Resin with self-repairing function for packaging substrate as well as preparation method and application of resin

Abstract

The invention provides a resin with a self-repairing function for a package carrier and a preparation method and application of the resin. According to the invention, a compound simultaneously containing a benzocyclobutene structure and an allyl structure and a bismaleimide monomer containing a boric acid ester bond are synthesized. Furthermore, the two monomers are pre-polymerized and blended with an olefin monomer containing a benzocyclobutene structure to prepare the resin for the packaging carrier plate. In the application, due to the introduction of a large number of benzocyclobutene structures, the crosslinking density and conformational change can be greatly improved after thermocuring, and the thermal expansion coefficient of the material can be greatly reduced. Meanwhile, the prepared resin contains boric acid ester bonds, so that dynamic exchange can be performed at a high temperature, the material is endowed with a self-repairing function, and the material is endowed with good heat resistance due to the high-rigidity structures of benzocyclobutene and bismaleimide. Therefore, the resin has a self-repairing function and also has the characteristics of low expansion and high heat resistance, so that the resin is an ideal semiconductor packaging material.

Description

Technical Field

[0001] This application relates to the field of semiconductor technology, and more specifically, to a self-healing resin for packaging substrates, its preparation method, and its application. Background Technology

[0002] As the semiconductor industry advances towards higher integration and computing power, the number of layers in packaging substrates is increasing, and the circuitry is becoming more intricate and complex. The connections between different layers are achieved through-hole vias, resulting in tens or even hundreds of thousands of through-hole vias in packaging substrates. However, due to the high glass transition temperature and high modulus of packaging substrates, the resin used in the insulating layer is brittle and prone to microcracks during drilling, leading to reliability risks such as localized short circuits or ion migration. Therefore, microcracks generated during drilling severely impact the processing yield of packaging substrates. How to avoid the generation of microcracks, or achieve efficient repair of microcracks, and fabricate high-quality through-hole vias has become a critical technology urgently needing breakthroughs in the semiconductor packaging substrate field.

[0003] Furthermore, with the development of high-performance chips, the number of connection points between them and the packaging substrate is increasing exponentially, especially with the development of advanced packaging such as FCBGA. In order to ensure high-precision packaging of the chip and the packaging substrate and meet extremely high reliability requirements, the thermal expansion properties of the packaging substrate and the chip must have a high degree of matching. Since the chip hardly undergoes thermal expansion, the packaging substrate material must also have an extremely low coefficient of thermal expansion.

[0004] BT resin, prepared based on bismaleimide monomers, possesses excellent heat resistance and is widely used in the fabrication of packaging substrates. However, its high brittleness makes it prone to microcracks during large-scale drilling, leading to product failure. Furthermore, its excessively high coefficient of thermal expansion makes it difficult to meet the advanced packaging requirements of high-performance chips. Therefore, developing high-performance resins that prevent microcrack formation during drilling or possess microcrack repair capabilities, along with a low coefficient of thermal expansion and high heat resistance, is of significant strategic importance to my country's semiconductor packaging industry. Summary of the Invention

[0005] To overcome at least one of the problems existing in the prior art, the primary objective of this application is to provide a self-healing resin for encapsulation substrates, its preparation method, and its applications. Furthermore, a self-healing composite material based on this resin is proposed. This application designs and synthesizes compounds containing benzocyclobutene and allyl structures, and a bismaleimide monomer containing borate ester bonds. These two synthesized compounds are prepolymerized with an olefin monomer containing benzocyclobutene structures via an ene (alder-ene reaction) chain extension reaction to obtain a self-healing resin for encapsulation substrates. The abundant introduction of borate ester bonds endows the resin with self-healing capabilities for microcracks, while the presence of numerous benzocyclobutene structures allows for further thermosetting, significantly increasing the crosslinking density of the material. Furthermore, the conformational changes of the cured product synergistically reduce the coefficient of thermal expansion. Therefore, when this resin is used to manufacture encapsulation substrates, it can repair microcracks generated during the drilling process, and its low coefficient of thermal expansion meets the high-precision and high-reliability encapsulation requirements of high-performance chips.

[0006] To achieve the above objectives, the technical solution adopted in this application is as follows: A self-healing encapsulation carrier resin comprises the following components in parts by weight: 75-216 parts of compounds containing benzocyclobutene and allyl structures, 100-200 parts of bismaleimide monomers containing borate ester bonds, and 70-200 parts of olefin monomers containing benzocyclobutene structures.

[0007] Furthermore, the compound containing benzocyclobutene and allyl structures described in this application is prepared from the following raw materials in parts by weight: 53-134 parts of hydroxyallyl compound, 53-183 parts of halobenzocyclobutene, 61-207 parts of acid-binding agent, and 300-800 parts of solvent.

[0008] Furthermore, the hydroxyallyl compound described in this application is one or a mixture of two or more compounds with the following structural formulas: ; .

[0009] Furthermore, the halobenzocyclobutene structure described in this application is as follows: or X is a halogen atom, preferably a chlorine atom or a bromine atom, and the substitution position is one or both of the 2, 3, 4 and 5 positions on the benzene ring.

[0010] Furthermore, the acid-binding agent described in this application is one or a mixture of two or more of potassium carbonate and triethylamine.

[0011] Furthermore, the solvent described in this application is one or a mixture of two or more of acetone, butanone, and tetrahydrofuran.

[0012] Another technical objective of this application is to provide a method for synthesizing compounds containing benzocyclobutene and allyl structures as described above, comprising the following steps: adding a hydroxyl-containing allyl compound, an acid-binding agent, and a solvent sequentially to a three-necked flask, heating to 60°C, then adding halobenzocyclobutene dropwise to the three-necked flask, continuing the reaction for 12 hours, filtering to remove the residue, removing the solvent by rotary evaporation of the filtrate to obtain a crude product, continuing to wash the crude product with methanol, repeating this process 3 times, and finally drying it in an 80°C vacuum oven for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0013] Furthermore, the boron ester bond-containing bismaleimide monomer structure described in this application is as follows: .

[0014] Furthermore, the bismaleimide monomer containing a borate ester bond described in this application is prepared from the following raw materials in parts by weight: 50-100 parts of compound 1, 15-32 parts of 1,4-phenylenediboric acid, and 1000-2500 parts of solvent. The structural formula of compound 1 is as follows: ; Formula 1.

[0015] Furthermore, the compound of formula 1 described in this application is prepared from the following raw materials in parts by weight: 40-140 parts of compound of formula 2, 20-75 parts of 3-amino-1,2-propanediol, and 180-800 parts of ethanol. The structural formula of the compound of formula 2 is as follows: ; Equation 2.

[0016] Furthermore, the compound of formula 2 described in this application is prepared from the following raw materials in parts by weight: 30-100 parts of maleic anhydride, 20-72 parts of furan, and 150-400 parts of ethyl acetate.

[0017] Another technical objective of this application is to provide a method for synthesizing the compound of Formula 2 as described above, comprising the following steps: at room temperature, furan, maleic anhydride and ethyl acetate are added sequentially to a beaker, and the mixture is continuously stirred magnetically. After reacting for 24 hours, a white solid is obtained by filtration. The white solid is then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain the compound of Formula 2.

[0018] Another technical objective of this application is to provide a method for synthesizing the compound of Formula 1 as described above, comprising the following steps: adding the compound of Formula 2, 3-amino-1,2-propanediol and ethanol sequentially into a three-necked flask, heating to 85°C and continuously stirring magnetically for 6 hours, then stopping the stirring and cooling to 4°C, maintaining the temperature for 4 hours to precipitate the product, filtering to obtain a solid product, washing the product with ethanol, and drying it under vacuum at 50°C to obtain the compound of Formula 1.

[0019] Another technical objective of this application is to provide a method for synthesizing the borate ester bond bismaleimide monomer as described above, comprising the following steps: adding the compound of formula 1 and the solvent sequentially to a three-necked flask, heating to 145°C while simultaneously stirring magnetically, maintaining the temperature for 1 hour, adding 1,4-phenyldiboronic acid, then continuously purging with nitrogen gas, reacting for 36 hours, stopping heating and cooling to room temperature, filtering to obtain a filtrate, removing the solution by rotary evaporation of the filtrate to obtain a solid, and further drying under vacuum at 80°C to obtain the borate ester bond bismaleimide monomer.

[0020] Furthermore, the olefin monomer containing the benzocyclobutene structure described in this application is one or a mixture of two or more compounds with the following structural formulas: .

[0021] Another technical objective of this application is to provide a method for preparing a self-healing encapsulation substrate resin as described above, comprising the following steps: sequentially adding compounds containing benzocyclobutene and allyl structures and bismaleimide monomers containing boron ester bonds into a three-necked flask, heating to 150°C, reacting for 1.5 h, then cooling to 125°C, adding olefin monomers containing benzocyclobutene structures and continuing mechanical stirring for 0.5 h, then removing the prepolymer and pulverizing it using a pulverizer to obtain the self-healing encapsulation substrate resin.

[0022] Another technical objective of this application is to provide a self-healing composite material, the raw material of which is the resin for encapsulation carrier plates with self-healing function as described above.

[0023] Compared with the prior art, the beneficial effects of this application are: 1. This application designs and synthesizes compounds containing benzocyclobutene and allyl structures. The allyl group can undergo chain extension reaction with bismaleimide monomers to obtain a uniform, non-phase-separated resin. At the same time, the introduced benzocyclobutene structure can be thermosetting to increase the crosslinking density of the material. Furthermore, the product can reduce the coefficient of thermal expansion of the material through conformational changes, thereby improving the high-precision and high-reliability packaging of high-performance chips by the packaging substrate.

[0024] 2. This application synthesizes a bismaleimide monomer containing borate ester bonds and prepares a resin for encapsulation substrates with self-healing function. Due to the dynamic exchange characteristics of borate ester bonds, microcracks generated during drilling in the encapsulation substrate can be repaired, significantly improving the processing yield and reliability of the encapsulation substrate. Attached Figure Description

[0025] Figure 1 The images show a comparison of the morphology of the composite materials in the embodiments and comparative examples of this application after cracking and after repair treatment. Detailed Implementation

[0026] The embodiments of this application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this application. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0027] It should be noted that: Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0028] In this application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0029] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to a person skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this application.

[0030] This application provides a self-healing encapsulation carrier resin comprising the following components in parts by weight: 75-216 parts of compounds containing benzocyclobutene and allyl structures, 100-200 parts of bismaleimide monomers containing borate ester bonds, and 70-200 parts of olefin monomers containing benzocyclobutene structures.

[0031] In some preferred embodiments, the compound containing benzocyclobutene and allyl structures is prepared by weight from the following raw materials: 53-134 parts of hydroxyallyl compound, 53-183 parts of halogenated benzocyclobutene, 61-207 parts of acid-binding agent, and 300-800 parts of solvent.

[0032] In some preferred embodiments, the hydroxyallyl compound is one or a mixture of two or more compounds with the following structural formulas: ; .

[0033] In some preferred embodiments, the halobenzocyclobutene structure described in this application is as follows: or X is a halogen atom, preferably a chlorine atom or a bromine atom, and the substitution position is one or both of the 2, 3, 4 and 5 positions on the benzene ring.

[0034] In some preferred embodiments, the acid-binding agent described in this application is one or a mixture of two or more of potassium carbonate and triethylamine.

[0035] In some preferred embodiments, the solvent described in this application is one or a mixture of two or more of acetone, butanone, and tetrahydrofuran.

[0036] This application also provides a method for synthesizing compounds containing benzocyclobutene and allyl structures as described above, comprising the following steps: adding a hydroxyl-containing allyl compound, an acid-binding agent, and a solvent sequentially to a three-necked flask, heating to 60°C, then adding halobenzocyclobutene dropwise to the three-necked flask, continuing the reaction for 12 hours, filtering to remove the residue, removing the solvent by rotary evaporation of the filtrate to obtain a crude product, continuing to wash the crude product with methanol, repeating 3 times, and finally drying it in an 80°C vacuum oven for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0037] In some preferred embodiments, the borate ester bond bismaleimide monomer structure described in this application is as follows: .

[0038] In some preferred embodiments, the bismaleimide monomer containing a borate ester bond described in this application is prepared from the following raw materials in parts by weight: 50-100 parts of compound of formula 1, 15-32 parts of 1,4-phenylenediboric acid, and 1000-2500 parts of solvent. The structural formula of compound of formula 1 is as follows: ; Formula 1.

[0039] In some preferred embodiments, the compound of formula 1 described in this application is prepared from the following raw materials in parts by weight: 40-140 parts of compound of formula 2, 20-75 parts of 3-amino-1,2-propanediol, and 180-800 parts of ethanol. The structural formula of the compound of formula 2 is as follows: ; Equation 2.

[0040] In some preferred embodiments, the compound of formula 2 is prepared from the following raw materials in parts by weight: 30-100 parts maleic anhydride, 20-72 parts furan, and 150-400 parts ethyl acetate.

[0041] This application also provides a method for synthesizing the compound of formula 2 as described above, comprising the following steps: at room temperature, furan, maleic anhydride and ethyl acetate are added sequentially to a beaker, and the mixture is continuously stirred magnetically. After reacting for 24 hours, a white solid is obtained by filtration. The white solid is then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain the compound of formula 2.

[0042] This application also provides a method for synthesizing the compound of Formula 1 as described above, comprising the following steps: adding the compound of Formula 2, 3-amino-1,2-propanediol and ethanol sequentially into a three-necked flask, heating to 85°C and continuously stirring magnetically for 6 hours, then stopping the stirring and cooling to 4°C, maintaining the temperature for 4 hours to precipitate the product, filtering to obtain a solid product, washing the product with ethanol, and drying it under vacuum at 50°C to obtain the compound of Formula 1.

[0043] This application also provides a method for synthesizing the borate ester bond bismaleimide monomer as described above, comprising the following steps: adding the compound of formula 1 and solvent sequentially to a three-necked flask, heating to 145°C while simultaneously stirring magnetically, maintaining the temperature for 1 hour, adding 1,4-phenyldiboronic acid, then continuously purging with nitrogen gas, reacting for 36 hours, stopping heating and cooling to room temperature, filtering to obtain a filtrate, removing the solution by rotary evaporation of the filtrate to obtain a solid, and further drying under vacuum at 80°C to obtain the borate ester bond bismaleimide monomer.

[0044] In some preferred embodiments, the benzocyclobutene-containing olefin monomer described in this application is one or a mixture of two or more compounds with the following structural formulas: .

[0045] Another technical objective of this application is to provide a method for preparing a self-healing encapsulation substrate resin as described above, comprising the following steps: sequentially adding compounds containing benzocyclobutene and allyl structures and bismaleimide monomers containing boron ester bonds into a three-necked flask, heating to 150°C, reacting for 1.5 h, then cooling to 125°C, adding olefin monomers containing benzocyclobutene structures and continuing mechanical stirring for 0.5 h, then removing the prepolymer and pulverizing it using a pulverizer to obtain the self-healing encapsulation substrate resin.

[0046] Another technical objective of this application is to provide a self-healing composite material, the raw material of which is the resin for encapsulation carrier plates with self-healing function as described above.

[0047] This application designs and synthesizes compounds containing benzocyclobutene and allyl structures, wherein the allyl group can undergo an ene chain extension reaction with a bismaleimide monomer (the chemical reaction is as follows). A uniform, phase-separated resin is obtained, and the introduced benzocyclobutene structure can be thermosetting to increase the crosslinking density of the material. Furthermore, the product can synergistically reduce the thermal expansion coefficient of the material through conformational changes (the thermosetting crosslinking and conformational change mechanism of benzocyclobutene is shown below), thereby improving the high-precision and high-reliability packaging of high-performance chips by the packaging substrate.

[0048] ; This application synthesizes a bismaleimide monomer containing borate ester bonds and prepares a resin for encapsulation substrates with self-healing capabilities. Due to the dynamic exchange properties of the borate ester bonds, microcracks generated during drilling in the encapsulation substrate can be repaired, significantly improving the processing yield and reliability of the encapsulation substrate. The dynamic exchange mechanism of the borate ester bonds is as follows: .

[0049] Next, specific embodiments will be used to describe in detail the preparation methods of the compounds containing benzocyclobutene and allyl structures, the bismaleimide monomer containing boron ester bonds, the resin for encapsulation substrates with self-healing function, and the self-healing composite materials of this application.

[0050] Example 1 Synthesis of compounds containing benzocyclobutene and allyl structures 58 parts of allyl alcohol, 207 parts of potassium carbonate, and 500 parts of acetone were added sequentially to a three-necked flask and heated to 60°C. Then, 131 parts of 2,5-dibromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0051] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 20 parts of furan, 30 parts of maleic anhydride and 150 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0052] 45 parts of compound 2, 23 parts of 3-amino-1,2-propanediol and 200 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0053] 50 parts of compound 1, 800 parts of N,N-dimethylformamide, and 200 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 16 parts of 1,4-phenyldiboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing a boron ester bond.

[0054] 3. Preparation of resin for encapsulation carrier with self-healing function 75 parts of compounds containing benzocyclobutene and allyl structures and 100 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 130 parts of BCB-St were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0055] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0056] Example 2 1. Synthesis of compounds containing benzocyclobutene and allyl structures 77 parts of 2,2'-diallylbisphenol A, 76 parts of triethylamine, and 400 parts of butanone were added sequentially to a three-necked flask and heated to 60°C. Then, 92 parts of 4-bromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0057] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 35 parts of furan, 55 parts of maleic anhydride and 250 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0058] 50 parts of compound 2, 26 parts of 3-amino-1,2-propanediol and 250 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated after being kept at the same temperature for 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0059] 85 parts of compound 1, 1500 parts of N,N-dimethylformamide, and 300 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 28 parts of 1,4-phenylenediboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing a boron ester bond.

[0060] 3. Preparation of resin for encapsulation carrier with self-healing function 176 parts of compounds containing benzocyclobutene and allyl structures and 150 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 150 parts of BCB-O-St were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0061] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0062] Example 3 1. Synthesis of compounds containing benzocyclobutene and allyl structures 104 parts of 2,2'-diallyl hexafluorobisphenol A, 155 parts of potassium carbonate, and 600 parts of tetrahydrofuran were added sequentially to a three-necked flask and heated to 60°C. Then, 92 parts of 4-bromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0063] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 38 parts of furan, 60 parts of maleic anhydride and 300 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0064] In a three-necked flask, 85 parts of compound 2, 45 parts of 3-amino-1,2-propanediol, and 400 parts of ethanol were added sequentially. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then, the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0065] 90 parts of compound 1, 1800 parts of N,N-dimethylformamide, and 500 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 30 parts of 1,4-phenyldiboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing a boron ester bond.

[0066] 3. Preparation of resin for encapsulation carrier with self-healing function 171 parts of compounds containing benzocyclobutene and allyl structures and 120 parts of bismaleimide monomers containing boron ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 70 parts of BCB-St-Ph were added, with mechanical stirring continued for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0067] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0068] Example 4 1. Synthesis of compounds containing benzocyclobutene and allyl structures In a three-necked flask, 82 parts of eugenol, 76 parts of triethylamine, and 300 parts of acetone were added sequentially and heated to 60°C. Then, 66 parts of 2,5-dibromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0069] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 50 parts of furan, 75 parts of maleic anhydride and 350 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0070] 120 parts of compound 2, 64 parts of 3-amino-1,2-propanediol and 600 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0071] 80 parts of compound 1, 1500 parts of N,N-dimethylformamide, and 400 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 27 parts of 1,4-phenyldiboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing boron ester bonds.

[0072] 3. Preparation of resin for encapsulation carrier with self-healing function 177 parts of compounds containing benzocyclobutene and allyl structures and 180 parts of bismaleimide monomers containing boron ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 150 parts of BCB-St-BCB were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0073] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0074] Example 5 1. Synthesis of compounds containing benzocyclobutene and allyl structures In a three-necked flask, 133 parts of magnolol, 207 parts of potassium carbonate, and 800 parts of butanone were added sequentially. The mixture was heated to 60°C, and then 183 parts of 4-bromobenzocyclobutene were added dropwise to the flask. The reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0075] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 72 parts of furan, 100 parts of maleic anhydride and 400 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0076] 140 parts of compound 2, 75 parts of 3-amino-1,2-propanediol and 800 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0077] 72 parts of compound 1, 1000 parts of N,N-dimethylformamide, and 250 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 22 parts of 1,4-phenylenediboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing boron ester bonds.

[0078] 3. Preparation of resin for encapsulation carrier with self-healing function 216 parts of compounds containing benzocyclobutene and allyl structures and 200 parts of bismaleimide monomers containing boron ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 180 parts of BCB-St-Si were added, with mechanical stirring continued for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0079] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0080] Example 6 1. Synthesis of compounds containing benzocyclobutene and allyl structures In a three-necked flask, 53 parts of magnolol, 61 parts of triethylamine, and 300 parts of tetrahydrofuran were added sequentially and heated to 60°C. Then, 73 parts of 4-bromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0081] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 55 parts of furan, 80 parts of maleic anhydride and 350 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0082] In a three-necked flask, 40 parts of compound 2, 20 parts of 3-amino-1,2-propanediol, and 180 parts of ethanol were added sequentially. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then, the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0083] 50 parts of compound 1, 800 parts of N,N-dimethylformamide, and 250 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 15 parts of 1,4-phenylenediboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing boron ester bonds.

[0084] 3. Preparation of resin for encapsulation carrier with self-healing function 162 parts of compounds containing benzocyclobutene and allyl structures and 150 parts of bismaleimide monomers containing boron ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 120 parts of BCB-St-Si were added, with mechanical stirring continued for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0085] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0086] Example 7 1. Synthesis of compounds containing benzocyclobutene and allyl structures 133 parts of isomagnolol, 104 parts of potassium carbonate and 500 parts of acetone were added sequentially to a three-necked flask and heated to 60°C. Then, 92 parts of 4-bromobenzocyclobutene were added dropwise to the three-necked flask and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0087] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 22 parts of furan, 30 parts of maleic anhydride and 150 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0088] 50 parts of compound 2, 25 parts of 3-amino-1,2-propanediol and 200 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0089] 90 parts of compound 1, 1800 parts of N,N-dimethylformamide, and 400 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 32 parts of 1,4-phenyldiboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing boron ester bonds.

[0090] 3. Preparation of resin for encapsulation carrier with self-healing function 101 parts of compounds containing benzocyclobutene and allyl structures and 120 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 120 parts of BCB-St-BCB were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0091] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0092] Example 8 1. Synthesis of compounds containing benzocyclobutene and allyl structures 67 parts of 2-allylphenol, 76 parts of triethylamine, and 300 parts of butanone were added sequentially to a three-necked flask and heated to 60°C. Then, 66 parts of 2,5-dibromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0093] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 33 parts of furan, 52 parts of maleic anhydride and 250 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0094] In a three-necked flask, 83 parts of compound 2, 43 parts of 3-amino-1,2-propanediol, and 370 parts of ethanol were added sequentially. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then, the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0095] 90 parts of compound 1, 2000 parts of N,N-dimethylformamide, and 400 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 30 parts of 1,4-phenyldiboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The filtrate was filtered, and the solution was removed by rotary evaporation to obtain a solid. The solid was then dried under vacuum at 80°C to obtain the bismaleimide monomer containing boron ester bonds.

[0096] 3. Preparation of resin for encapsulation carrier with self-healing function 152 parts of compounds containing benzocyclobutene and allyl structures and 180 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 200 parts of BCB-St-Ph were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0097] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0098] Example 9 1. Synthesis of compounds containing benzocyclobutene and allyl structures 54 parts of 3-allylphenol, 83 parts of potassium carbonate, and 300 parts of tetrahydrofuran were added sequentially to a three-necked flask and heated to 60°C. Then, 53 parts of 2,5-dibromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0099] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 40 parts of furan, 62 parts of maleic anhydride and 300 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0100] 120 parts of compound 2, 62 parts of 3-amino-1,2-propanediol and 550 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0101] 78 parts of compound 1, 1500 parts of N,N-dimethylformamide, and 350 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 25 parts of 1,4-phenyldiboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing boron ester bonds.

[0102] 3. Preparation of resin for encapsulation carrier with self-healing function 101 parts of compounds containing benzocyclobutene and allyl structures and 120 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 120 parts of BCB-O-St were added, with mechanical stirring continued for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0103] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0104] Example 10 1. Synthesis of compounds containing benzocyclobutene and allyl structures 134 parts of 4-allylphenol, 152 parts of triethylamine, and 600 parts of acetone were added sequentially to a three-necked flask and heated to 60°C. Then, 131 parts of 2,5-dibromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0105] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 50 parts of furan, 73 parts of maleic anhydride and 350 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0106] 140 parts of compound 2, 72 parts of 3-amino-1,2-propanediol and 750 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0107] 72 parts of compound 1, 1500 parts of N,N-dimethylformamide, and 300 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 23 parts of 1,4-phenylenediboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing boron ester bonds.

[0108] 3. Preparation of resin for encapsulation carrier with self-healing function 84 parts of compounds containing benzocyclobutene and allyl structures and 100 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 130 parts of BCB-St were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0109] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0110] Example 11 1. Synthesis of compounds containing benzocyclobutene and allyl structures 95 parts of 2,5-diallyl hydroquinone, 207 parts of potassium carbonate, and 600 parts of butanone were added sequentially to a three-necked flask and heated to 60°C. Then, 183 parts of 4-bromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0111] 2. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 68 parts of furan, 100 parts of maleic anhydride and 400 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0112] 66 parts of compound 2, 35 parts of 3-amino-1,2-propanediol and 400 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated by holding the temperature at 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0113] 100 parts of compound 1, 2000 parts of N,N-dimethylformamide, and 500 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 32 parts of 1,4-phenylenediboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing a borate ester bond.

[0114] 3. Preparation of resin for encapsulation carrier with self-healing function 136 parts of compounds containing benzocyclobutene and allyl structures and 150 parts of bismaleimide monomers containing borate ester bonds were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 120 parts of BCB-O-St were added, with mechanical stirring continued for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0115] 4. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0116] Comparative Example 1 1. Preparation of resin for encapsulation substrate 176 parts of 2,2'-diallyl bisphenol A and 150 parts of diphenylmethane bismaleimide were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 150 parts of bisphenol A cyanate ester resin were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0117] 2. Preparation of composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0118] Comparative Example 2 1. Synthesis of compounds containing benzocyclobutene and allyl structures 77 parts of 2,2'-diallylbisphenol A, 76 parts of triethylamine, and 400 parts of butanone were added sequentially to a three-necked flask and heated to 60°C. Then, 92 parts of 4-bromobenzocyclobutene were added dropwise to the three-necked flask, and the reaction was continued for 12 hours. The residue was removed by filtration, and the solvent was removed by rotary evaporation of the filtrate to obtain the crude product. The crude product was washed with methanol three times. Finally, it was dried in a vacuum oven at 80°C for 4 hours to obtain a compound containing benzocyclobutene and allyl structures.

[0119] 2. Preparation of resin for encapsulation substrate 176 parts of compounds containing benzocyclobutene and allyl structures and 150 parts of diphenylmethane bismaleimide were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 150 parts of BCB-O-St were added, with mechanical stirring continuing for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0120] 3. Preparation of composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0121] Comparative Example 3 1. Synthesis of bismaleimide monomers containing boron ester bonds At room temperature, 35 parts of furan, 55 parts of maleic anhydride and 250 parts of ethyl acetate were added to a beaker in sequence and the mixture was continuously stirred magnetically. After reacting for 24 hours, the mixture was filtered to obtain a white solid. The white solid was then washed three times with ethyl acetate and dried under vacuum at 50°C to obtain compound 2.

[0122] 50 parts of compound 2, 26 parts of 3-amino-1,2-propanediol and 250 parts of ethanol were added sequentially to a three-necked flask. The mixture was heated to 85°C and continuously stirred magnetically for 6 hours. Then the stirring was stopped and the temperature was lowered to 4°C. The product was precipitated after being kept at the same temperature for 4 hours. The solid product was obtained by filtration. The product was washed with ethanol and dried under vacuum at 50°C to obtain compound 1.

[0123] 85 parts of compound 1, 1500 parts of N,N-dimethylformamide, and 300 parts of toluene were added sequentially to a three-necked flask. The mixture was heated to 145°C and magnetically stirred simultaneously. After maintaining the temperature for 1 hour, 28 parts of 1,4-phenylenediboronic acid were added, and nitrogen gas was continuously introduced. After reacting for 36 hours, heating was stopped and the mixture was cooled to room temperature. The mixture was filtered to obtain a filtrate. The filtrate was then rotary evaporated to remove the solution and obtain a solid. The solid was further dried under vacuum at 80°C to obtain a bismaleimide monomer containing a boron ester bond.

[0124] 2. Preparation of resin for self-healing encapsulation substrates 176 parts of 2,2'-diallyl bisphenol A and 150 parts of borate ester bond-containing bismaleimide monomer were sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. The temperature was then lowered to 125°C, and 150 parts of bisphenol A type cyanate ester resin were added, with mechanical stirring continued for another 0.5 h. The prepolymer was then removed and pulverized using a pulverizer to obtain a self-healing encapsulation substrate resin.

[0125] 3. Preparation of self-healing composite materials Place 6.5 parts of the self-healing resin into a 100*100*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, and place it in a vacuum press with a pressure set to 28 kgf / cm². 2 The material is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a self-healing composite material with a thickness of 0.5 mm.

[0126] II. Effect Test (1) Glass transition temperature The composite materials from the examples and comparative examples were cut into strips with dimensions of 6cm x 1cm. The glass transition temperature of the materials was measured using a TA DMA850 dynamic thermomechanical analyzer. The test conditions were: heating from 50°C to 300°C at a rate of 3°C / min, a frequency of 1Hz, and a deformation of 20μm.

[0127] (2) Coefficient of thermal expansion The composite materials used in the examples and comparative examples were cut into test samples with dimensions of 0.6 cm x 0.6 cm. The coefficient of thermal expansion of the samples was measured using a TA Instruments TMA450 static thermomechanical analyzer. The test conditions were as follows: heating from 50 °C to 300 °C at a rate of 10 °C / min, then cooling to 50 °C, and then heating again to 300 °C, with a load of 0.05 N. The coefficient of thermal expansion between 75 and 150 °C during the second heating process was obtained.

[0128] (3) Repair effect Use a blade to make cracks on the surface of the composite material, then place the composite material in a 100*100*0.5mm stainless steel mold frame, cover it with polytetrafluoroethylene film on the top and bottom, and place it in a vacuum press with a pressure set to 10 kgf / cm². 2 The composite materials were pressed at 250°C for 1 hour for repair treatment, and then removed after cooling. The morphology of the composite materials in the examples and comparative examples after scratching and after repair treatment was observed using a Keyence VHX-1000 ultra-depth-of-field 3D microscope (e.g., ...). Figure 1 As shown in the figure, determine whether the crack has been repaired.

[0129] Table 1. Glass transition temperature, coefficient of thermal expansion and crack repair effect of the composite materials in Examples 1-11 and Comparative Examples 1-3.

[0130] ; As shown in Comparative Example 1 in Table 1, traditional encapsulation substrate materials generally use 2,2'-diallyl bisphenol A and cyanate ester to modify bismaleimide to obtain the resin for encapsulation substrates. Due to its high brittleness, the corresponding encapsulation substrate is prone to microcracks during drilling, leading to short circuits and ion migration, severely affecting product yield and reliability. Furthermore, this resin has a glass transition temperature of only 197℃ and a coefficient of thermal expansion as high as 63.8. As shown in Comparative Example 2, by introducing a large number of benzocyclobutene structures, its thermosetting specificity not only increases the crosslinking density, thereby increasing the glass transition temperature and reducing the coefficient of thermal expansion, but also further reduces the coefficient of thermal expansion through conformational changes. However, due to the lack of self-healing function, it is prone to microcracks, leading to product failure. As shown in Comparative Example 3, by introducing dynamic borate ester bonds, the composite material is endowed with self-healing function. However, the composite material obtained by modifying traditional 2,2'-diallyl bisphenol A and cyanate ester has a coefficient of thermal expansion as high as 66.2, which is difficult to meet the high-precision packaging requirements of high-performance chips.

[0131] As shown in Examples 1-11, this invention synthesizes compounds containing benzocyclobutene and allyl structures, as well as bismaleimide monomers containing borate ester bonds. These compounds are prepolymerized via an ene chain extension reaction. Simultaneously, olefin monomers containing benzocyclobutene structures are added to further increase the benzocyclobutene content, resulting in a resin for encapsulation substrates. The introduction of numerous dynamic borate ester bonds endows the composite material with self-healing capabilities. Furthermore, to significantly reduce the coefficient of thermal expansion of the composite material and meet the low thermal expansion coefficient requirements of high-precision, high-reliability packaging for high-performance chips, a large number of benzocyclobutene structures are introduced. During hot pressing, this structure further crosslinks, significantly increasing the crosslinking density, raising the glass transition temperature, and reducing the coefficient of thermal expansion. The resulting eight-membered ring structure can further reduce the coefficient of thermal expansion of the composite material through conformational changes. The resulting composite material has a glass transition temperature as high as 210-221℃ and a coefficient of thermal expansion as low as 33.3-40.5ppm / ℃. The resin designed in this invention has a high glass transition temperature and a low coefficient of thermal expansion, which can meet the stringent requirements of semiconductor packaging substrate materials for heat resistance and dimensional stability. At the same time, its self-healing function can repair microcracks generated during the fabrication of through-holes and blind holes, greatly improving reliability and product yield. It is evident that this resin has broad application potential in the field of semiconductor packaging substrates.

[0132] This application relates to the synthesis of compounds containing benzocyclobutene and allyl structures. The allyl group can undergo chain extension reaction with bismaleimide monomers to obtain a uniform, non-phase-separated resin. At the same time, the introduced benzocyclobutene structure can be thermosetting to increase the crosslinking density of the material. Furthermore, the product can synergistically reduce the coefficient of thermal expansion of the material through conformational changes, thereby improving the high-precision and high-reliability packaging of high-performance chips by the packaging substrate.

[0133] This application synthesizes and prepolymerizes a bismaleimide monomer containing borate ester bonds to obtain a self-healing resin for encapsulation substrates. Due to the dynamic exchange characteristics of the borate ester bonds, the microcracks generated during drilling in the encapsulation substrate can be repaired, significantly improving the processing yield and reliability of the encapsulation substrate.

[0134] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0135] Although several embodiments of this application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this application, the scope of which is defined by the claims and their equivalents.

Claims

1. A resin for encapsulation carriers with self-healing function, characterized in that, The components include the following parts by weight: 75-216 parts of compounds containing benzocyclobutene and allyl structures, 100-200 parts of bismaleimide monomers containing borate ester bonds, and 70-200 parts of olefin monomers containing benzocyclobutene structures.

2. The resin for encapsulation carrier with self-healing function according to claim 1, characterized in that: The compound containing benzocyclobutene and allyl structures is prepared by weight from the following raw materials: 53-134 parts of hydroxyl-containing allyl compound, 53-183 parts of halobenzocyclobutene, 61-207 parts of acid-binding agent, and 300-800 parts of solvent.

3. The resin for encapsulation carriers with self-healing function according to claim 2, characterized in that: The hydroxy-containing allyl compound is one or a mixture of two or more compounds with the following structural formulas: 、 、 、 、 、 、 、 、 、 、 。 4. The resin for encapsulation carriers with self-healing function according to claim 2, characterized in that, The halobenzocyclobutene structure is as follows: or , where X is a chlorine atom or a bromine atom, and the substitution position is one or both of the 2, 3, 4, and 5 positions on the benzene ring.

5. The resin for encapsulation carriers with self-healing function according to claim 2, characterized in that, The acid-binding agent is one or a mixture of potassium carbonate and triethylamine.

6. The resin for encapsulation carrier with self-healing function according to claim 2, characterized in that: The solvent is one or a mixture of two or more of acetone, butanone, and tetrahydrofuran.

7. The resin for encapsulation carriers with self-healing function according to claim 1, characterized in that, The boron ester bond-containing bismaleimide monomer has the following structure: .

8. The resin for encapsulation carrier with self-healing function according to claim 1, characterized in that, The olefin monomer containing the benzocyclobutene structure is one or a mixture of two or more compounds with the following structural formulas: 、 、 、 、 。 9. A method for preparing a self-healing encapsulation carrier resin as described in claim 1, characterized in that, The process includes the following steps: compounds containing benzocyclobutene and allyl structures and bismaleimide monomers containing borate ester bonds are sequentially added to a three-necked flask, heated to 150°C, and reacted for 1.5 h. Then, the temperature is lowered to 125°C, olefin monomers containing benzocyclobutene structures are added, and the reaction is continued with mechanical stirring for 0.5 h. The prepolymer is then removed and pulverized using a pulverizer to obtain a resin for encapsulation substrates with self-healing function.

10. A self-healing composite material, characterized in that, The raw material for preparation is the self-healing resin for encapsulation substrates as described in claim 1.

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