A boronic ester bond-containing maleimide monomer and a self-repairing resin for packaging boards prepared by a synthesis method

Abstract

This application provides a borate ester bond-containing maleimide monomer and a low-dielectric self-healing resin for packaging substrates prepared therefrom, relating to the field of semiconductor technology. The borate ester bond-containing maleimide monomer has the structure of Formula 1. The monomer, maleimide monomer, and fluorinated allyl compound are prepolymerized to obtain a prepolymer resin, which can be used to fabricate semiconductor packaging substrates. Because the resin contains a large number of borate ester bonds, these bonds can exchange at high temperatures, thereby endowing the material with self-healing capabilities. This allows it to repair microcracks generated in the packaging substrate during drilling and other processing, significantly improving the reliability and production yield of the packaging substrate.

Description

Technical Field

[0001] This application relates to the field of semiconductor technology, and more specifically, to a borate ester bond-containing maleimide monomer, its synthesis method, and the self-healing resin for packaging substrates prepared therefrom. Background Technology

[0002] In recent years, Moore's Law has gradually become ineffective, and improving single-chip performance has become increasingly difficult. Advanced packaging, through "integration as king," directly improves computing density and energy efficiency, continuously driving breakthroughs in high-performance computing. As the core material of advanced packaging substrates, the performance of the packaging substrate material is mainly affected by the resin medium within it. Bismaleimide resins, due to their good heat resistance, dimensional stability, and mechanical properties, have gradually become the main resins for preparing packaging substrate materials. However, bismaleimide resins are relatively brittle, and during the packaging substrate processing, especially in the drilling process for creating through-holes and blind vias, they are prone to microcracks, leading to problems such as micro-short circuits, ion migration, and difficulty in fabricating fine circuits, seriously affecting the integration, reliability, and production yield of the packaging substrate. Therefore, the industry commonly uses bismaleimide monomers to prepolymerize with DABPA, DABPS, etc., to achieve toughening, thereby improving drilling defects. Nevertheless, due to the need to balance heat resistance, dielectric properties, and mechanical properties, the toughening range needs to be strictly controlled, thus still making it difficult to completely solve the problem of microcracks generated during drilling. Meanwhile, the toughening modifiers DABPA and DABPS contain a large number of highly polar hydroxyl groups, which leads to a significant decrease in the dielectric properties of the material, seriously affecting the computing power and energy consumption of the semiconductor integrated system.

[0003] Therefore, how to solve the processing problem of poor drilling of packaging substrates through material innovation, while taking into account other comprehensive performance, is of great strategic significance to my country's semiconductor packaging field.

[0004] Application content To overcome at least one of the problems existing in the prior art, the primary objective of this application is to provide a borate ester maleimide monomer, its synthesis method, and a self-healing resin for encapsulation substrates prepared therefrom. Furthermore, it proposes fluorine-modified diallyl hexafluorobisphenol A and a self-healing composite material prepared based on the self-healing resin. By designing and synthesizing the borate ester maleimide monomer and fluorine-modified diallyl hexafluorobisphenol A, further prepolymerizing them with a bismaleimide monomer yields a self-healing resin for encapsulation substrates. This resin possesses self-healing capabilities, significantly improving the quality of through-hole and blind via fabrication in encapsulation substrates, enhancing the reliability and yield of the encapsulation substrates. Simultaneously, the introduction of fluorine imparts low dielectric properties to the encapsulation substrates, increasing system computing power and reducing power consumption.

[0005] To achieve the above objectives, the technical solution adopted in this application is as follows: A boron ester bond-containing maleimide monomer, wherein the boron ester bond-containing maleimide monomer has the following structure: ; Formula 1; Where n1≥2, 6≥m1>2, and n1 and m1 are both positive integers.

[0006] Furthermore, the maleimide monomer containing borate ester bonds described in this application is prepared from the following raw materials by weight: 16.6-97.6 parts of phenylboronic acid compound, 47.8-224.8 parts of compound of formula 2, 1200-4500 parts of polar solvent, and 300-1500 parts of nonpolar solvent, wherein the structure of compound of formula 2 is as follows: ; Formula 2; Where n2≥2, and n2 is a positive integer.

[0007] Furthermore, the structure of the phenylboronic acid compounds described in this application is shown in Formula 3: ; Formula 3; Where 6≥m2≥1, and m2 are all positive integers.

[0008] Furthermore, the compound of formula 2 described in this application is prepared from the following raw materials in parts by weight: 22.75-133 parts of an aminodiol compound, 41.5-166 parts of a compound of formula 4, and 150-600 parts of ethanol, wherein the structural formula of the compound of formula 4 is as follows: ; Formula 4.

[0009] Furthermore, the compound of formula 4 described in this application is prepared from the following raw materials in parts by weight: 49-147 parts of maleic anhydride, 34-102 parts of furan, and 200-600 parts of ethyl acetate.

[0010] Another objective of this application is to provide a method for synthesizing the above-mentioned compound 4, comprising the following steps: adding furan, maleic anhydride and ethyl acetate sequentially to a beaker, continuously stirring with a magnetic force, reacting at room temperature for 24 hours, then filtering to obtain a white solid, washing the white solid with ethyl acetate, and then drying it under vacuum at 50°C to obtain compound 4.

[0011] Furthermore, the structure of the aminodiol-containing compound described in this application is shown in Formula 5: ; Formula 5; Where n3≥1, and n3 are all positive integers.

[0012] Another objective of this application is to provide a method for synthesizing the above-mentioned compound of formula 2, comprising the following steps: sequentially adding compound of formula 4, amino diol-containing compound and ethanol into a flask, continuously stirring with a magnetic force, heating to 85°C for reflux, reacting for 6 hours, then cooling to 4°C, holding at the temperature for 4 hours, filtering to obtain a solid, washing with ethanol, and drying under vacuum at 50°C to obtain compound of formula 2.

[0013] Furthermore, the polar solvent described in this application is one or a mixture of two or more of N,N-dimethylformamide and N,N-dimethylacetamide.

[0014] Furthermore, the non-polar solvent described in this application is one or a mixture of two or more of toluene and xylene.

[0015] Another technical objective of this application is to provide a method for synthesizing the above-mentioned borate ester bond maleimide monomer, comprising the following steps: sequentially adding the compound of formula 2, a polar solvent, and a nonpolar solvent into a three-necked flask, continuously stirring with a magnetic force, heating to 145°C, maintaining the temperature for 1 hour, adding a phenylboronic acid compound, then continuously purging with nitrogen gas, continuing the reaction for 36 hours, stopping the heating and allowing it to cool naturally to room temperature, further filtering to obtain a filtrate, removing the solution from the filtrate by rotary evaporation to obtain a solid, and placing it at 80°C for vacuum drying to obtain the borate ester bond maleimide monomer.

[0016] Another technical objective of this application is to provide a self-healing resin for encapsulating substrates, wherein the formulation comprises the following raw material components by weight: 34.8-111.2 parts of boron ester bond maleimide monomer, 35-140 parts of fluorinated diallyl hexafluorobisphenol A, and 41.4-85.5 parts of bismaleimide monomer.

[0017] Furthermore, the structure of the fluorine-modified diallyl hexafluorobisphenol A described in this application is shown in Formula 6.

[0018] ; Formula 6.

[0019] Furthermore, the fluorine-modified diallyl hexafluorobisphenol A described in this application is prepared from the following raw materials by weight: 15.4-61.6 parts of diallyl hexafluorobisphenol A, 23.3-93 parts of 1-bromoperfluoro-3-methylbutane, 150-400 parts of chloroform, and 40-140 parts of potassium carbonate.

[0020] Another technical objective of this application is to provide a method for synthesizing the above-mentioned fluorine-modified diallyl hexafluorobisphenol A, comprising the following steps: chloroform, diallyl hexafluorobisphenol A, and potassium carbonate are sequentially added to a three-necked flask, placed in an ice bath and continuously magnetically stirred, and then 1-bromoperfluoro-3-methylbutane is gradually added dropwise to the three-necked flask. After the addition is complete, the reaction continues for 24 hours, then the residue is removed by filtration, the filtrate is washed 6 times with deionized water, and the aqueous layer is removed by a separatory funnel while retaining the organic layer. Then, the solvent is further removed by rotary evaporation to obtain fluorine-modified diallyl hexafluorobisphenol A.

[0021] Furthermore, the bismaleimide monomer described in this application is selected from one or a mixture of two or more of the following: 1,6-dimaleimide hexane, 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione, N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylenebismaleimide, 2,2′-bis[4-(4-maleimide-phenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, and 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione.

[0022] Another technical objective of this application is to provide a prepolymerization method for the above-mentioned self-healing resin for encapsulation substrates, comprising the following steps: adding boron ester bond maleimide monomer, fluorinated diallyl hexafluorobisphenol A, and bismaleimide monomer sequentially into a three-necked flask, continuously stirring mechanically, heating to 130-180℃, reacting for 0.5-3 hours, naturally cooling, removing the prepolymer, and pulverizing it using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0023] Another technical objective of this application is to provide a self-healing composite material, the raw material of which is the self-healing resin for encapsulation substrates as described above.

[0024] Compared with the prior art, the beneficial effects of this application are: 1. The maleimide monomer containing borate ester bonds synthesized in this application has a self-healing function after further prepolymerization and curing due to the introduction of dynamically exchangeable borate ester bonds. When used as a resin for encapsulation substrate materials, it can significantly reduce microcracks generated during drilling, thereby improving the quality of through-holes and blind holes, and enhancing the reliability and production yield of the encapsulation substrate.

[0025] 2. This application uses diallyl hexafluorobisphenol A as a raw material. Through fluorine modification, the hydroxyl groups are completely consumed. At the same time, the low dielectric properties of fluorine atoms avoid the influence of traditional 2,2'-diallyl bisphenol A on dielectric properties. After prepolymerization with maleimide monomer, its low dielectric properties can ensure the high computing power and low power consumption of high-performance chips. Attached Figure Description

[0026] Figure 1 This is a comparison image of the morphology of the self-healing composite material of this application after a crack was drawn and after repair treatment. Detailed Implementation

[0027] 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.

[0028] It should be noted that: Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0029] 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.

[0030] 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.

[0031] This application provides a maleimide monomer containing a borate ester bond, having the molecular structure shown below: ; Formula 1; Where n1≥2, 6≥m1>2, and n1 and m1 are both positive integers.

[0032] In some preferred embodiments, the borate-containing maleimide monomer is prepared from the following raw materials by weight: 16.6-97.6 parts of a phenylboronic acid compound, 47.8-224.8 parts of the compound of formula 2, 1200-4500 parts of a polar solvent, and 300-1500 parts of a nonpolar solvent, wherein the structure of the compound of formula 2 is as follows: ; Formula 2; Where n2≥2, and n2 is a positive integer.

[0033] In some more preferred embodiments, the phenylboronic acid compound has the structure shown in Formula 3: ; Formula 3; Where 6≥m2≥1, and m2 are all positive integers.

[0034] In some preferred embodiments, the compound of formula 2 is prepared from the following raw materials by weight: 22.75-133 parts of an aminodiol compound, 41.5-166 parts of a compound of formula 4, and 150-600 parts of ethanol, wherein the structural formula of the compound of formula 4 is as follows: ; Formula 4.

[0035] In some preferred embodiments, the compound of formula 4 is prepared from the following raw materials in parts by weight: 49-147 parts of maleic anhydride, 34-102 parts of furan, and 200-600 parts of ethyl acetate.

[0036] In some preferred embodiments, the amino-diol-containing compound has the structure shown in Formula 5: ; Formula 5; Where n3≥1, and n3 are all positive integers.

[0037] This application also provides a method for synthesizing the above-mentioned compound of formula 2, comprising the following steps: sequentially adding compound of formula 4, amino diol-containing compound and ethanol into a flask, continuously stirring with magnetic force, heating to 85°C for reflux, reacting for 6 hours, then cooling to 4°C, holding at the temperature for 4 hours, filtering to obtain a solid, washing with ethanol, and drying under vacuum at 50°C to obtain compound of formula 2.

[0038] In some preferred embodiments, the polar solvent described in this application is one or a mixture of two or more of N,N-dimethylformamide and N,N-dimethylacetamide.

[0039] In some preferred embodiments, the nonpolar solvent described in this application is one or a mixture of two or more of toluene and xylene.

[0040] This application also provides a method for synthesizing the aforementioned borate ester bond-containing maleimide monomer, comprising the following steps: sequentially adding the compound of formula 2, a polar solvent, and a nonpolar solvent into a three-necked flask, continuously stirring with a magnetic force, heating to 145°C, maintaining the temperature for 1 hour, adding a phenylboronic acid compound, then continuously purging with nitrogen gas, continuing the reaction for 36 hours, stopping the heating and allowing it to cool naturally to room temperature, further filtering to obtain a filtrate, removing the solution from the filtrate by rotary evaporation to obtain a solid, and placing it at 80°C for vacuum drying to obtain the borate ester bond-containing maleimide monomer.

[0041] This application also provides a self-healing resin for encapsulating substrates, the formulation of which, by weight, comprises the following raw material components: 34.8-111.2 parts of boron ester bond maleimide monomer, 35-140 parts of fluorinated diallyl hexafluorobisphenol A, and 41.4-85.5 parts of bismaleimide monomer.

[0042] In some preferred embodiments, the structure of the fluorine-modified diallyl hexafluorobisphenol A is shown in Formula 6: ; Formula 6.

[0043] In some preferred embodiments, the fluorinated diallyl hexafluorobisphenol A is prepared from the following raw materials by weight: 15.4-61.6 parts diallyl hexafluorobisphenol A, 23.3-93 parts 1-bromoperfluoro-3-methylbutane, 150-400 parts chloroform, and 40-140 parts potassium carbonate.

[0044] This application also provides a method for synthesizing the above-mentioned fluorinated diallyl hexafluorobisphenol A, comprising the following steps: chloroform, diallyl hexafluorobisphenol A, and potassium carbonate are sequentially added to a three-necked flask, placed in an ice bath and continuously magnetically stirred, and then 1-bromoperfluoro-3-methylbutane is gradually added dropwise to the three-necked flask. After the addition is complete, the reaction continues for 24 hours, then the residue is removed by filtration, the filtrate is washed 6 times with deionized water, and the aqueous layer is removed by a separatory funnel, retaining the organic layer. Then, the solvent is further removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0045] In some preferred embodiments, the bismaleimide monomer described in this application is selected from one or more of the following: 1,6-dimaleimide hexane, 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione, N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylenebismaleimide, 2,2′-bis[4-(4-maleimide-phenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, and 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione.

[0046] Another technical objective of this application is to provide a prepolymerization method for the above-mentioned self-healing resin for encapsulation substrates, comprising the following steps: adding boron ester bond maleimide monomer, fluorinated diallyl hexafluorobisphenol A, and bismaleimide monomer sequentially into a three-necked flask, continuously stirring mechanically, heating to 130-180℃, reacting for 0.5-3 hours, naturally cooling, removing the prepolymer, and pulverizing it using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0047] Another technical objective of this application is to provide a self-healing composite material, the raw material of which is the self-healing resin for encapsulation substrates as described above.

[0048] 1. The maleimide monomer containing boronic ester bonds designed and synthesized in this application introduces dynamically exchangeable boronic ester bonds. The specific chemical structure principle is shown in the following schematic diagram: The composite material, after further prepolymerization and curing, has a self-healing function (i.e., microcracks can be repaired). When used as a resin for encapsulation substrates, it can significantly reduce microcracks generated during drilling, thereby improving the quality of through-holes and blind holes, and enhancing the reliability and production yield of encapsulation substrates.

[0049] 2. This application uses diallyl hexafluorobisphenol A as a raw material. Through fluorine modification, the hydroxyl groups are completely consumed. At the same time, the low dielectric properties of fluorine atoms avoid the influence of traditional 2,2'-diallyl bisphenol A on dielectric properties. After prepolymerization with maleimide monomer, its low dielectric properties can ensure the high computing power and low power consumption of high-performance chips.

[0050] Next, specific embodiments will be used to describe in detail the preparation methods of the boron ester bond maleimide monomer, fluorine-modified diallyl hexafluorobisphenol A, self-healing resin, and self-healing composite material of this application.

[0051] Example 1 1. Synthesis of Compound 4 34 parts of furan, 49 parts of maleic anhydride and 200 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0052] 2. Synthesis of Compound 2 41.5 parts of the above-mentioned compound of formula 4, 22.75 parts of 3-amino-1,2-propanediol and 150 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0053] 3. Synthesis of maleimide monomers containing boron ester bonds 47.8 parts of the above-mentioned compound of formula 2, 1200 parts of N,N-dimethylformamide, and 300 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 24.4 parts of phenylboronic acid were added, and nitrogen gas was continuously introduced. The reaction was continued for 36 hours. Heating was stopped and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0054] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 250 parts of chloroform, 30.8 parts of diallyl hexafluorobisphenol A, and 69 parts of potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 46.5 parts of 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0055] 5. Preparation of self-healing resin for encapsulation substrate 77.1 parts of the above-mentioned borate ester bond maleimide monomer, 70 parts of fluorinated diallyl hexafluorobisphenol A, and 41.4 parts of 1,6-dimaleimide hexane were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 150°C. After reacting for 2 hours, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0056] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0057] Example 2 1. Synthesis of Compound 4 68 parts of furan, 98 parts of maleic anhydride and 400 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0058] 2. Synthesis of Compound 2 83 parts of the above-mentioned compound of formula 4, 52.5 parts of 4-amino-1,2-butanediol and 300 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0059] 3. Synthesis of maleimide monomers containing boron ester bonds 101.2 parts of the above-mentioned compound of formula 2, 1800 parts of N,N-dimethylformamide, and 700 parts of xylene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 33.2 parts of 1,2-phenylenediboric acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0060] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 200 parts chloroform, 30.8 parts diallyl hexafluorobisphenol A, and 82.8 parts potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 46.5 parts 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0061] 5. Preparation of self-healing resin for encapsulation substrate 69.6 parts of the above-mentioned borate ester bond maleimide monomer, 70 parts of fluorine-modified diallyl hexafluorobisphenol A, and 47.7 parts of 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione were sequentially added to a three-necked flask, mechanically stirred continuously, and heated to 180°C. After reacting for 0.5 h, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0062] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0063] Example 3 1. Synthesis of Compound 4 102 parts of furan, 147 parts of maleic anhydride and 600 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0064] 2. Synthesis of Compound 2 124.5 parts of the above-mentioned compound of formula 4, 89.25 parts of 5-amino-1,2-pentanediol and 450 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and held at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0065] 3. Synthesis of maleimide monomers containing boron ester bonds 160.2 parts of the above-mentioned compound (Formula 2), 3000 parts of N,N-dimethylacetamide, and 1000 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 49.8 parts of 1,3-phenylenediboric acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0066] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 350 parts chloroform, 46.2 parts diallyl hexafluorobisphenol A, and 124 parts potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 70 parts 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0067] 5. Preparation of self-healing resin for encapsulation substrate 110.7 parts of the above-mentioned borate ester bond maleimide monomer, 105 parts of fluorinated diallyl hexafluorobisphenol A, and 80.6 parts of N,N'-(4,4'-methylenediphenyl)bismaleimide were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 130°C. After reacting for 3 hours, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0068] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*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.

[0069] Example 4 1. Synthesis of Compound 4 102 parts of furan, 147 parts of maleic anhydride and 600 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0070] 2. Synthesis of Compound 2 166 parts of the above-mentioned compound of formula 4, 133 parts of 6-amino-1,2-hexanediol and 600 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0071] 3. Synthesis of maleimide monomers containing boron ester bonds 224.8 parts of the above-mentioned compound (Formula 2), 4500 parts of N,N-dimethylformamide, and 1500 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 66.4 parts of 1,4-phenylenediboric acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0072] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 400 parts of chloroform, 61.6 parts of diallyl hexafluorobisphenol A, and 140 parts of potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 93 parts of 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0073] 5. Preparation of self-healing resin for encapsulation substrate 156.0 parts of the above-mentioned borate ester bond maleimide monomer, 140 parts of fluorine-modified diallyl hexafluorobisphenol A, and 80.4 parts of N,N'-m-phenylenebismaleimide were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0074] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0075] Example 5 1. Synthesis of Compound 4 68 parts of furan, 98 parts of maleic anhydride and 400 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0076] 2. Synthesis of Compound 2 124.5 parts of the above-mentioned compound of formula 4, 99.75 parts of 6-amino-1,2-hexanediol and 450 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and held at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0077] 3. Synthesis of maleimide monomers containing boron ester bonds 168.6 parts of the above-mentioned compound (Formula 2), 3000 parts of N,N-dimethylacetamide, and 1000 parts of xylene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 42 parts of benzene-1,3,5-trimethyltriboronic acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and obtain a solid. The solid was then dried under vacuum at 80°C to obtain the borate ester bond-containing maleimide monomer.

[0078] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 300 parts chloroform, 46.2 parts diallyl hexafluorobisphenol A, and 110 parts potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 70 parts 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0079] 5. Preparation of self-healing resin for encapsulation substrate 111.2 parts of the above-mentioned borate ester bond maleimide monomer, 105 parts of fluorinated diallyl hexafluorobisphenol A, and 85.5 parts of 2,2′-bis[4-(4-maleimide phenoxy)phenyl]propane were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 170°C. After reacting for 0.5 h, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0080] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0081] Example 6 1. Synthesis of Compound 4 34 parts of furan, 49 parts of maleic anhydride and 200 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0082] 2. Synthesis of Compound 2 83 parts of the above-mentioned compound of formula 4, 59.5 parts of 5-amino-1,2-pentanediol and 300 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0083] 3. Synthesis of maleimide monomers containing boron ester bonds 106.8 parts of the above-mentioned compound of formula 2, 2300 parts of N,N-dimethylformamide, and 700 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 33.2 parts of 1,4-phenylenediboric acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0084] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 250 parts of chloroform, 30.8 parts of diallyl hexafluorobisphenol A, and 82.8 parts of potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 46.5 parts of 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0085] 5. Preparation of self-healing resin for encapsulation substrate 73.8 parts of the above-mentioned boron ester bond maleimide monomer, 70 parts of fluorinated diallyl hexafluorobisphenol A, and 66.3 parts of bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0086] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0087] Example 7 1. Synthesis of Compound 4 34 parts of furan, 49 parts of maleic anhydride and 200 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0088] 2. Synthesis of Compound 2 41.5 parts of the above-mentioned compound of formula 4, 26.25 parts of 4-amino-1,2-butanediol and 150 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0089] 3. Synthesis of maleimide monomers containing boron ester bonds 50.6 parts of the above-mentioned compound of formula 2, 1200 parts of N,N-dimethylformamide, and 300 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 16.6 parts of 1,3-phenyldiboronic acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0090] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 150 parts chloroform, 15.4 parts diallyl hexafluorobisphenol A, and 40 parts potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 23.3 parts 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0091] 5. Preparation of self-healing resin for encapsulation substrate 34.8 parts of the above-mentioned borate ester bond maleimide monomer, 35 parts of fluorine-modified diallyl hexafluorobisphenol A, and 21.2 parts of 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione were sequentially added to a three-necked flask, mechanically stirred continuously, and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0092] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0093] Example 8 1. Synthesis of Compound 4 68 parts of furan, 98 parts of maleic anhydride and 400 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0094] 2. Synthesis of Compound 2 124.5 parts of the above-mentioned compound of formula 4, 68.25 parts of 3-amino-1,2-propanediol and 450 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0095] 3. Synthesis of maleimide monomers containing boron ester bonds 143.4 parts of the compound of formula 2 above, 3000 parts of N,N-dimethylformamide, and 1000 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 49.8 parts of 1,2-phenylenediboric acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0096] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 200 parts chloroform, 30.8 parts diallyl hexafluorobisphenol A, and 69 parts potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 46.5 parts 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0097] 5. Preparation of self-healing resin for encapsulation substrate 65.4 parts of the above-mentioned borate ester bond maleimide monomer, 70 parts of fluorinated diallyl hexafluorobisphenol A, and 41.4 parts of 1,6-dimaleimide hexane were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0098] 6. Preparation of self-healing composite materials 2.5 parts of the self-healing resin were placed in a 50*80*0.5mm stainless steel mold frame, covered with polytetrafluoroethylene film on both the top and bottom, and placed in a vacuum press. The pressure was set to 28 kgf / cm², and the mixture was pressed at 200°C for 2 hours. Then, the temperature was increased to 220°C and pressed for another hour. Finally, after cooling, the mixture was removed, thus obtaining a self-healing composite material with a thickness of 0.5mm. The morphology of this self-healing composite material after a crack is scratched is similar to that after repair treatment. Figure 1 As shown.

[0099] Example 9 1. Synthesis of Compound 4 102 parts of furan, 147 parts of maleic anhydride and 600 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0100] 2. Synthesis of Compound 2 166 parts of the above-mentioned compound of formula 4, 91 parts of 3-amino-1,2-propanediol and 600 parts of ethanol were added sequentially to a flask, and the mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at the temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0101] 3. Synthesis of maleimide monomers containing boron ester bonds 191.2 parts of the above-mentioned compound of formula 2, 4500 parts of N,N-dimethylformamide, and 1500 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 97.6 parts of phenylboronic acid were added, and nitrogen gas was continuously introduced. The reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain a maleimide monomer containing boron ester bonds.

[0102] 4. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 350 parts of chloroform, 46.2 parts of diallyl hexafluorobisphenol A, and 110 parts of potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 70 parts of 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0103] 5. Preparation of self-healing resin for encapsulation substrate 102.8 parts of the above-mentioned borate ester bond maleimide monomer, 105 parts of fluorinated diallyl hexafluorobisphenol A, and 55.2 parts of 1,6-dimaleimide hexane were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0104] 6. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0105] Comparative Example 1 1. Synthesis of Fluorine-Modified Diallyl Hexafluorobisphenol A 200 parts chloroform, 30.8 parts diallyl hexafluorobisphenol A, and 69 parts potassium carbonate were sequentially added to a three-necked flask, which was placed in an ice bath and continuously stirred magnetically. Then, 46.5 parts 1-bromoperfluoro-3-methylbutane were gradually added dropwise to the three-necked flask. After the addition was complete, the reaction continued for 24 hours. The residue was then removed by filtration, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain fluorinated diallyl hexafluorobisphenol A.

[0106] 2. Preparation of prepolymer resin for encapsulation substrate 70 parts of fluorinated diallyl hexafluorobisphenol A and 106.8 parts of 1,6-dimaleimide hexane were added sequentially to a three-necked flask, and the mixture was continuously stirred mechanically and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally. The prepolymer was then removed and pulverized using a pulverizer to obtain the prepolymer resin for encapsulation substrates.

[0107] 3. Preparation of composite materials The above-mentioned encapsulation carrier plate was placed in a 50*80*0.5mm stainless steel mold frame with 2.5 parts of prepolymer resin. Polytetrafluoroethylene film was covered on the top and bottom. The mold frame was placed in a vacuum press with a pressure of 28kgf / cm2 and pressed at 200℃ for 2 hours. Then the temperature was raised to 220℃ and pressed for another hour. Finally, the mold frame was cooled and removed to obtain a composite material with a thickness of 0.5mm.

[0108] Comparative Example 2 1. Synthesis of Compound 4 68 parts of furan, 98 parts of maleic anhydride and 400 parts of ethyl acetate were added to a beaker in sequence, and the mixture was continuously stirred magnetically. The reaction was carried out at room temperature for 24 hours. The mixture was then filtered to obtain a white solid, which was washed with ethyl acetate and then dried under vacuum at 50°C to obtain compound 4.

[0109] 2. Synthesis of Compound 2 124.5 parts of the above-mentioned compound of formula 4, 68.25 parts of 3-amino-1,2-propanediol and 450 parts of ethanol were added sequentially to a flask. The mixture was continuously stirred magnetically and heated to 85°C for reflux. The reaction was carried out for 6 hours, then cooled to 4°C and kept at that temperature for 4 hours. The solid was obtained by filtration, washed with ethanol, and dried under vacuum at 50°C to obtain compound of formula 2.

[0110] 3. Synthesis of maleimide monomers containing boron ester bonds 143.4 parts of the compound of formula 2 above, 3000 parts of N,N-dimethylformamide, and 1000 parts of toluene were added sequentially to a three-necked flask. The mixture was continuously stirred magnetically and heated to 145°C. After holding at this temperature for 1 hour, 49.8 parts of 1,2-phenylenediboric acid were added. Nitrogen gas was then continuously introduced, and the reaction was continued for 36 hours. Heating was stopped, and the mixture was allowed to cool naturally to room temperature. The mixture was then filtered to obtain a filtrate. The filtrate was rotary evaporated to remove the solution and a solid was obtained. The solid was then dried under vacuum at 80°C to obtain the maleimide monomer containing boron ester bonds.

[0111] 4. Preparation of self-healing resin for encapsulation substrate 65.4 parts of the above-mentioned borate ester bond maleimide monomer, 70 parts of 2,2'-diallylbisphenol A, and 41.4 parts of 1,6-dimaleimide hexane were sequentially added to a three-necked flask, and the mixture was continuously mechanically stirred and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally, and the prepolymer was removed and pulverized using a pulverizer to obtain the self-healing resin for encapsulation substrates.

[0112] 5. Preparation of self-healing composite materials Place 2.5 parts of the self-healing resin into a 50*80*0.5mm stainless steel mold frame, cover the top and bottom with polytetrafluoroethylene film, place it in a vacuum press, set the pressure to 28kgf / cm2, press at 200℃ for 2 hours, then raise the temperature to 220℃ and continue pressing for 1 hour, and finally cool and take it out to prepare a self-healing composite material with a thickness of 0.5mm.

[0113] Comparative Example 3 1. Preparation of prepolymer resin for encapsulation substrate 70 parts of 2,2'-diallylbisphenol A and 106.8 parts of 1,6-dimaleimide hexane were added sequentially to a three-necked flask, and the mixture was continuously stirred mechanically and heated to 160°C. After reacting for 1 hour, the mixture was allowed to cool naturally. The prepolymer was then removed and pulverized using a pulverizer to obtain the prepolymer resin for the encapsulation substrate.

[0114] 2. Preparation of self-healing composite materials The above-mentioned encapsulation carrier plate was placed in a 50*80*0.5mm stainless steel mold frame with 2.5 parts of prepolymer resin. Polytetrafluoroethylene film was covered on the top and bottom. The mold frame was placed in a vacuum press with a pressure of 28kgf / cm2 and pressed at 200℃ for 2 hours. Then the temperature was raised to 220℃ and pressed for another hour. Finally, the mold frame was cooled and removed to obtain a composite material with a thickness of 0.5mm.

[0115] 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.

[0116] (2) Dielectric properties The dielectric constant Dk and dielectric loss Df of the composite materials in the examples and comparative examples were measured at a frequency of 10 GHz using a KEYSIGHT N5224B vector network analyzer.

[0117] (3) Repair effect Cracks were made on the surface of the composite material using a blade. The composite material was then placed in a 50*80*0.5mm stainless steel mold frame, covered with PTFE films from both the top and bottom, and placed in a vacuum press. The pressure was set to 10 kgf / cm², and the mixture was pressed at 250°C for 1 hour for repair. After cooling, the composite material was removed. The morphology of the composite materials in the examples and comparative examples after cracking and after repair was observed using a Keyence VHX-1000 ultra-depth-of-field 3D microscope to determine whether the cracks were repaired.

[0118] Table 1. Glass transition temperature, dielectric properties, and crack repair effect of the composite materials in Examples 1-9 and Comparative Examples 1-3.

[0119] ; Analyzing the data in Table 1, in the traditional method, as shown in Comparative Example 3, the composite material prepared by modifying bismaleimide with 2,2'-diallylbisphenol A lacks self-healing ability for microcracks and has poor dielectric properties, with Dk and Df as high as 3.15 and 0.0132, respectively. The composite material prepared using the boron ester bond maleimide monomer synthesized in this invention and traditional 2,2'-diallylbisphenol A, as shown in Comparative Example 2, although possessing self-healing ability, has a high dielectric constant and dielectric loss of 3.12 and 0.0128, respectively, making it difficult to guarantee the high computing power and low power consumption of high-performance chips after being made into a packaging substrate. The composite material made using fluorinated diallyl hexafluorobisphenol A and ordinary bismaleimide (Comparative Example 1) has lower dielectric constant and dielectric loss, but due to the lack of self-healing ability, it faces a high quality risk during the drilling process of the packaging substrate because it is prone to microcracks.

[0120] The borate ester bond-containing maleimide monomer synthesized in this invention can dynamically exchange its borate ester bonds, allowing for the repair of microcracks through high-temperature hot pressing. Simultaneously, the synthesized fluorinated diallyl hexafluorobisphenol A, by consuming all its hydroxyl groups and introducing a large number of fluorine atoms, increases the material's free volume, thereby reducing its dielectric constant (≤2.73) and dielectric loss (≤0.0053). Therefore, by using an ene reaction to prepolymerize and further solidify the borate ester bond-containing maleimide monomer, fluorinated diallyl hexafluorobisphenol A, and bismaleimide monomer into a composite material, it not only possesses self-healing capabilities for microcracks but also exhibits excellent dielectric properties. This prepolymer material, used in the preparation of packaging substrates, can significantly improve processing yield and reliability, while ensuring high computing power and low power consumption of high-performance chips. Although the glass transition temperature of this self-healing composite material is slightly lower than that of traditional modified bismaleimide resins, it is still above 201℃, exhibiting good heat resistance and meeting application requirements.

[0121] 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.

[0122] 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 maleimide monomer containing a boron ester bond, characterized in that, The boron ester bond-containing maleimide monomer has the following structure: ； Formula 1; Where n1≥2, 6≥m1>2, and n1 and m1 are both positive integers.

2. The maleimide monomer containing boron ester bonds according to claim 1, characterized in that: The boron ester bond-containing maleimide monomer is prepared from the following raw materials by weight: 16.6-97.6 parts of a phenylboronic acid compound, 47.8-224.8 parts of the compound of formula 2, 1200-4500 parts of a polar solvent, and 300-1500 parts of a nonpolar solvent, wherein the structure of the compound of formula 2 is as follows: ； Formula 2; Where n2≥2, and n2 is a positive integer.

3. The boron ester bond-containing maleimide monomer according to claim 2, characterized in that: The structure of the phenylboronic acid compound is shown in Formula 3: ； Formula 3; Where 6≥m2≥1, and m2 are all positive integers.

4. The maleimide monomer containing a boron ester bond according to claim 2, characterized in that, The compound of formula 2 is prepared from the following raw materials by weight: 22.75-133 parts of an aminodiol compound, 41.5-166 parts of a compound of formula 4, and 150-600 parts of ethanol, wherein the structural formula of the compound of formula 4 is as follows: ； Formula 4.

5. The maleimide monomer containing a boron ester bond according to claim 4, characterized in that, The compound of Formula 4 is prepared from the following raw materials in parts by weight: 49-147 parts maleic anhydride, 34-102 parts furan, and 200-600 parts ethyl acetate.

6. The boron ester bond-containing maleimide monomer according to claim 4, characterized in that: The structure of the aminodiol-containing compound is shown in Formula 5: ； Formula 5; Where n3≥1, and n3 are all positive integers.

7. A method for synthesizing a maleimide monomer containing a boron ester bond as described in claim 1, characterized in that, The process includes the following steps: adding the compound of formula 2, a polar solvent, and a nonpolar solvent sequentially into a three-necked flask, continuously stirring with a magnetic force, heating to 145°C, maintaining the temperature for 1 hour, adding a phenylboronic acid compound, then continuously purging with nitrogen gas, continuing the reaction for 36 hours, stopping the heating and allowing it to cool naturally to room temperature, further filtering to obtain a filtrate, removing the solution from the filtrate by rotary evaporation to obtain a solid, and then drying it under vacuum at 80°C to obtain a maleimide monomer containing a borate ester bond.

8. A self-healing resin for encapsulating a substrate, characterized in that, By weight, its formulation includes the following raw material components: 34.8-111.2 parts of boron ester bond maleimide monomer, 35-140 parts of fluorinated diallyl hexafluorobisphenol A, and 41.4-85.5 parts of bismaleimide monomer.

9. The self-healing resin for encapsulation substrates according to claim 8, characterized in that, The structure of the fluorine-modified diallyl hexafluorobisphenol A is shown in Formula 6: ； Formula 6.

10. The self-healing resin for encapsulating substrates according to claim 8, characterized in that, The fluorine-modified diallyl hexafluorobisphenol A is prepared from the following raw materials in parts by weight: 15.4-61.6 parts diallyl hexafluorobisphenol A, 23.3-93 parts 1-bromoperfluoro-3-methylbutane, 150-400 parts chloroform, and 40-140 parts potassium carbonate.

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