Reinforced and toughened normal-temperature self-repairing material as well as preparation method and application thereof

Abstract

The embodiment of the invention relates to the technical field of high polymer materials, and particularly discloses a reinforced and toughened normal-temperature self-repairing material as well as a preparation method and application thereof. The self-repairing material comprises the following raw materials: a binary epoxy monomer or polymer, a monoamine monomer, a binary isocyanate monomer, a diamine monomer or polymer and a monophenylboronic acid monomer. According to the embodiment of the invention, various raw materials are reasonably used, and a dynamic borate bond is formed by chemical reaction, so that the compatibility of polar and non-polar chains is remarkably improved, the material is reinforced and toughened, the material is endowed with self-repairing capability at normal temperature, and the service life of the material is prolonged. The problem that an existing high polymer material is insufficient in self-repairing capacity when being used for electronic packaging is solved. Moreover, the preparation method provided by the embodiment of the invention is simple, the prepared material can be applied to the field of electronic packaging, electronic elements can be effectively protected, the reliability of electronic equipment is improved, the service life of the electronic equipment is prolonged, and the application prospect is good.

Description

Technical Field

[0001] The embodiments of the present invention belong to the technical field of polymer materials, and specifically relate to a reinforced, toughened and room-temperature self-healing material, its preparation method and application. Background Art

[0002] With the continuous development of material technology, polymer materials play an important role in industries such as electronic information due to their unique physical and chemical properties. Therefore, in the field of polymer materials, the research and development of new materials with multiple excellent properties is of crucial significance for promoting the development of numerous industries. Especially in the field of electronic packaging, material properties directly affect the reliability and service life of electronic devices. Materials with excellent strength and toughness can effectively protect internal electronic components from external physical impacts and mechanical stresses; while the self-healing function can deal with damages such as cracks and scratches that occur during long-term use of materials, reduce maintenance costs, and ensure the stable operation of electronic devices.

[0003] Currently, a large amount of research resources have been invested in the field of polymer materials in the market to develop high-performance materials. In the aspect of electronic packaging materials, certain progress has been made, and some materials have reached certain standards in terms of strength and toughness, and can meet the basic physical protection requirements of electronic components. However, existing materials generally have the problem of insufficient self-healing ability. Traditional electronic packaging materials are difficult to self-repair after being damaged, and often require manual intervention or direct replacement, which not only increases maintenance costs, but also may cause electronic devices to shut down and affect their normal use.

[0004] Therefore, the above-mentioned existing technical solutions have the following defects: the polymer materials in the prior art have the problem of insufficient self-healing ability when used for electronic packaging. For this reason, developing a material with enhanced toughness and room-temperature self-healing ability has become a key research direction in the material field and is of great significance for promoting the development of the electronic industry. Summary of the Invention

[0005] The purpose of the embodiments of the present invention is to provide a reinforced, toughened and room-temperature self-healing material to solve the problem of insufficient self-healing ability of existing polymer materials when used for electronic packaging as proposed in the above background art.

[0006] To achieve the above purpose, the embodiments of the present invention provide the following technical solutions:

[0007] A reinforced, toughened and room-temperature self-healing material, comprising the following raw materials: a diol-based linear polymer, a polyurea-based linear polymer; wherein, the diol-based linear polymer is prepared from a monoamine monomer and a diepoxy monomer or polymer; the polyurea-based linear polymer is prepared from a diisocyanate monomer, a monoboronic acid monomer, and a diamine monomer or polymer.

[0008] In the embodiment of the present invention, the enhanced toughened room-temperature self-healing material uses binary epoxy monomers or polymers, primary amine monomers, binary isocyanate monomers, binary amine monomers or polymers, and primary phenylboronic acid monomers as raw materials. Through effective regulation of the ratio, chemical reactions occur between the raw materials to form a dynamic borate ester bond with boron-nitrogen inner coordination, which greatly promotes the compatibility of polar and non-polar chains. This compatibility makes the internal structure of the material more stable. At the microscopic level, the polar and non-polar regions can cooperate better. When the material is damaged, the dynamic characteristics of the borate ester bond promote the exchange reaction between reversible dynamic borate ester bonds, realizing the self-healing of the material at room temperature. At the same time, the good combination of polar and non-polar chains enhances the internal interaction of the material, significantly improving the mechanical properties of the material, effectively enhancing and toughening, solving the problem of insufficient self-healing ability of existing polymer materials when used in electronic packaging, and providing new ideas and theoretical basis for the structural design and performance optimization of polymer materials.

[0009] Preferably, the enhanced toughened room-temperature self-healing material comprises the following raw materials by weight percentage: 3-10% of primary amine monomers, 10-50% of binary epoxy monomers or polymers, 8-15% of binary isocyanate monomers, 40-60% of binary amine monomers or polymers, and 5-10% of primary phenylboronic acid monomers.

[0010] Another object of the embodiment of the present invention is to provide a preparation method of an enhanced toughened room-temperature self-healing material, and the preparation method specifically comprises the following steps:

[0011] (1) Mix the binary epoxy monomer or polymer with the primary amine monomer evenly, and react at 40°C - 100°C for 6 h - 12 h to obtain a diol linear polymer;

[0012] (2) Mix the binary isocyanate monomer with the binary amine monomer or polymer evenly, react at 50°C - 80°C for 3 h - 10 h, then add the primary phenylboronic acid monomer and continue to react at 50°C - 80°C for 3 h - 10 h to obtain a polyurea linear polymer;

[0013] (3) Mix the diol linear polymer in step (1) with the polyurea linear polymer in step (2) evenly, react at 50°C - 100°C for 10 h - 24 h to obtain a uniform crosslinked polymer, and then perform a drying treatment to obtain the enhanced toughened room-temperature self-healing material.

[0014] Another object of the embodiments of the present invention is to provide an application of the above-mentioned enhanced toughened room-temperature self-healing material in electronic packaging. Its uniqueness lies in that the borate ester bonds formed by the reaction can bridge the silane chains (non-polar) and carbon chains (polar), significantly improving the compatibility of polar and non-polar chains. This not only enhances and toughens the material, endowing it with good mechanical properties, but also imparts the material with self-healing ability at room temperature. This material can be applied to the field of electronic packaging, effectively protecting electronic components and improving the reliability and service life of electronic devices.

[0015] Compared with the prior art, the beneficial effects of the embodiments of the present invention are as follows:

[0016] The enhanced toughened room-temperature self-healing material provided by the embodiments of the present invention promotes the compatibility of polar and non-polar chains to a great extent by reasonably using raw materials such as binary epoxy monomers or polymers, monoamine monomers, diisocyanate monomers, diamine monomers or polymers, and monobenzeneboronic acid monomers, and forming dynamic borate ester bonds with boron-nitrogen inner coordination through chemical reactions. When the self-healing material is damaged, the dynamic characteristics of the borate ester bonds promote the exchange reaction between reversible dynamic borate ester bonds, realizing the self-healing of the material at room temperature and solving the problem of insufficient self-healing ability of existing polymer materials when used in electronic packaging. Moreover, the preparation method of the enhanced toughened room-temperature self-healing material provided by the embodiments of the present invention is simple. The good combination of polar and non-polar chains enhances the internal interaction of the material, significantly improving the mechanical properties of the material and achieving the effect of enhancement and toughening, with broad market prospects. Description of the Drawings

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention.

[0018] Figure 1 Scanning electron microscope (SEM) images of the enhanced toughened room-temperature self-healing materials in Embodiment 1 and Embodiment 2 of the present invention at different magnifications.

[0019] Figure 2 Transmission electron microscope (TEM) images of the enhanced toughened room-temperature self-healing materials in Embodiment 1 and Embodiment 2 of the present invention at different magnifications.

[0020] Figure 3 Infrared spectrum of the enhanced toughened room-temperature self-healing material in Embodiment 1 of the present invention.

[0021] Figure 4 XPS spectrum of the enhanced toughened room-temperature self-healing material in Embodiment 1 of the present invention.

[0022] Figure 5 This is the tensile test diagram of the enhanced and toughened room-temperature self-healing material in Embodiment 1 and Embodiment 2 of the present invention. Detailed implementation manners

[0023] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention and the accompanying drawings. Obviously, the following embodiments will help those skilled in the art to further understand the embodiments of the present invention, but do not limit the embodiments of the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the embodiments of the present invention, several deformations and improvements can still be made. These all belong to the protection scope of the embodiments of the present invention.

[0024] The following describes the specific implementation of the present invention in detail in conjunction with specific embodiments.

[0025] First of all, it should be noted that in the field of electronic packaging, material properties are directly related to the reliability and service life of electronic devices. Therefore, materials with excellent strength and toughness can effectively protect internal electronic components from external physical impacts and mechanical stresses; while the self-healing function can deal with damages such as cracks and scratches that occur during the long-term use of materials, reduce maintenance costs, and ensure the stable operation of electronic devices. In recent years, a large amount of research resources have been invested in the field of polymer materials at home and abroad to develop high-performance materials. In terms of electronic packaging materials, certain progress has been made, and some materials have reached certain standards in terms of strength and toughness, and can meet the basic physical protection requirements of electronic components. However, existing materials generally have the problem of insufficient self-healing ability. Traditional electronic packaging materials are difficult to self-repair after being damaged, and often require manual intervention or direct replacement, which not only increases maintenance costs, but also may cause electronic devices to stop operating, affecting their normal use. By delving into the root causes of these problems, it is found that they are mainly due to the limitations of the internal structure and chemical bonds of the materials. The poor compatibility between polar chains and non-polar chains makes it difficult for the materials to form a stable and efficient self-healing and enhanced and toughened structure. During the self-healing process, the interaction between polar and non-polar regions is weak, and it is unable to effectively guide crack repair; when under external force, the synergy between different polar regions is insufficient, limiting the improvement of material strength and toughness. Therefore, developing a material with enhanced toughness and room-temperature self-healing ability has become an urgent problem to be solved at present, and it is also a key research direction in the field of materials, which has an important role in improving the performance of electronic devices, reducing maintenance costs, and promoting the sustainable development of the electronic industry.

[0026] Therefore, to solve the problem of insufficient self-healing ability of the above-mentioned existing polymer materials when used in electronic packaging, an enhanced and toughened room-temperature self-healing material, its preparation method and application provided by the embodiments of the present invention. The enhanced and toughened room-temperature self-healing material is specifically a material that realizes the combination of polar and non-polar chains through borate esters, and then enhances toughness and has room-temperature self-healing performance. It includes the following raw materials:

[0027] A diol linear polymer and a polyurea linear polymer; wherein, the diol linear polymer is prepared from a monoamine monomer and a diepoxy monomer or polymer; the polyurea linear polymer is prepared from a diisocyanate monomer, a monoboronic acid monomer, and a diamine monomer or polymer.

[0028] In the embodiments of the present invention, a diepoxy monomer or polymer, a monoamine monomer, a diisocyanate monomer, a diamine monomer or polymer, and a monoboronic acid monomer are innovatively selected as raw materials. Through the chemical reactions between these raw materials, a dynamic borate ester bond with boron-nitrogen inner coordination is formed. The unique structure of the borate ester bond can bridge the silane chain (non-polar) and the carbon chain (polar), greatly promoting the compatibility of polar and non-polar chains. This compatibility makes the internal structure of the material more stable. At the microscopic level, the polar and non-polar regions can cooperate better. When the material is damaged, the dynamic characteristics of the borate ester bond promote the exchange reaction between reversible dynamic borate ester bonds, realizing the self-healing of the material at room temperature; at the same time, the good combination of polar and non-polar chains enhances the internal interaction of the material, significantly improving the mechanical properties of the material, effectively enhancing toughness, and solving the problem of insufficient self-healing ability of the existing polymer materials when used in electronic packaging.

[0029] As another preferred embodiment of the embodiments of the present invention, the enhanced and toughened room-temperature self-healing material includes the following raw materials by weight percentage: 3-10% of monoamine monomer, 10-50% of diepoxy monomer or polymer, 8-15% of diisocyanate monomer, 40-60% of diamine monomer or polymer, and 5-10% of monoboronic acid monomer.

[0030] As another preferred embodiment of the embodiments of the present invention, the diepoxy monomer or polymer is selected from at least one of poly(dimethylsiloxane), diglycidyl ether-terminated, 3,3'5,5'-tetramethylbiphenol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, bisphenol C diglycidyl ether, and polyethylene glycol diglycidyl ether.

[0031] As another preferred embodiment of the embodiments of the present invention, the monoamine monomer is at least one of n-butylamine, cyclopropylamine, p-toluidine, and aniline.

[0032] As another preferred embodiment of the embodiment of the present invention, the binary isocyanate monomer is at least one of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, and hexamethylene diisocyanate.

[0033] As another preferred embodiment of the embodiment of the present invention, the diamine monomer or polymer is at least one of polyetheramine, amino-terminated polydimethylsiloxane, 1,4-cyclohexanediamine, and p-phenylenediamine.

[0034] As another preferred embodiment of the embodiment of the present invention, the monoboronic acid monomer is at least one of 2-aminophenylboronic acid, 3-aminophenylboronic acid, and 4-aminophenylboronic acid.

[0035] It should be noted that for the problem in the prior art that it is difficult to effectively combine polar chains and non-polar chains, resulting in limited self-healing ability and mechanical properties of materials, the enhanced and toughened room-temperature self-healing material provided by the embodiment of the present invention uses monoboronic acid monomers and the like as raw materials, and forms dynamic borate ester bonds with boron-nitrogen inner coordination through chemical reactions between materials. The unique structure of the borate ester bond can bridge the silane chain (non-polar) and the carbon chain (polar), greatly promoting the compatibility of polar and non-polar chains. This compatibility makes the internal structure of the material more stable, and at the microscopic level, the polar and non-polar regions can better cooperate. When the material is damaged, the dynamic characteristics of the borate ester bond promote the exchange reaction between reversible dynamic borate ester bonds, realizing the self-healing of the material at room temperature; at the same time, the good combination of polar and non-polar chains enhances the interaction inside the material, significantly improving the mechanical properties of the material and effectively enhancing and toughening.

[0036] The embodiment of the present invention also provides a preparation method of an enhanced and toughened room-temperature self-healing material. The preparation method of the enhanced and toughened room-temperature self-healing material specifically includes the following steps:

[0037] (1) Mix the binary epoxy monomer or polymer with the monoamine monomer evenly, and react at 40°C - 100°C for 6 h - 12 h to obtain a binary alcohol linear polymer;

[0038] (2) Mix the binary isocyanate monomer with the diamine monomer or polymer evenly, react at 50°C - 80°C for 3 h - 10 h, and then add the monoboronic acid monomer and continue to react at 50°C - 80°C for 3 h - 10 h to obtain a polyurea linear polymer;

[0039] (3) Mix the binary alcohol linear polymer in step (1) with the polyurea linear polymer in step (2) evenly, react at 50°C - 100°C for 6 h - 24 h to obtain a uniform crosslinked polymer, and then perform a drying treatment to obtain the enhanced and toughened room-temperature self-healing material.

[0040] As another preferred embodiment of the embodiment of the present invention, in the preparation method of the enhanced toughened room-temperature self-healing material, the drying treatment is to dry the uniform cross-linked polymer at 70°C - 120°C for 12 h - 24 h, and then place it in a vacuum oven for drying for 72 h - 84 h.

[0041] Preferably, the preparation method of the enhanced toughened room-temperature self-healing material includes the following steps:

[0042] (1) Synthesis of diol linear polymer: The binary epoxy monomer or polymer and the monoamine monomer are fully mixed and reacted in the temperature range of 40°C - 100°C for 6 h - 12 h to obtain a uniform diol linear polymer; a linear polymer is prepared by the epoxy ring-opening reaction of the amino group on the binary epoxy monomer or polymer and the monoamine monomer, and a claw-like structure of diol is formed in the middle of the chain.

[0043] (2) Synthesis of polyurea linear polymer: The binary isocyanate monomer and the diamine monomer or polymer are uniformly mixed and reacted under the condition of 50°C - 80°C for 3 h - 10 h, and the mono phenylboronic acid monomer is added and continued to react at 50°C - 80°C for 3 h - 10 h to obtain a uniform polyurea linear polymer, that is, a phenylboronic acid-terminated linear polymer.

[0044] (3) Synthesis of cross-linked polymer: The solutions after the reactions in the above two steps (that is, the diol linear polymer in step (1) and the polyurea linear polymer in step (2)) are fully mixed and reacted at a temperature of 50°C - 100°C for 10 h - 24 h, so that the phenylboronic acid-terminated linear polymer reacts with the linear polymer with diol formed in the middle of the chain to obtain a cross-linked polymer containing a boron-nitrogen inner coordination borate bond. In this process, the borate bond bridges the silane chain (non-polar) and the carbon chain (polar), promoting the good compatibility of the polar and non-polar chains.

[0045] (4) The cross-linked polymer obtained in step (3) is placed in an oven at 70°C - 120°C for drying for 12 h - 24 h to preliminarily remove the moisture and volatile substances in the mixture and achieve the preliminary curing of the material; then it is placed in a vacuum oven for drying for 72 h - 84 h to finally obtain a self-healing material with excellent performance.

[0046] The embodiment of the present invention also provides an enhanced toughened room-temperature self-healing material prepared by using the above preparation method.

[0047] An embodiment of the present invention also provides an application of the above-mentioned enhanced toughened room-temperature self-healing material in electronic packaging. This enhanced toughened room-temperature self-healing material has good self-healing performance, can effectively protect electronic components, improve the reliability and stability of electronic devices, and thus extend the service life of electronic devices.

[0048] It should be further noted that the method adopted in the present invention is of great significance in both scientific research and engineering application fields. From the perspective of scientific research, it provides new ideas and theoretical bases for the structural design and performance optimization of polymer materials, deepens the understanding of the interaction between polar and non-polar chains and the mechanism of regulating material properties by dynamic chemical bonds, and promotes the development of the basic theory of materials science. In terms of engineering application, this enhanced toughened room-temperature self-healing material can be widely used in the field of electronic packaging, improve the reliability and stability of electronic devices, reduce the equipment maintenance cost, provide strong material support for the development of the electronic industry, promote the innovation and progress of related engineering technologies, and play a positive role in promoting the progress of human science and technology and social development.

[0049] The following further illustrates the technical effects of the enhanced toughened room-temperature self-healing material of the embodiments of the present invention by listing specific examples.

[0050] Example 1

[0051] An enhanced toughened room-temperature self-healing material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: poly(dimethylsiloxane), diglycidyl ether-terminated 20%, n-butylamine 5%, isophorone diisocyanate 10%, polyetheramine 55%, 3-aminophenylboronic acid 10%.

[0052] In this embodiment, the preparation method of the enhanced toughened room-temperature self-healing material specifically includes the following steps:

[0053] (1) Mix and stir poly(dimethylsiloxane), diglycidyl ether-terminated and n-butylamine, react at 40 °C for 3 h, then react at 60 °C for 3 h, and finally continue to react at 100 °C for 6 h;

[0054] (2) Drop polyetheramine into isophorone diisocyanate at a dropping rate of 6 - 8 drops / s. After the dropping is completed, react at 60 °C for 6 h, and then add 3-aminophenylboronic acid and react at 60 °C for 6 h;

[0055] (3) Mix and stir the solutions obtained from steps (1) and (2), react at 60 °C for 6 h, then degas under vacuum at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced-air oven at 80 °C for 12 h, and then transfer to a vacuum oven and cure at 80 °C for 72 h to obtain the enhanced toughened room-temperature self-healing material.

[0056] Example 2

[0057] An enhanced toughened room-temperature self-healing material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: 20% of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether, 5% of n-butylamine, 10% of isophorone diisocyanate, 55% of polyetheramine, and 10% of 3-aminophenylboronic acid.

[0058] In this example, the preparation method of the enhanced toughened room-temperature self-healing material specifically includes the following steps:

[0059] (1) Mix and stir 3,3',5,5'-tetramethylbiphenyl diglycidyl ether and n-butylamine, react at 40 °C for 3 h, then react at 60 °C for 3 h, and finally continue to react at 100 °C for 6 h;

[0060] (2) Drop polyetheramine into isophorone diisocyanate at a dropping rate of 6 - 8 drops / s. After dropping, react at 60 °C for 6 h, and then add 3-aminophenylboronic acid and react at 60 °C for 6 h;

[0061] (3) Mix and stir the solutions after the reactions in steps (1) and (2), react at 60 °C for 6 h, then vacuum degas at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure at 80 °C in a forced-air oven for 12 h, and then transfer to a vacuum oven and cure at 80 °C for 72 h to obtain the enhanced toughened room-temperature self-healing material.

[0062] Example 3

[0063] An enhanced toughened room-temperature self-healing material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: 15% of 1,2-cyclohexanediol diglycidyl ether, 8% of p-toluidine, 12% of toluene diisocyanate, 55% of 1,4-cyclohexanediamine, and 10% of 4-aminophenylboronic acid.

[0064] In this example, the preparation method of the enhanced toughened room-temperature self-healing material specifically includes the following steps:

[0065] (1) Mix and stir 1,2-cyclohexanediol diglycidyl ether and p-toluidine, react at 40 °C for 3 h, then react at 60 °C for 3 h, and finally continue to react at 100 °C for 6 h;

[0066] (2) Drop 1,4-cyclohexanediamine into toluene diisocyanate at a dropping rate of 6–8 drops / s. After dropping, react at 60 °C for 6 h, and then add 4-aminophenylboronic acid and react at 60 °C for 6 h;

[0067] (3) Mix and stir the solutions after the reactions in (1) and (2), react at 60 °C for 6 h, then perform vacuum degassing at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure at 80 °C in a forced-air oven for 12 h, and then transfer to a vacuum oven to cure at 80 °C for 72 h to obtain the enhanced and toughened room-temperature self-healing material.

[0068] Example 4

[0069] An enhanced and toughened room-temperature self-healing material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: bisphenol C diglycidyl ether 25%, aniline 6%, p-xylylene diisocyanate 10%, p-phenylenediamine 54%, 2-aminophenylboronic acid 5%.

[0070] In this example, the preparation method of the enhanced and toughened room-temperature self-healing material specifically includes the following steps:

[0071] (1) Mix and stir bisphenol C diglycidyl ether and aniline, react at 40 °C for 3 h, then react at 60 °C for 3 h, and finally continue to react at 100 °C for 6 h;

[0072] (2) Drop p-phenylenediamine into p-xylylene diisocyanate at a dropping rate of 6 - 8 drops / s. After the dropping is completed, react at 60 °C for 6 h, and then add 3-aminophenylboronic acid and react at 60 °C for 6 h;

[0073] (3) Mix and stir the solutions after the reactions in steps (1) and (2), react at 60 °C for 6 h, then perform vacuum degassing at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure at 80 °C in a forced-air oven for 12 h, and then transfer to a vacuum oven to cure at 80 °C for 72 h to obtain the enhanced and toughened room-temperature self-healing material.

[0074] Example 5

[0075] An enhanced and toughened room-temperature self-healing material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: polyethylene glycol diglycidyl ether 10%, n-butylamine 7%, hexamethylene diisocyanate 15%, polyetheramine 63%, 3-aminophenylboronic acid 5%.

[0076] In this example, the preparation method of the enhanced and toughened room-temperature self-healing material specifically includes the following steps:

[0077] (1) Mix and stir polyethylene glycol diglycidyl ether and n-butylamine, react at 40 °C for 3 h, then react at 60 °C for 3 h, and finally continue to react at 100 °C for 6 h;

[0078] (2) The polyetheramine was added dropwise to hexamethylene diisocyanate at a dropping rate of 6 - 8 drops per second. After the addition was completed, the reaction was carried out at 60 °C for 6 h, and then 3 - aminophenylboronic acid was added and the reaction was carried out at 60 °C for 6 h;

[0079] (3) The solutions obtained from steps (1) and (2) were mixed and stirred. After reacting at 60 °C for 6 h, vacuum degassing was carried out at room temperature for half an hour. Finally, the mixture was poured into a polytetrafluoroethylene mold and cured in a forced - air oven at 80 °C for 12 h, and then transferred to a vacuum oven and cured at 80 °C for 72 h to obtain the enhanced and toughened room - temperature self - healing material.

[0080] Example 6

[0081] Compared with Example 1, except that the amounts of each component of the specific raw materials of the enhanced and toughened room - temperature self - healing material (by weight percentage) are poly(dimethylsiloxane), diglycidyl ether - terminated 10%, n - butylamine 10%, isophorone diisocyanate 15%, polyetheramine 60%, 3 - aminophenylboronic acid 5%, the others are the same.

[0082] Example 7

[0083] Compared with Example 1, except that the amounts of each component of the specific raw materials of the enhanced and toughened room - temperature self - healing material (by weight percentage) are poly(dimethylsiloxane), diglycidyl ether - terminated 40%, n - butylamine 3%, isophorone diisocyanate 8%, polyetheramine 40%, 3 - aminophenylboronic acid 9%, the others are the same.

[0084] Example 8

[0085] Compared with Example 1, except that the amounts of each component of the specific raw materials of the enhanced and toughened room - temperature self - healing material (by weight percentage) are poly(dimethylsiloxane), diglycidyl ether - terminated 50%, n - butylamine 3%, isophorone diisocyanate 8%, polyetheramine 29%, 3 - aminophenylboronic acid 10%, the others are the same.

[0086] Example 9

[0087] Compared with Example 1, except that n - butylamine was replaced by cyclopropylamine, the others are the same as Example 1.

[0088] Example 10

[0089] Compared with Example 1, except that n - butylamine was replaced by aniline, the others are the same as Example 1.

[0090] Example 11

[0091] Compared with Example 1, except that polyetheramine was replaced by amino - terminated polydimethylsiloxane, the others are the same as Example 1.

[0092] Example 12

[0093] Compared with Example 1, except that the poly(dimethylsiloxane), diglycidyl ether end-capping is replaced with a mixture of bisphenol C diglycidyl ether and polyethylene glycol diglycidyl ether of equal weight, the others are the same as in Example 1.

[0094] Example 13

[0095] Compared with Example 4, except that terephthalylidene diisocyanate is replaced with diphenylmethane diisocyanate, the others are the same as in Example 4.

[0096] Example 14

[0097] Compared with Example 4, except that terephthalylidene diisocyanate is replaced with hexamethylene diisocyanate, the others are the same as in Example 4.

[0098] Example 15

[0099] Compared with Example 1, except that the reaction temperature in step (2) is 80 °C and the reaction temperature in step (3) is 50 °C, the others are the same.

[0100] Example 16

[0101] Compared with Example 1, except that the reaction temperature in step (2) is 50 °C and the reaction temperature in step (3) is 100 °C, the others are the same.

[0102] Example 17

[0103] Compared with Example 1, except that the reaction temperature in step (2) is 70 °C and the reaction temperature in step (3) is 60 °C, the others are the same.

[0104] Example 18

[0105] Compared with Example 1, except that the reaction temperature in step (2) is 50 °C and the reaction temperature in step (3) is 90 °C, the others are the same.

[0106] In order to verify the performance of the enhanced and toughened room-temperature self-healing material, Comparative Example 1, Comparative Example 2, and Comparative Example 3 are set for comparison, and the specific raw material ratios of each comparative example are shown in Table 1.

[0107] Table 1 Raw material component table of different samples (%)

[0108]

[0109] Combined with the raw material component table of different samples in Table 1, the specific raw material ratios of Comparative Example 1, Comparative Example 2, and Comparative Example 3 are as follows.

[0110] Comparative Example 1

[0111] According to the component dosages in Table 1 (by weight percentage): polyethylene glycol diglycidyl ether 25%, aniline 6%, toluene diisocyanate 11%, 1,4 - cyclohexanediamine 58%. The specific preparation method is as follows:

[0112] (1) Mix polyethylene glycol diglycidyl ether and aniline, stir and react at 40°C for 3 h, then react at 60°C for 3 h, and finally continue to react at 100°C for 6 h;

[0113] (2) Dropwise add 1,4 - cyclohexanediamine to toluene diisocyanate at a dropping rate of 1 drop every 6 - 8 s. After the dropping is completed, react at 60°C for 6 h;

[0114] (3) Mix the solutions obtained from (1) and (2), stir and react at 60°C for 6 h, then perform vacuum degassing at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced - air oven at 80°C for 12 h, and then transfer to a vacuum oven and cure at 80°C for 72 h.

[0115] Comparative Example 2

[0116] According to the component dosages in Table 1 (by weight percentage): 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether 25%, cyclopropylamine 4%, diphenylmethane diisocyanate 11%, amino - terminated polydimethylsiloxane 54%. The specific preparation method is as follows:

[0117] (1) Mix 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether and cyclopropylamine, stir and react at 40°C for 3 h, then react at 60°C for 3 h, and finally continue to react at 100°C for 6 h;

[0118] (2) Dropwise add amino - terminated polydimethylsiloxane to diphenylmethane diisocyanate at a dropping rate of 1 drop every 6 - 8 s. After the dropping is completed, react at 60°C for 6 h;

[0119] (3) Mix the solutions obtained from (1) and (2), stir and react at 60°C for 6 h, then perform vacuum degassing at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced - air oven at 80°C for 12 h, and then transfer to a vacuum oven and cure at 80°C for 72 h.

[0120] Comparative Example 3

[0121] According to the component dosages in Table 1 (by weight percentage): poly(dimethylsiloxane), diglycidyl ether - terminated 20%, n - butylamine 5%, isophorone diisocyanate 10%, polyetheramine 65%. The specific preparation method is as follows:

[0122] (1) Mix poly(dimethylsiloxane), diglycidyl ether-terminated, and n-butylamine, stir, and react at 40 °C for 3 h, then react at 60 °C for 3 h, and finally continue to react at 100 °C for 6 h;

[0123] (2) Dropwise add polyetheramine to isophorone diisocyanate at a dropping rate of one drop every 6 - 8 s. After the dropping is completed, react at 60 °C for 6 h;

[0124] (3) Mix the solutions after the reactions in (1) and (2), stir, and react at 60 °C for 6 h. Then, perform vacuum degassing at room temperature for half an hour. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced-air oven at 80 °C for 12 h, and then transfer to a vacuum oven and cure at 80 °C for 72 h.

[0125] Next, use a scanning electron microscope (SEM) and a transmission electron microscope (TEM) to analyze the surface morphology of the materials prepared in the examples. The scanning electron microscope (SEM) and transmission electron microscope (TEM) images obtained are shown respectively as Figure 1 and Figure 2 shown. Specifically, Figure 1 are scanning electron microscope (SEM) images of the enhanced and toughened room-temperature self-healing materials in Example 1 and Example 2 of the present invention at different magnifications. Figure 2 are transmission electron microscope (TEM) images of the enhanced and toughened room-temperature self-healing materials in Example 1 and Example 2 of the present invention at different magnifications. Among them, Figure 1 in (a) and (b) are SEM images of the enhanced and toughened room-temperature self-healing materials of Example 1 and Example 2 at a magnification of 2000; (c) and (d) are SEM images of the enhanced and toughened room-temperature self-healing materials of Example 1 and Example 2 at a magnification of 5000. Figure 2 in (a) and (b) are TEM images of the enhanced and toughened room-temperature self-healing materials of Example 1 and Example 2 at a magnification of 3000; (c) and (d) are TEM images of the enhanced and toughened room-temperature self-healing materials of Example 1 and Example 2 at a magnification of 5000. We can observe that with the change of the binary epoxy monomer or polymer, the phase domain size of the material changes significantly. With the change of the phase domain size, the mechanical properties of the material are significantly improved.

[0126] In addition, analyze the sample of Example 1. First is infrared analysis. Specifically, use the KBr tablet method for infrared characterization with a scanning range: 400 cm -1 ~4000 cm -1 , and the obtained infrared spectrum is as shown in Figure 3 shown. We can see that the characteristic peak of NCO at 2260 cm -1 disappears, and instead, there is a peak at 3350 cm -1There is a stretching vibration peak of NH at; 1367 cm -1 There is an absorption peak of B-C at; 1300 cm -1 There is an absorption peak of B-O at, which to a certain extent indicates the synthesis of the reaction product.

[0127] Figure 4 This is the XPS spectrum of the enhanced and toughened room-temperature self-healing material in Example 1 of the present invention. Among them, (a) is the full spectrum; (b) is the peak-fitting spectrum of B 1s in Example 1, which proves the formation of the B←N coordination bond, that is, the successful construction of the borate ester bond, which provides strong chemical evidence for the combination of polar and non-polar chains. The discrete points raw in the figure are the original data, and fitted is the fitted main curve.

[0128] In addition, the performance of different materials was tested. Specifically, the performance was tested by tensile testing. Figure 5 This is the tensile test diagram of the enhanced and toughened room-temperature self-healing materials in Example 1 and Example 2 of the present invention. Among them, (a) is the tensile stress-strain curve of Example 1; (b) is the tensile stress-strain curve of Example 2. The specific performance test results are shown in Table 2.

[0129] Table 2 Test results of self-healing performance of different materials

[0130]

[0131] It can be seen from Table 2 that since phenylboronic acid was not added and no nitrogen-coordinated borate ester bond and crosslinked network were formed in the polymer (Comparative Examples 1-3), its mechanical properties and self-healing efficiency are far lower than those of the examples. The present invention bridges the silane chain and the carbon chain by introducing nitrogen-coordinated borate ester, which improves the compatibility while also improving the self-healing efficiency and mechanical properties, and can well meet the application of the material in the field of electronic components.

[0132] In summary, the present invention realizes the effective combination of polar and non-polar chains through borate esters, improves the comprehensive performance of the material, and has broad application prospects in the field of electronic packaging. In the embodiments of the present invention, by using linear polymers such as diol-based linear polymers and polyurea-based linear polymers as raw materials, borate ester bonds are generated through the reaction of linear polymers capped with boric acid and linear polymers containing a large number of hydroxyl groups, and dynamic borate ester bonds are introduced during the cross-linking of polymers. This not only greatly improves the compatibility between silane chains and carbon chains, but also significantly enhances the internal structure of the material, playing a role in strengthening and toughening the material; from the microscopic structure, the presence of borate ester bonds makes the polar and non-polar chains intertwine more tightly, and the phase domain size is more uniform, improving the comprehensive performance of the material, thereby achieving the effects of improving compatibility and enhancing toughening. In addition, the self-healing material prepared in the embodiments of the present invention has excellent self-healing performance and long service life. The reaction of isocyanate and diamine provides a good mechanical property basis for the material; at the same time, at room temperature, borate ester bonds can undergo an exchange reaction, endowing the material with good self-healing performance, thereby realizing the self-healing of the material at room temperature and extending the service life of the material. This material is particularly suitable for the field of electronic packaging, can effectively protect electronic components, improve the reliability and stability of electronic devices, and solves the problem of insufficient self-healing ability of existing polymer materials when used for electronic packaging. Moreover, the preparation method of the strengthening and toughening room-temperature self-healing material provided by the embodiments of the present invention is simple. The good combination of polar and non-polar chains enhances the internal interaction of the material, significantly improves the mechanical properties of the material, realizes the strengthening and toughening effect, and has broad market prospects.

[0133] In addition, it should be particularly noted that the core of the present invention lies in using the chemical reaction between specific raw materials to form dynamic borate ester bonds with boron-nitrogen inner coordination. Its preparation method includes steps such as the synthesis of diol-based linear polymers and polyurea-based linear polymers, the synthesis of cross-linked polymers, and the curing of self-healing materials, and needs to react under specific temperature and time conditions. The unique structure of borate ester bonds enables them to act as a "bridge", connecting non-polar chains such as silane chains at one end and polar chains such as carbon chains at the other end, greatly promoting the interaction between polar and non-polar chains and significantly improving their compatibility. This good compatibility makes the internal structure of the material more stable. At the microscopic level, the polar and non-polar regions can work better together. When the material is damaged, the dynamic characteristics of borate ester bonds play a role, promoting the exchange reaction between reversible dynamic borate ester bonds, enabling the material to achieve self-healing at room temperature. At the same time, the tight combination of polar and non-polar chains enhances the internal interaction force of the material, effectively improving the mechanical properties of the material and realizing the strengthening and toughening of the material. For example, when subjected to external tensile force, the polar and non-polar chains are connected through borate ester bonds and can jointly bear the tensile force, avoiding local stress concentration, thereby improving the tensile strength of the material.

[0134] Finally, it should also be noted that there are various optional raw materials for various monomers or polymers in the above embodiments of the present invention. Raw materials such as polyethylene glycol diglycidyl ether and aniline in the specific embodiments are all commercially available products from existing manufacturers. For example, aniline, also known as aminobenzene, is an organic compound with the chemical formula C 6 H 7 N. It is a colorless oily liquid that decomposes when heated to 370 °C, is slightly soluble in water, and is easily soluble in organic solvents such as ethanol and ether. The commercially available product from Shandong Xuchen Chemical Technology Co., Ltd. can be used. Of course, it can also be prepared through relevant chemical reactions according to needs. For example, the process of directly synthesizing aniline from benzene, ammonia, and oxygen, or the outline of directly oxidizing and aminating benzene with hydrogen peroxide as the oxidant can be adopted. It can actually be selected according to needs and will not be elaborated here.

[0135] The above has described in detail the preferred embodiments of the present invention, describing the basic principles, main features, and advantages of the present invention. However, those skilled in the art should understand that the embodiments of the present invention are not limited to the above embodiments. The above embodiments and the descriptions in the specification are only preferred examples of the present invention and are not used to limit the present invention. Within the scope of knowledge possessed by ordinary technicians in the art, various changes can be made without departing from the purpose of the embodiments of the present invention. It is not necessary and impossible to enumerate all the embodiments here. And the obvious changes or variations derived therefrom are still within the protection scope of the embodiments of the present invention.

Claims

1. A reinforced and toughened room temperature self-repairing material, characterized in that: The reinforced and toughened room-temperature self-healing material includes the following raw materials: diol linear polymers and polyurea linear polymers; wherein the diol linear polymers are prepared using monoamine monomers and diepoxy monomers or polymers as raw materials; and the polyurea linear polymers are prepared using diisocyanate monomers, monophenylboronic acid monomers, and diamine monomers or polymers as raw materials.

2. The reinforced and toughened room temperature self-repairing material according to claim 1, characterized in that: The reinforced and toughened room-temperature self-repairing material comprises the following raw materials calculated by weight percentage: 3-10% monoamine monomer, 10-50% diepoxy monomer or polymer, 8-15% diisocyanate monomer, 40-60% diamine monomer or polymer, and 5-10% monophenylboric acid monomer.

3. The reinforced and toughened room temperature self-repairing material according to claim 2, characterized in that: The divalent epoxy monomer or polymer is selected from at least one of poly(dimethylsiloxane), diglycidyl ether end-capping, 3,3'5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, bisphenol C diglycidyl ether, and polyethylene glycol diglycidyl ether.

4. The reinforced and toughened room temperature self-repairing material according to claim 3, characterized in that: The monoamine monomer is at least one of n-butylamine, cyclopropylamine, p-methylaniline and aniline.

5. The reinforced and toughened room temperature self-repairing material according to claim 4, characterized in that: The diisocyanate monomer is at least one of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, para-xylylene diisocyanate and hexamethylene diisocyanate.

6. The reinforced and toughened room temperature self-repairing material according to claim 5, characterized in that: The diamine monomer or polymer is at least one of polyetheramine, amino-terminated polydimethylsiloxane, 1,4-cyclohexanediamine and p-phenylenediamine.

7. The reinforced and toughened room temperature self-repairing material according to claim 6, characterized in that: The monophenylboronic acid monomer is at least one of 2-aminophenylboronic acid, 3-aminophenylboronic acid and 4-aminophenylboronic acid.

8. A method for preparing a reinforced and toughened room temperature self-repairing material according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) mixing a binary epoxy monomer or polymer with a monoamine monomer uniformly, reacting at 40°C-100°C for 6 h-12 h to obtain a binary alcohol linear polymer; (2) mixing a diisocyanate monomer and a diamine monomer or polymer uniformly, reacting at 50°C-80°C for 3 h-10 h, then adding a monophenylboronic acid monomer and continuing to react at 50°C-80°C for 3 h-10 h to obtain a polyurea linear polymer; (3) The diol linear polymer in step (1) and the polyurea linear polymer in step (2) are uniformly mixed, reacted at 50° C.-100° C. to obtain a uniform cross-linked polymer, and then dried to obtain the reinforced and toughened room temperature self-healing material.

9. The method for preparing the reinforced and toughened room temperature self-repairing material according to claim 8, characterized in that: In the preparation method of the reinforced and toughened room-temperature self-repairing material, the drying treatment is to dry the uniform cross-linked polymer at 70°C-120°C for 12 h-24 h, and then place it in a vacuum oven for drying for 72 h-84 h.

10. Use of the reinforced and toughened room-temperature self-repairing material as claimed in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 in electronic packaging.

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