration loss rate at high temperatures and ensure long-term performance stability compared to straight-chain plasticizers (such as DINP). In addition, the glass transition temperature of diisononyl hexahydrophthalate is extremely low, which can improve the flexibility of the glue layer at -40°C and alleviate the interfacial stress during low-temperature charging and discharging of the power battery.

[0037] Preferably, the mass ratio of component A to component B is 1-2:1; through the complementary advantages of silane-modified polyether resin and epoxy resin, a hybrid material system with both flexibility and rigidity is constructed.

[0038] Component A includes the following components by weight: 60-90 parts of silane-modified polyether resin, 5-10 parts of polysiloxane-polyether epoxy block copolymer, 0.1-5 parts of silane coupling agent, 0.1-5 parts of antioxidant, 0.1-0.5 parts of epoxy resin curing accelerator, 5-10 parts of first filler, and 0.1-1 parts of first catalyst;

[0039] Calculated by weight, component B includes the following components: 30-80 parts of epoxy resin, 0.1-5 parts of silane coupling agent, 20-50 parts of plasticizer, 0.1-0.5 parts of silane-modified polyether resin curing accelerator, 5-10 parts of second filler, and 0.1-1 parts of second catalyst.

[0040] 60-90 parts of silane-modified polyether resin in component A provide excellent elastic recovery and weather resistance, and 5-10 parts of polysiloxane-polyether epoxy block copolymer as a compatibilizer significantly improves the interfacial compatibility with 30-80 parts of epoxy resin in component B. The cured material has both high elongation of the siloxane phase and high strength of the epoxy phase, overcoming the defects of insufficient performance of the traditional single resin system.

[0041] Another object of the present invention is to provide a method for preparing a MS resin-epoxy resin two-component hybrid adhesive, comprising the following steps:

[0042] (1) Preparation of Component A: After vacuum dehydrating the silane-modified polyether resin, polysiloxane-polyether epoxy block copolymer and the first filler, maintain the vacuum condition and cool to room temperature to avoid pre-hydrolysis of subsequent silane coupling agents (such as KH-560) and consumption of active groups. The dehydration temperature is controlled at 80 - 100 °C, the vacuum degree is ≤ -0.095 MPa, and the time is 1 - 2 hours to balance efficiency and energy consumption. Then add other components in Component A, and stir and mix evenly to obtain Component A; prevent the thermal-sensitive additive from decomposing and failing at high temperatures.

[0043] (2) Preparation of Component B: Mix the components in Component B evenly to obtain Component B.

[0044] (3) Then mix the obtained Component A and Component B to get a two-component hybrid adhesive. The mass ratio of A / B components is 1 - 2:1, and only need to stir at a low speed of 100 - 200 rpm for 5 - 10 minutes to be uniform.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0046] For the MS resin-epoxy resin two-component hybrid adhesive of the present invention, by adding a polysiloxane-polyether epoxy block copolymer, the compatibility of the MS resin-epoxy resin two-component is improved, and effective chemical cross-linking is formed between the MS resin component and the epoxy resin component, enhancing the performance of the two-component hybrid adhesive. In addition, the present invention uses a bifunctional silane coupling agent, one end of which reacts with the silanol group of the MS resin, and the other end reacts with the epoxy group to form a chemical bridge, further improving the bonding effect. Detailed Embodiments

[0047] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments.

[0048] The raw materials or reagents used in the embodiments and / or comparative examples of the present invention are all purchased from mainstream manufacturers in the market. Those without indicating the manufacturer or the concentration are all raw materials or reagents of analytical pure grade that can be obtained conventionally, as long as they can play the expected role, there is no special limitation.

[0049]

[0050]

[0051] Example 1

[0052] An MS resin-epoxy resin two-component hybrid adhesive, comprising component A and component B; the mass ratio of component A to component B is 2:1; by mass parts, component A comprises the following components: 80 parts of silane-modified polyether Excestar, 5 parts of polysiloxane-polyether epoxy block copolymer, 0.5 part of silane coupling agent, 0.1 part of antioxidant, 0.2 part of epoxy resin curing accelerator, 5 parts of first filler, 0.2 part of first catalyst; by mass parts, component B comprises the following components: 50 parts of epoxy resin, 0.5 part of silane coupling agent, 30 parts of plasticizer, 0.1 part of silane-modified polyether resin curing accelerator, 5 parts of second filler, 0.2 part of second catalyst.

[0053] Among them, the polysiloxane-polyether epoxy block copolymer is prepared by the following preparation method:

[0054] (1) Synthesize a hydroxyl-terminated polysiloxane segment

[0055] Under nitrogen protection, 200 g of octamethylcyclotetrasiloxane D4, 10 g of hexamethyldisiloxane MM and 1 g of catalyst concentrated sulfuric acid are heated to 80 °C and stirred for reaction for 6 h. After the reaction is completed, it is neutralized with sodium bicarbonate, the precipitate is filtered off, and the unreacted monomers are removed by vacuum distillation to obtain hydroxyl-terminated polydimethylsiloxane PDMS-OH;

[0056] (2) Synthesize an epoxy-terminated polyether segment

[0057] 100 g of polyethylene glycol diglycidyl ether is dissolved in tetrahydrofuran THF, 1 g of catalyst DMP-30 is added, under nitrogen protection, 0.5 g of initiator ethylenediamine is added dropwise, and the reaction is stirred at 50 °C for 4 h. Then 20 g of epichlorohydrin is added for end-capping, and after the reaction for 2 h, an epoxy-terminated polyether segment PEG-EPOXY is obtained. It is precipitated with methanol, filtered and dried in vacuum;

[0058] (3) Couple the siloxane and polyether segments

[0059] 50 g of hydroxyl-terminated polydimethylsiloxane PDMS-OH and 50 g of epoxy-terminated polyether segment PEG-EPOXY are dissolved in toluene, 15 g of diisocyanate and 0.2 g of catalyst dibutyltin dilaurate are added, and the reaction is carried out at 80 °C for 8 h under nitrogen protection to make the -NCO group react with -OH and epoxy groups. Then methanol is added to terminate the reaction, the precipitate is dissolved with THF, and then small molecule by-products are removed by dialysis and dried in vacuum to obtain the final block copolymer PDMS-PEG-EPOXY.

[0060] Both the first filler and the second filler are prepared by mixing nano calcium carbonate and boron nitride in a mass ratio of 1:1.

[0061] The epoxy resin curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

[0062] The curing accelerator for the silane-modified polyether resin is water.

[0063] The antioxidant is BASF antioxidant 1010.

[0064] The first catalyst is the chelating tin catalyst U-220H from Nitto Kasei, and the second catalyst is the tertiary amine catalyst DMP-30.

[0065] The plasticizer is diisononyl hexahydrophthalate.

[0066] A method for preparing a two-component hybrid adhesive of MS resin-epoxy resin includes the following steps:

[0067] (1) Prepare component A: After vacuum dehydrating the silane-modified polyether resin, polyorganosiloxane-polyether epoxy block copolymer and the first filler, maintain the vacuum condition and cool to room temperature, then add other components in component A, and stir and mix evenly to obtain component A;

[0068] (2) Prepare component B: Mix the components in component B evenly to obtain component B;

[0069] (3) Then mix the obtained component A and component B to obtain the two-component hybrid adhesive.

[0070] Example 2

[0071] A two-component hybrid adhesive of MS resin-epoxy resin includes component A and component B; the mass ratio of component A to component B is 2:1; by mass, component A includes the following components: 70 parts of silane-modified polyether resin, 8 parts of polyorganosiloxane-polyether epoxy block copolymer, 0.8 part of silane coupling agent, 0.2 part of antioxidant, 0.2 part of epoxy resin curing accelerator, 7 parts of the first filler, 0.2 part of the first catalyst; by mass, component B includes the following components: 40 parts of epoxy resin, 0.8 part of silane coupling agent, 40 parts of plasticizer, 0.1 part of silane-modified polyether resin curing accelerator, 7 parts of the second filler, 0.2 part of the second catalyst.

[0072] Among them, the polyorganosiloxane-polyether epoxy block copolymer is prepared by the following preparation method:

[0073] (1) Synthesize a hydroxyl-terminated polyorganosiloxane segment

[0074] Under nitrogen protection, 200 g of octamethylcyclotetrasiloxane D4, 10 g of hexamethyldisiloxane MM and 1 g of catalyst concentrated sulfuric acid were heated to 80 °C and stirred for reaction for 6 h. After the reaction, it was neutralized with sodium bicarbonate, the precipitate was filtered off, and the unreacted monomers were removed by vacuum distillation to obtain hydroxyl-terminated polydimethylsiloxane PDMS-OH;

[0075] (2) Synthesis of epoxy-terminated polyether segment

[0076] 100 g of polyethylene glycol diglycidyl ether was dissolved in tetrahydrofuran THF, 1 g of catalyst DMP-30 was added, and under nitrogen protection, 0.5 g of initiator ethylenediamine was added dropwise. The reaction was stirred at 50 °C for 4 h, and then 20 g of epichlorohydrin was added for end-capping. After reacting for 2 h, epoxy-terminated polyether segment PEG-EPOXY was obtained. Methanol was added for precipitation, and after filtration, it was dried in vacuum;

[0077] (3) Coupling of siloxane and polyether segment

[0078] 50 g of hydroxyl-terminated polydimethylsiloxane PDMS-OH and 50 g of epoxy-terminated polyether segment PEG-EPOXY were dissolved in toluene, 15 g of diisocyanate and 0.2 g of catalyst dibutyltin dilaurate were added. Under nitrogen protection, the reaction was carried out at 80 °C for 8 h to make the -NCO group react with -OH and epoxy groups. Then methanol was added to terminate the reaction. After precipitation, it was dissolved in THF, and then small molecule by-products were removed by dialysis and dried in vacuum to obtain the final block copolymer PDMS-PEG-EPOXY.

[0079] Both the first filler and the second filler were prepared by mixing nano calcium carbonate and aluminum hydroxide in a mass ratio of 1:1.

[0080] The epoxy resin curing accelerator was 2,4,6-tris(dimethylaminomethyl)phenol.

[0081] The curing accelerator for the silane-modified polyether resin was water.

[0082] The antioxidant was BASF antioxidant 1010.

[0083] The first catalyst was the chelating tin catalyst U-220H of Nitto Kasei, and the second catalyst was the tertiary amine catalyst DMP-30.

[0084] The plasticizer was diisononyl hexahydrophthalate.

[0085] A preparation method of an MS resin-epoxy resin two-component hybrid adhesive, comprising the following steps:

[0086] (1) Preparation of Component A: After vacuum dehydrating the silane-modified polyether resin, polyorganosiloxane-polyether epoxy block copolymer, and the first filler, maintain the vacuum condition and cool to room temperature. Then add the other components in Component A, and stir and mix evenly to obtain Component A;

[0087] (2) Preparation of Component B: Mix the components in Component B evenly to obtain Component B;

[0088] (3) Then mix the obtained Component A and Component B to obtain a two-component hybrid adhesive.

[0089] Example 3

[0090] An MS resin-epoxy resin two-component hybrid adhesive, comprising Component A and Component B; the mass ratio of Component A to Component B is 1:1; by mass parts, Component A includes the following components: 90 parts of silane-modified polyether resin, 10 parts of polyorganosiloxane-polyether epoxy block copolymer, 1 part of silane coupling agent, 0.2 part of antioxidant, 0.2 part of epoxy resin curing accelerator, 10 parts of the first filler, 0.5 part of the first catalyst; by mass parts, Component B includes the following components: 50 parts of epoxy resin, 1 part of silane coupling agent, 40 parts of plasticizer, 0.2 part of silane-modified polyether resin curing accelerator, 8 parts of the second filler, 0.5 part of the second catalyst.

[0091] Among them, the polyorganosiloxane-polyether epoxy block copolymer is prepared by the following preparation method:

[0092] (1) Synthesis of a hydroxyl-terminated polyorganosiloxane segment

[0093] Under the protection of nitrogen, heat 200 g of octamethylcyclotetrasiloxane D4, 10 g of hexamethyldisiloxane MM, and 1 g of catalyst concentrated sulfuric acid to 80 °C and stir for 6 h. After the reaction, neutralize with sodium bicarbonate, filter to remove the precipitate, and then distill under reduced pressure to remove the unreacted monomers to obtain hydroxyl-terminated polydimethylsiloxane PDMS-OH;

[0094] (2) Synthesis of an epoxy-terminated polyether segment

[0095] Dissolve 100 g of polyethylene glycol diglycidyl ether in tetrahydrofuran THF, add 1 g of catalyst DMP-30, under the protection of nitrogen, dropwise add 0.5 g of initiator ethylenediamine, stir at 50 °C for 4 h, then add 20 g of epichlorohydrin for end-capping, and react for 2 h to obtain an epoxy-terminated polyether segment PEG-EPOXY. Add methanol for precipitation, filter, and dry under vacuum;

[0096] (3) Coupling the siloxane and polyether segments

[0097] 50 g of hydroxyl-terminated polydimethylsiloxane PDMS-OH and 50 g of epoxy-terminated polyether segment PEG-EPOXY were dissolved in toluene. 15 g of diisocyanate and 0.2 g of catalyst dibutyltin dilaurate were added. Under nitrogen protection, the reaction was carried out at 80 °C for 8 h to react the -NCO groups with -OH and epoxy groups. Then methanol was added to terminate the reaction. After precipitation, it was dissolved in THF, and then dialyzed to remove small molecule by-products. Vacuum drying was carried out to obtain the final block copolymer PDMS-PEG-EPOXY.

[0098] Both the first filler and the second filler were prepared by mixing nano calcium carbonate, boron nitride and aluminum hydroxide in a mass ratio of 1:1:1.

[0099] The epoxy resin curing accelerator was 2,4,6-tris(dimethylaminomethyl)phenol.

[0100] The curing accelerator for the silane-modified polyether resin was water.

[0101] The antioxidant was BASF antioxidant 1010.

[0102] The first catalyst was the chelating tin catalyst U-220H of Nitto Kasei, and the second catalyst was the tertiary amine catalyst DMP-30.

[0103] The plasticizer was diisononyl hexahydrophthalate.

[0104] A preparation method of an MS resin-epoxy resin two-component hybrid adhesive, comprising the following steps:

[0105] (1) Preparation of component A: After the silane-modified polyether resin, the polysiloxane-polyether epoxy block copolymer and the first filler were vacuum dehydrated, the vacuum condition was maintained and cooled to room temperature, and then other components in component A were added, and they were stirred and mixed evenly to obtain component A;

[0106] (2) Preparation of component B: Each component in component B was mixed evenly to obtain component B;

[0107] (3) Then the obtained component A and component B were mixed to obtain a two-component hybrid adhesive.

[0108] Comparative Example 1

[0109] The difference from Example 1 was only that: the polysiloxane-polyether epoxy block copolymer was not added.

[0110] Comparative Example 2

[0111] The difference from Example 1 was only that: KH-560 was used for all the silane coupling agents.

[0112] The cured samples formed by mixing and curing the two-component hybrid adhesives of Examples 1-3 and Comparative Examples 1-2 were subjected to mechanical property tests; the cured samples were tested for tensile strength, shear strength, and elongation at break; among them, the tensile strength and elongation at break were tested according to GBT 528-2009; the shear strength was tested according to GB / T 7124-2008, and the results are shown in Table 1:

[0113] Table 1 Mechanical property test results of Examples 1-3 and Comparative Examples 1-2

[0114] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile strength / MPa 5.1 4.9 5.2 4.0 4.7 Elongation at break / % 160 170 154 100 134 Shear strength / MPa 5.4 5.0 5.7 4.1 4.8

[0115] The cured samples formed by mixing and curing the two-component hybrid adhesives of Examples 1-3 and Comparative Examples 1-2 were subjected to aging tests. The test method was based on the standard of "GB / T 2423.22-2002. Environmental Tests for Electric and Electronic Products - Part 2: Test Methods - Test N: Change of Temperature". The samples to be tested were placed in an alternating temperature environment of -40°C to 85°C, and the conversion time between the two extreme temperatures was within 3 minutes, with 2 hours for one cycle and 500 cycles, for a total of 1000 hours of aging. Then, the shear strength, tensile strength, and elongation at break were tested according to the methods in the above performance tests, and the results are shown in Table 2:

[0116] Table 2 Mechanical property test results after aging of Examples 1-3 and Comparative Examples 1-2

[0117] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile strength / MPa 4.7 4.5 4.6 3.1 3.8 Elongation at break / % 145 158 141 70 93 Shear strength / MPa 5.1 4.8 5.7 3.5 4.0

[0118] Those skilled in the art should understand that the present invention is not limited by the above embodiments. What is described in the above embodiments and the specification only illustrates the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A two-component hybrid adhesive of MS resin - epoxy resin, characterized in that: It includes Component A and Component B; Component A includes silane-modified polyether resin, polysiloxane-polyether epoxy block copolymer, silane coupling agent, antioxidant, epoxy resin curing accelerator, first filler, and first catalyst; Component B includes epoxy resin, silane coupling agent, plasticizer, silane-modified polyether resin curing accelerator, second filler, and second catalyst; The polysiloxane-polyether epoxy block copolymer is a block copolymer formed by coupling a hydroxyl-terminated polysiloxane segment and an epoxy-terminated polyether segment through a diisocyanate.

2. The MS resin-epoxy resin two-component hybrid adhesive according to claim 1, wherein: The polysiloxane-polyether epoxy block copolymer is prepared by the following preparation method: S1 React a cyclic siloxane monomer with a capping agent under the action of a catalyst to generate a hydroxyl-terminated polysiloxane segment; S2 React polyethylene glycol diglycidyl ether with epichlorohydrin to generate an epoxy-terminated polyether segment; S3 Dissolve the hydroxyl-terminated polysiloxane segment obtained in step S1 and the epoxy-terminated polyether segment obtained in step S2 in an organic solvent, add a diisocyanate and a catalyst, and react under nitrogen protection, followed by purification to obtain the block copolymer.

3. The MS resin-epoxy resin two-component hybrid adhesive according to claim 1, wherein: The silane coupling agents in Component A and Component B are a compound of silanes with different functional groups. The silane coupling agent in Component A contains an epoxy group, and the silane coupling agent in Component B contains an amino group.

4. The MS resin-epoxy resin two-component hybrid adhesive according to claim 3, characterized in that: The silane coupling agent in Component A is KH-560, and the silane coupling agent in Component B is KH-792.

5. The MS resin-epoxy resin two-component hybrid adhesive according to claim 1, characterized in that: The first filler is at least one of a reinforcing filler, a flame retardant filler, and a thermal conductive filler, and the second filler is at least one of a reinforcing filler, a flame retardant filler, and a thermal conductive filler.

6. The MS resin-epoxy resin two-component hybrid adhesive according to claim 1, characterized in that: The epoxy resin curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol, and the silane-modified polyether resin curing accelerator is water.

7. The MS resin-epoxy resin two-component hybrid adhesive according to claim 1, wherein: The antioxidant is at least one of antioxidant 1010 and antioxidant 2246.

8. The MS resin-epoxy resin two-component hybrid adhesive according to claim 1, wherein: The first catalyst is a chelating tin catalyst, and the second catalyst is a tertiary amine catalyst.

9. The MS resin-epoxy resin two-component hybrid adhesive according to any one of claims 1-8, characterized in that: The mass ratio of Component A to Component B is 1-2:1; By mass, Component A includes the following components: 60-90 parts of silane-modified polyether resin, 5-10 parts of polysiloxane-polyether epoxy block copolymer, 0.1-5 parts of silane coupling agent, 0.1-5 parts of antioxidant, 0.1-0.5 parts of epoxy resin curing accelerator, 5-10 parts of first filler, and 0.1-1 part of first catalyst; By mass, Component B includes the following components: 30-80 parts of epoxy resin, 0.1-5 parts of silane coupling agent, 20-50 parts of plasticizer, 0.1-0.5 parts of silane-modified polyether resin curing accelerator, 5-10 parts of second filler, and 0.1-1 part of second catalyst.

10. A method for preparing the MS resin-epoxy resin two-component hybrid adhesive as described in claim 9, characterized in that: It includes the following steps: (1) Weigh each component in proportion. After vacuum dehydrating the silane-modified polyether resin, polysiloxane-polyether epoxy block copolymer, and first filler, maintain the vacuum condition and cool to room temperature, then add the silane coupling agent, antioxidant, epoxy resin curing accelerator, and first catalyst, and stir and mix evenly to obtain Component A; (2) Weigh each component proportionally, and mix epoxy resin, silane coupling agent, plasticizer, curing accelerator for silane-modified polyether resin, second filler, and second catalyst evenly to obtain Component B. (3) Mix the obtained Component A and Component B to obtain the two-component hybrid adhesive.

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