Room-temperature self-repairing high-molecular polymer blending material as well as preparation method and application thereof

Abstract

The embodiment of the invention relates to the technical field of high-molecular materials, and particularly discloses a room-temperature self-repairing high-molecular polymer blending material as well as a preparation method and application thereof. The high-molecular polymer blending material comprises the following raw materials: a binary epoxy monomer, a monoamine monomer, a binary isocyanate monomer, a diamine monomer, a ternary amine monomer and a monoaldehyde monomer. According to the invention, through reasonable use of various raw materials, polymer components with different polarities are combined by covalent bonds through chemical reaction, the polymer material with small phase separation size and excellent comprehensive performance is prepared, the compatibility of polar chains and non-polar chains is remarkably improved, and the performance of the polymer material is improved. The problem that good self-repairing performance cannot be provided while the mechanical property is guaranteed due to the fact that existing different-polarity room-temperature self-repairing high-molecular polymer blending materials have the compatibility problem is solved. Moreover, the preparation method is simple, and the prepared material can be applied to the field of electronic packaging and has a good application prospect.

Description

Technical Field

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

[0002] With the rapid development of modern industry and technology, polymer materials are increasingly used in daily life and industrial production. Especially in the field of electronic packaging, polymer materials with excellent performance are of great significance to the reliability and service life of electronic equipment. For example, excellent mechanical properties (such as impact resistance, tensile strength, etc.) can effectively protect electronic components from external physical impact and mechanical stress damage, and excellent self-healing properties can cope with cracks, scratches and other damages that occur in the material during long-term use, prevent circuit failure, and thus reduce maintenance costs.

[0003] However, single-component polymer materials often have difficulty meeting other functional requirements (such as self-healing properties, toughness, flame retardancy or biocompatibility) while meeting a certain specific performance (such as mechanical strength, thermal stability or processing performance). For this reason, blending and modifying a variety of polymers by physical or chemical methods to prepare composite materials with multiple properties has become an important research direction in the current field of materials science and engineering. However, in the blending system, the compatibility problem between polymers of different polarities is still a scientific problem that needs to be solved urgently. The polymer molecules with high polarity contain more polar groups, and the interaction forces between these groups are strong, so that the distance between polymer molecules is closer and the arrangement is tight. The interaction force between non-polar polymer molecules is weak, the distance between molecules is farther, and the arrangement is loose. When the two are mixed, due to the difference in the intermolecular interaction force, it is difficult to form a stable blending system between polymers of different polarities, resulting in poor compatibility, and thus it is not possible to meet other functional requirements while meeting a certain specific performance.

[0004] Therefore, the above-mentioned prior art solutions have the following defects: In the prior art, the existing room temperature self-healing polymer blend materials of different polarities have compatibility problems, resulting in the problem of being unable to provide good self-healing properties while ensuring mechanical properties. Summary of the invention

[0005] The purpose of the embodiments of the present invention is to provide a room temperature self-healing polymer blend material to solve the compatibility problem of existing room temperature self-healing polymer blend materials of different polarities mentioned in the above background technology, which makes it impossible to provide good self-healing performance while ensuring mechanical properties.

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

[0007] A room-temperature self-healing polymer blend material, comprising the following raw materials: a polyol linear polymer, a polyurea linear polymer; wherein, the polyol linear polymer is prepared from a binary epoxy monomer and a primary amine monomer; the polyurea linear polymer is prepared from a diisocyanate monomer, a diamine monomer, a triamine monomer, and a monoaldehyde monomer.

[0008] In the embodiment of the present invention, the room-temperature self-healing polymer blend material is prepared by using a binary epoxy monomer, a primary amine monomer, a diisocyanate monomer, a diamine monomer, a triamine monomer, and a monoaldehyde monomer as raw materials. Through effective regulation of the ratio, chemical reactions occur between the raw materials, and different polar polymer components are covalently bonded through chemical reactions, thereby preparing a room-temperature self-healing polymer blend material with small phase separation size and excellent comprehensive performance, realizing better compatibility between polar polymer chains and non-polar polymer chains. It not only exhibits higher mechanical properties (such as tensile strength and toughness) and smaller phase separation size, but also endows the material with excellent recycling and reprocessing properties and room-temperature self-healing properties (self-healing efficiency exceeds 90%) due to the reversible characteristics of dynamic bonds, solving the problem of compatibility difficulties existing in existing room-temperature self-healing polymer blend materials with different polarities, which leads to the inability to provide good self-healing properties while ensuring mechanical properties, and opening up a new way for the design and preparation of high-performance room-temperature self-healing polymer blend materials.

[0009] Preferably, the room-temperature self-healing polymer blend material comprises the following raw materials by weight percentage: 10-30% of binary epoxy monomer, 1-5% of primary amine monomer, 10-20% of diisocyanate monomer, 30-70% of diamine monomer, 3-20% of triamine monomer, and 1-10% of monoaldehyde monomer.

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

[0011] (1) Mix the binary epoxy monomer and the primary amine monomer evenly, and react at 50°C - 100°C for 6h - 12h to obtain a polyol linear polymer;

[0012] (2) Mix the monoaldehyde monomer and the triamine monomer evenly, react at 40 - 80°C for 6h - 12h, then mix evenly with the diisocyanate monomer and the diamine monomer, and react at 30°C - 80°C for 3h - 10h to obtain a polyurea linear polymer;

[0013] (3) Mix the polyol linear polymer in step (1) with the polyurea linear polymer in step (2) evenly, and carry out the reaction at 50°C - 100°C to obtain a uniform cross-linked polymer, and then heat and cure to obtain the room-temperature self-healing polymer blend material.

[0014] Another object of the embodiments of the present invention is to provide an application of the above-mentioned room-temperature self-healing polymer blend material in electronic packaging. Its uniqueness lies in that it reacts to form a dynamic borate ester bond with boron-nitrogen inner coordination, which greatly promotes the exchange reaction between reversible dynamic borate ester bonds, improves the repair efficiency, and bridges the silane chain and the carbon chain through the borate ester bond, promoting better compatibility between polar polymer chains and non-polar polymer chains, thereby endowing the material with room-temperature self-healing performance and recycling and reprocessing performance. This material is especially suitable for the field of electronic packaging, and can effectively protect electronic components and improve 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:

[0016] The room-temperature self-healing polymer blend material provided by the embodiments of the present invention rationally uses raw materials such as binary epoxy monomers, monoamine monomers, diisocyanate monomers, diamine monomers, triamine monomers, and monoaldehyde monomers, and uses chemical reactions to form dynamic borate ester bonds with boron-nitrogen inner coordination, which greatly promotes better compatibility between polar polymer chains and non-polar polymer chains. It not only exhibits higher mechanical properties, but also endows the material with room-temperature self-healing performance (self-healing efficiency exceeds 90%), solving the problem that existing room-temperature self-healing polymer blend materials with different polarities have compatibility problems, resulting in the inability to provide good self-healing performance while ensuring mechanical properties. Moreover, the preparation method of the room-temperature self-healing polymer blend material provided by the embodiments of the present invention is simple, and the good combination of polar chains and non-polar chains enhances the internal interaction of the material, providing good mechanical properties and self-healing performance of the material, and having 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 It is a scanning electron microscope (SEM) image of the room-temperature self-healing polymer blend material in Embodiment 1 of the present invention.

[0019] Figure 2 It is a transmission electron microscope (TEM) image of the room-temperature self-healing polymer blend material in Embodiment 1 of the present invention.

[0020] Figure 3 This is the infrared spectrum of the room temperature self-healing polymer blend material in Example 1 of the present invention.

[0021] Figure 4 This is the XPS spectrum of the room temperature self-healing polymer blend material in Example 1 of the present invention.

[0022] Figure 5 This is a tensile test diagram of the room temperature self-healing polymer blend material in Example 1 of the present invention. DETAILED DESCRIPTION

[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 combination 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 pointed out that for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the embodiments of the present invention. These all belong to the protection scope of the embodiments of the present invention.

[0024] The specific implementation of the present invention is described in detail below in conjunction with specific embodiments.

[0025] First of all, it should be noted that in the field of electronic packaging, high molecular polymer materials with excellent performance are of great significance to the reliability and service life of electronic devices. However, high molecular polymer materials with a single component often have difficulty in meeting other functional requirements (such as self-healing performance, toughness, flame retardancy or biocompatibility) while meeting a certain specific performance (such as mechanical strength, thermal stability or processing performance). To this end, blending and modifying multiple polymers by physical or chemical methods to prepare composite materials with multiple properties has become an important research direction in the current field of materials science and engineering. However, in the blending system, the compatibility problem between polymers of different polarities is still a scientific problem that needs to be solved urgently, especially in terms of interface interaction, phase structure regulation and performance stability. In addition, these blended materials are often difficult to achieve efficient recycling during the recycling and reprocessing process after the end of their life cycle due to problems such as phase separation or degradation, which has also become a key bottleneck restricting their sustainable development. Therefore, in-depth research on the compatibility mechanism of polymer blending and its recycling and reuse technology is of great significance to promote the greening and high performance of polymer materials.

[0026] Therefore, solving the compatibility problem of room temperature self-healing polymer blends of different polarities, and thereby enabling the room temperature self-healing polymer blends of different polarities to provide good self-healing properties while ensuring mechanical properties, has become an urgent problem that needs to be solved. It is also a key research direction in the field of materials, and plays an important role in improving the performance of electronic equipment, reducing maintenance costs, and promoting the sustainable development of the electronics industry.

[0027] In recent years, polymer blending technology has become an important strategy to improve material performance by introducing compatibilizers to achieve effective combination of different components. For example, Weifu Dong et al. used modified tannic acid with a star-shaped multi-arm structure as a compatibilizer in their research and successfully applied it to the blending system of polylactic acid (PLA) and polypropylene carbonate (PPC) to prepare a composite material with high strength, high toughness and excellent barrier properties. In addition, Pires et al. used maleic anhydride grafted polypropylene (PP-g-MAH) as a reactive compatibilizer to significantly improve the interfacial compatibility of polypropylene (PP) and nylon 6 (PA6), thereby improving the mechanical properties and thermal stability of the blended material. However, although compatibilizers play an important role in polymer blending, existing methods still have certain limitations. On the one hand, the selection and application of compatibilizers usually depend on the chemical properties of a specific polymer system and lack universality; on the other hand, compatibilizers mainly bind different components by generating physical or chemical interactions at the interface, which is difficult to fundamentally solve the phase separation problem, resulting in a larger internal phase region size of the material, thereby restricting the further improvement of its comprehensive performance. Therefore, the development of new and efficient compatibility methods remains a key scientific issue that needs to be urgently addressed in the field of polymer blending.

[0028] Therefore, based on the above background, the embodiment of the present invention provides a room temperature self-healing polymer blend material and a preparation method thereof, as an innovative polymer blending strategy, which opens up a new way for the design and preparation of high-performance room temperature self-healing polymer blend materials. Specifically, the room temperature self-healing polymer blend material is a room temperature self-healing material with excellent compatibility of different polar chains inside. The polymer components of different polarities are covalently bonded by chemical reactions to prepare a room temperature self-healing polymer blend material with small phase separation size and excellent comprehensive performance. The room temperature self-healing polymer blend material specifically includes the following raw materials:

[0029] Polyol linear polymers and polyurea linear polymers; wherein the polyol linear polymers are prepared using divalent epoxy monomers and monovalent amine monomers as raw materials; and the polyurea linear polymers are prepared using divalent isocyanate monomers, divalent amine monomers, trivalent amine monomers and monovalent aldehyde monomers as raw materials.

[0030] In the embodiments of the present invention, binary epoxy monomers, primary amine monomers, diisocyanate monomers, diamine monomers, triamine monomers, and primary aldehyde monomers are innovatively selected as raw materials. Through the chemical reactions between these raw materials, polymer components with different polarities are covalently bonded, thereby preparing a room-temperature self-healing polymer blend material with small phase separation size and excellent comprehensive properties. Specifically, reaction sites are first constructed on two polymer chains with different polarities: on the one hand, a polymer with a polyhydroxy structure between chains is synthesized by reacting a binary epoxy monomer with a primary amine monomer; on the other hand, a polymer chain with phenylboronic acid groups on the side chains is prepared by reacting a triamine monomer, a primary aldehyde monomer, a diamine monomer, and a diisocyanate monomer. Among them, the two polymer chains are respectively based on siloxane chains and carbon chains, with significant polarity differences. Subsequently, a boroxine dynamic covalent bond with a boron-nitrogen inner coordination structure is successfully constructed through the specific reaction between phenylboronic acid groups and hydroxyl groups, realizing the efficient cross-linking of the two polymers. Experimental results show that compared with the direct blending system without dynamic bonds, the prepared material not only exhibits higher mechanical properties (such as tensile strength and toughness) and smaller phase separation size, but also endows the material with excellent recycling and reprocessing properties and room-temperature self-healing ability (self-healing efficiency exceeds 90%) due to the reversible characteristics of the dynamic bonds. Therefore, the present invention not only provides a novel compatibilization strategy, but also opens up a new way for the design and preparation of high-performance polymer blend materials, with important scientific significance and application prospects.

[0031] As another preferred embodiment of the embodiments of the present invention, the room-temperature self-healing polymer blend material comprises the following raw materials by weight percentage: 10-30% of binary epoxy monomers, 1-5% of primary amine monomers, 10-20% of diisocyanate monomers, 30-70% of diamine monomers, 3-20% of triamine monomers, and 1-10% of primary aldehyde monomers.

[0032] As another preferred embodiment of the embodiments of the present invention, the binary epoxy monomers are selected from at least one of poly(dimethylsiloxane) diglycidyl ether-terminated, 3,3',5,5'-tetramethylbiphenol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, and polyethylene glycol diglycidyl ether.

[0033] As another preferred embodiment of the embodiments of the present invention, the primary amine monomers are at least one of n-butylamine, n-pentylamine, n-hexylamine, 2-amino-2-methyl-1-propanol, and 3-methyl-1-pentylamine.

[0034] As another preferred embodiment of the embodiments 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.

[0035] As another preferred embodiment of the embodiments of the present invention, the diamine monomer is at least one of polyetheramine, amino-terminated polydimethylsiloxane, 1,4-cyclohexanediamine, p-phenylenediamine, and isophorone diamine.

[0036] As another preferred embodiment of the embodiments of the present invention, the triamine monomer is at least one of trimethylolpropane tripropyleneglycol ether (amino-terminated), melamine, and three-arm polyethylene glycol amine.

[0037] As another preferred embodiment of the embodiments of the present invention, the monoaldehyde monomer is at least one of 2-formylbenzeneboronic acid, 3-formylbenzeneboronic acid, 4-formylbenzeneboronic acid, and benzaldehyde.

[0038] The embodiments of the present invention also provide a preparation method of a room-temperature self-healing polymer blend material. The preparation method of the room-temperature self-healing polymer blend material specifically includes the following steps:

[0039] (1) Mix the binary epoxy monomer and the monoamine monomer evenly, and react at 50°C - 100°C for 6h - 12h to obtain a polyol linear polymer;

[0040] (2) Mix the monoaldehyde monomer and the triamine monomer evenly, react at 40 - 80°C for 6h - 12h, and then mix evenly with the binary isocyanate monomer and the diamine monomer, and react at 30°C - 80°C for 3h - 10h to obtain a polyurea linear polymer;

[0041] (3) Mix the polyol linear polymer in step (1) and the polyurea linear polymer in step (2) evenly, react at 50°C - 100°C for 6h - 24h to obtain a uniform crosslinked polymer, and then heat and cure to obtain the room-temperature self-healing polymer blend material.

[0042] As another preferred embodiment of the embodiments of the present invention, in the preparation method of the room-temperature self-healing polymer blend material, the heat curing is to first mix and defoam in a vacuum defoaming machine for 10min - 30min and then place it in an oven at 70°C - 120°C to dry for 12h - 24h to preliminarily remove moisture and volatile substances in the mixture and achieve preliminary curing of the material; then place it in a vacuum oven to dry for 72h - 84h to finally obtain a room-temperature self-healing polymer blend material with excellent performance.

[0043] Preferably, the preparation method of the room-temperature self-healing polymer blend material comprises the following steps:

[0044] (1) Synthesis of polyol linear polymer: Mix a binary epoxy monomer and a primary amine monomer evenly, and react for 6 h - 12 h in the temperature range of 50°C - 100°C to obtain a uniform polyol linear polymer; specifically, by using the epoxy groups on the binary epoxy monomer and the amino groups on the primary amine monomer to carry out an epoxy ring-opening reaction, multiple claw-shaped structures of diols are formed in the middle of the prepared linear polymer chain.

[0045] (2) Synthesis of polyurea linear polymer: Mix a primary aldehyde monomer and a tertiary amine monomer evenly, react at 40 - 80°C for 6 h - 12 h to obtain a branched diamine, and then evenly mix a diisocyanate monomer and a series of diamines (i.e., the diamine monomer and the obtained branched diamine), and react at 30°C - 80°C for 3 h - 10 h to obtain a uniform polyurea linear polymer; specifically, a linear polymer with phenylboronic acid branches is prepared by using a tertiary amine monomer, a primary aldehyde monomer, a diisocyanate monomer, and a diamine monomer.

[0046] (3) Synthesis of crosslinked polymer: Thoroughly mix the solutions after the reactions in the above two steps (i.e., the polyol linear polymer in step (1) and the polyurea linear polymer in step (2)), and react at 50°C - 100°C for 10 h - 24 h to obtain a crosslinked polymer, that is, a crosslinked polymer containing a boron-nitrogen inner coordination borate bond; due to the nitrogen-coordinated borate bonds and hydrogen bonds contained in this network, the polymer can have excellent self-healing properties at room temperature.

[0047] (4) First, mix and defoam the crosslinked polymer obtained in step (3) in a vacuum defoaming machine for 10 min - 30 min, and then place it in an oven at 70°C - 120°C to dry for 12 h - 24 h to preliminarily remove the moisture and volatile substances in the mixture and achieve the preliminary curing of the material; subsequently, place it in a vacuum oven to dry for 72 h - 84 h, and finally obtain a room-temperature self-healing polymer blend material with excellent performance, which can be used as a self-healing material in electronic packaging.

[0048] An embodiment of the present invention also provides a room-temperature self-healing polymer blend material prepared by using the above preparation method.

[0049] An embodiment of the present invention also provides an application of the above room-temperature self-healing polymer blend material in electronic packaging. This room-temperature self-healing polymer blend material has good self-healing properties, can effectively protect electronic components, improve the reliability and stability of electronic devices, and thus extend the service life of electronic devices.

[0050] The technical effects of the room-temperature self-healing polymer blend material of the embodiments of the present invention are further described below by way of specific examples.

[0051] Example 1

[0052] A room-temperature self-healing polymer blend material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: 18% of polydimethylsiloxane diglycidyl ether capped, 2% of n-butylamine, 10% of trimethylolpropane tripropyleneglycol ether (amino-capped), 5% of 4-formylphenylboronic acid, 15% of isophorone diisocyanate, 50% of polyetheramine.

[0053] In this example, the preparation method of the room-temperature self-healing polymer blend material specifically includes the following steps:

[0054] (1) Mix and stir polydimethylsiloxane diglycidyl ether capped and n-butylamine, react at 60 °C for 3 h, and then react at 100 °C for 3 h;

[0055] (2) Mix trimethylolpropane tripropyleneglycol ether (amino-capped) and 4-formylphenylboronic acid evenly, and react at 60 °C for 12 h; then mix the reactants with polyetheramine evenly and place them in an ice-water bath, and slowly add isophorone diisocyanate dropwise thereto. After the dropwise addition is completed, react at 60 °C for 6 h;

[0056] (3) Mix the solutions after the reactions (1) and (2), stir and react at 60 °C for 6 h, then carry out vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced-air oven at 80 °C for 24 h, then cure at 100 °C for 24 h, and finally transfer to a vacuum oven and cure at 80 °C for 72 h to obtain the room-temperature self-healing polymer blend material.

[0057] Example 2

[0058] A room-temperature self-healing polymer blend material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: 15% of 1,6-hexanediol diglycidyl ether, 2% of n-pentylamine, 13% of melamine, 5% of 3-formylphenylboronic acid, 13% of hexamethylene diisocyanate, 52% of polydimethylsiloxane amino-capped.

[0059] In this example, the preparation method of the room-temperature self-healing polymer blend material specifically includes the following steps:

[0060] (1) Mix and stir 1,6-hexanediol diglycidyl ether and n-pentylamine, react at 60 °C for 3 h, and then react at 100 °C for 3 h;

[0061] (2) Mix melamine and 3-formylphenylboronic acid evenly and react at 60 °C for 12 h; then mix the reactants with amino-terminated polydimethylsiloxane evenly and place them in an ice-water bath, and slowly add hexamethylene diisocyanate dropwise thereto. After the addition is completed, react at 60 °C for 6 h;

[0062] (3) After mixing and stirring the solutions after the reactions in (1) and (2) and reacting at 60 °C for 6 h, carry out vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure it in a forced-air oven at 80 °C for 24 h, then cure it at 100 °C for 24 h, and finally transfer it to a vacuum oven and cure it at 80 °C for 72 h to obtain a room-temperature self-healing polymer blend material.

[0063] Example 3

[0064] A room-temperature self-healing polymer blend material, and the dosage of each component of the specific raw materials (by weight percentage) is as follows: diglycidyl cyclohexane-1,2-dicarboxylate 20%, n-hexylamine 3%, tri-arm polyethylene glycol amine 15%, 2-formylphenylboronic acid 5%, toluene diisocyanate 15%, polyetheramine 22%, amino-terminated polydimethylsiloxane 20%.

[0065] In this example, the preparation method of the room-temperature self-healing polymer blend material specifically includes the following steps:

[0066] (1) Mix diglycidyl cyclohexane-1,2-dicarboxylate and n-hexylamine and stir at 60 °C for 3 h, and then react at 100 °C for 3 h;

[0067] (2) Mix tri-arm polyethylene glycol amine and 2-formylphenylboronic acid evenly and react at 60 °C for 12 h; then mix the reactants with polyetheramine and amino-terminated polydimethylsiloxane evenly and place them in an ice-water bath, and slowly add toluene diisocyanate dropwise thereto. After the addition is completed, react at 60 °C for 6 h;

[0068] (3) After mixing and stirring the solutions after the reactions in (1) and (2) and reacting at 60 °C for 6 h, carry out vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure it in a forced-air oven at 80 °C for 24 h, then cure it at 100 °C for 24 h, and finally transfer it to a vacuum oven and cure it at 80 °C for 72 h to obtain a room-temperature self-healing polymer blend material.

[0069] Example 4

[0070] A room-temperature self-healing polymer blend material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: 3,3',5,5'-tetramethylbiphenyl diglycidyl ether 20%, 2-amino-2-methyl-1-propanol 5%, trimethylolpropane tripropyleneglycol ether (amino-terminated) 15%, 4-formylphenylboronic acid 5%, diphenylmethane diisocyanate 15%, 1,4-cyclohexanediamine 20%, polydimethylsiloxane amino-terminated 20%.

[0071] In this example, the preparation method of the room-temperature self-healing polymer blend material specifically includes the following steps:

[0072] (1) Mix 3,3',5,5'-tetramethylbiphenyl diglycidyl ether and 2-amino-2-methyl-1-propanol, stir and react at 60 °C for 3 h, and then react at 100 °C for 3 h;

[0073] (2) Mix trimethylolpropane tripropyleneglycol ether (amino-terminated) and 4-formylphenylboronic acid evenly, and react at 60 °C for 12 h; then mix the reactants with 1,4-cyclohexanediamine and polydimethylsiloxane amino-terminated evenly, place them in an ice-water bath, and slowly dropwise add diphenylmethane diisocyanate thereto. After the dropping is completed, react at 60 °C for 6 h;

[0074] (3) Mix the solutions after the reactions (1) and (2), stir and react at 60 °C for 6 h, then vacuum degas at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced-air oven at 80 °C for 24 h, then cure at 100 °C for 24 h, and finally transfer to a vacuum oven and cure at 80 °C for 72 h to obtain the room-temperature self-healing polymer blend material.

[0075] Example 5

[0076] A room-temperature self-healing polymer blend material, the dosage of each component of the specific raw materials (by weight percentage) is as follows: polyethylene glycol diglycidyl ether 18%, 3-methyl-1-pentylamine 4%, trimethylolpropane tripropyleneglycol ether (amino-terminated) 18%, 4-formylphenylboronic acid 6%, p-phenylene diisocyanate 16%, p-phenylenediamine 19%, polydimethylsiloxane amino-terminated 19%.

[0077] In this example, the preparation method of the room-temperature self-healing polymer blend material specifically includes the following steps:

[0078] (1) Mix polyethylene glycol diglycidyl ether and 3-methyl-1-pentylamine, stir and react at 60 °C for 3 h, and then react at 100 °C for 3 h;

[0079] (2) Mix trimethylolpropane tripropylene glycol ether (amino-terminated) and 4-formylphenylboronic acid evenly, and react at 60 °C for 12 h; then mix the reactants with p-phenylenediamine and polydimethylsiloxane amino-terminated evenly and place them in an ice-water bath, and slowly add p-phenylenediisocyanate dropwise thereto. After the addition is completed, react at 60 °C for 6 h;

[0080] (3) After mixing and stirring the solutions obtained from (1) and (2) and reacting at 60 °C for 6 h, carry out vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure at 80 °C in a forced-air oven for 24 h, then cure at 100 °C for 24 h, and finally transfer to a vacuum oven and cure at 80 °C for 72 h to obtain a room-temperature self-healing polymer blend material.

[0081] Example 6

[0082] Compared with Example 1, except that the amounts of each component of the specific raw materials of the room-temperature self-healing polymer blend material (by weight percentage) are 10% of polydimethylsiloxane diglycidyl ether-terminated, 1% of n-butylamine, 8% of trimethylolpropane tripropylene glycol ether (amino-terminated), 1% of 4-formylphenylboronic acid, 10% of isophorone diisocyanate, and 70% of polyetheramine, the others are the same.

[0083] Example 7

[0084] Compared with Example 1, except that the amounts of each component of the specific raw materials of the room-temperature self-healing polymer blend material (by weight percentage) are 30% of polydimethylsiloxane diglycidyl ether-terminated, 5% of n-butylamine, 20% of trimethylolpropane tripropylene glycol ether (amino-terminated), 5% of 4-formylphenylboronic acid, 10% of isophorone diisocyanate, and 30% of polyetheramine, the others are the same.

[0085] Example 8

[0086] Compared with Example 1, except that the amounts of each component of the specific raw materials of the room-temperature self-healing polymer blend material (by weight percentage) are 25% of polydimethylsiloxane diglycidyl ether-terminated, 2% of n-butylamine, 3% of trimethylolpropane tripropylene glycol ether (amino-terminated), 10% of 4-formylphenylboronic acid, 20% of isophorone diisocyanate, and 40% of polyetheramine, the others are the same.

[0087] Example 9

[0088] Compared with Example 1, except that the amounts of each component of the specific raw materials of the room-temperature self-healing polymer blend material (by weight percentage) are 20% of polydimethylsiloxane diglycidyl ether-terminated, 2% of n-butylamine, 10% of trimethylolpropane tripropylene glycol ether (amino-terminated), 5% of 4-formylphenylboronic acid, 13% of isophorone diisocyanate, and 50% of polyetheramine, the others are the same.

[0089] Example 10

[0090] Compared with Example 1, except that the dosage of each component of the specific raw materials of the room temperature self-healing polymer blend material (by weight percentage) is 23% of polydimethylsiloxane diglycidyl ether capped, 2% of n-butylamine, 10% of trimethylolpropane tripropylene glycol ether (amino-capped), 5% of 4-formylphenylboronic acid, 10% of isophorone diisocyanate, and 50% of polyetheramine, others are the same.

[0091] Example 11

[0092] Compared with Example 1, except that the polydimethylsiloxane diglycidyl ether capped is replaced with a mixture of cyclohexane-1,2-dicarboxylic acid diglycidyl ester and polyethylene glycol diglycidyl ether of equal weight, others are the same as Example 1.

[0093] Example 12

[0094] Compared with Example 1, except that the n-butylamine is replaced with n-hexylamine, others are the same as Example 1.

[0095] Example 13

[0096] Compared with Example 1, except that the polyetheramine is replaced with amino-capped polydimethylsiloxane, others are the same as Example 1.

[0097] Example 14

[0098] Compared with Example 1, except that in step (1), the polydimethylsiloxane diglycidyl ether capped and n-butylamine are mixed and stirred at 50 °C for 6 h, and then reacted at 100 °C for 6 h, others are the same.

[0099] Example 15

[0100] Compared with Example 1, except that in step (2), the trimethylolpropane tripropylene glycol ether (amino-capped) and 4-formylphenylboronic acid are mixed evenly and reacted at 40 °C for 12 h; then the reactants are mixed evenly with polyetheramine and placed in an ice-water bath, and isophorone diisocyanate is slowly added dropwise thereto, and after the addition is completed, the reaction is carried out at 80 °C for 6 h, others are the same.

[0101] Example 16

[0102] Compared with Example 1, except that in step (2), the trimethylolpropane tripropylene glycol ether (amino-capped) and 4-formylphenylboronic acid are mixed evenly and reacted at 80 °C for 12 h; then the reactants are mixed evenly with polyetheramine and placed in an ice-water bath, and isophorone diisocyanate is slowly added dropwise thereto, and after the addition is completed, the reaction is carried out at 30 °C for 6 h, others are the same.

[0103] Example 17

[0104] Compared with Example 1, everything is the same except that the reaction temperature in step (3) is 50 °C.

[0105] Example 18

[0106] Compared with Example 1, everything is the same except that the reaction temperature in step (3) is 100 °C.

[0107] In order to verify the performance of the room-temperature self-healing polymer blend material, Comparative Example 1, Comparative Example 2, and Comparative Example 3 are set for comparison. The specific raw material ratios of each comparative example are shown in Table 1.

[0108] Table 1 Raw material component table of different samples (%)

[0109]

[0110]

[0111]

[0112] 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.

[0113] Comparative Example 1

[0114] According to the component dosages in Table 1 (by weight percentage): 18% of polydimethylsiloxane diglycidyl ether end-capped, 2% of n-butylamine, 10% of trimethylolpropane tripropyleneglycol ether (amine-terminated), 4% of benzaldehyde, 15% of isophorone diisocyanate, 51% of polyetheramine; the specific preparation method is as follows:

[0115] (1) Mix and stir polydimethylsiloxane diglycidyl ether end-capped and n-butylamine, react at 60 °C for 3 h, and then react at 100 °C for 3 h;

[0116] (2) Mix trimethylolpropane tripropyleneglycol ether (amine-terminated) and benzaldehyde evenly, react at 60 °C for 12 h; then mix the reactants with polyetheramine evenly, and slowly add isophorone diisocyanate dropwise thereto. After the dropwise addition is completed, react at 60 °C for 6 h;

[0117] (3) Mix the solutions after the reactions (1) and (2), stir and react at 60 °C for 6 h, then perform vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced-air oven at 80 °C for 24 h, then cure at 100 °C for 24 h, and finally transfer to a vacuum oven and cure at 80 °C for 72 h.

[0118] Comparative Example 2

[0119] According to the component dosages in Table 1 (by weight percentage): 1,6 - hexanediol diglycidyl ether 20%, n - hexylamine 5%, hexamethylene diisocyanate 15%, amino - terminated polydimethylsiloxane 60%; the specific preparation method is as follows:

[0120] (1) Mix 1,6 - hexanediol diglycidyl ether and n - hexylamine, stir and react at 60 °C for 3 h, then react at 100 °C for 3 h;

[0121] (2) Slowly drop - wise add hexamethylene diisocyanate to amino - terminated polydimethylsiloxane, and react at 60 °C for 6 h after the addition is completed;

[0122] (3) Mix the solutions after the reactions in (1) and (2), stir and react at 60 °C for 6 h, then carry out vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced - air oven at 80 °C for 24 h, then cure at 100 °C for 24 h, and finally transfer to a vacuum oven and cure at 80 °C for 72 h.

[0123] Comparative Example 3

[0124] According to the component dosages in Table 1 (by weight percentage): 3,3',5,5' - tetramethylbiphenol diglycidyl ether 25%, 3 - methyl - 1 - pentylamine 7%, diphenylmethane diisocyanate 18%, isophorone diamine 25%, amino - terminated polydimethylsiloxane 25%; the specific preparation method is as follows:

[0125] (1) Mix 3,3',5,5' - tetramethylbiphenol diglycidyl ether and 3 - methyl - 1 - pentylamine, stir and react at 60 °C for 3 h, then react at 100 °C for 3 h;

[0126] (2) Mix amino - terminated polydimethylsiloxane and isophorone diamine evenly, and slowly drop - wise add diphenylmethane diisocyanate to it, and react at 60 °C for 6 h after the addition is completed;

[0127] (3) Mix the solutions after the reactions in (1) and (2), stir and react at 60 °C for 6 h, then carry out vacuum degassing at room temperature for 10 min. Finally, pour the mixture into a polytetrafluoroethylene mold, cure in a forced - air oven at 80 °C for 24 h, then cure at 100 °C for 24 h, and finally transfer to a vacuum oven and cure at 80 °C for 72 h.

[0128] Next, the surface morphology of the materials prepared in the examples was analyzed using a scanning electron microscope (SEM) and a transmission electron microscope (TEM). 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 is the scanning electron microscope (SEM) image of the room - temperature self - healing polymer blend material in Example 1 of the present invention.Figure 2 This is the transmission electron microscope (TEM) image of the room-temperature self-healing polymer blend material in Example 1 of the present invention. It can be seen that the scale of phase separation inside the material containing the boron-oxygen bond with boron-nitrogen coordination is very small, indicating that the two polymer chains with different polarities inside the material have good compatibility.

[0129] In addition, the sample of Example 1 was analyzed. First was the infrared analysis. Specifically, the KBr tablet pressing method was used for infrared characterization, with the scanning range: 400 cm -1 ~4000 cm -1 . The obtained infrared spectrum is as shown in Figure 3 . It can be seen that there is no obvious characteristic peak of NCO at 2260 cm -1 . Instead, there is a stretching vibration peak of N-H at 3350 cm -1 , a characteristic peak of C=O at 1643 cm -1 , and an absorption peak of B-O at 1300 cm -1 , which to a certain extent indicates the synthesis of the reaction product.

[0130] Figure 4 This is the XPS spectrum of the room-temperature self-healing polymer blend material in Example 1 of the present invention. Among them, (a) is the B spectrum; (b) is the C spectrum, (c) is the N spectrum; (d) is the full spectrum, which proves the formation of the B←N coordination bond, that is, the successful construction of the borate ester bond, providing strong chemical evidence for the combination of polar chains and non-polar chains. The discrete points raw in the figure are the original data, and fitted is the fitted main curve.

[0131] In addition, the performance of different materials was detected. Specifically, the performance was detected by tensile testing. Figure 5 This is the tensile test image of the room-temperature self-healing polymer blend material in Example 1, with Comparative Example 1 as a control at the same time. Among them, (a) is the tensile stress-strain curve of Example 1; (b) is the tensile stress-strain curve of Comparative Example 1. The specific performance test results are shown in Table 2.

[0132] Table 2 Self-healing performance test results of different materials

[0133]

[0134] As can be seen from Table 2, since phenylboronic acid was not added, nitrogen-coordinated borate ester bonds and cross-linked networks were not formed in the polymer (Comparative Examples 1-3), so its mechanical properties and self-healing efficiency were much lower than those of the examples. Moreover, with the change of the binary epoxy monomer or polymer, the phase domain size of the material changed significantly, and with the change of the phase domain size, the mechanical properties of the material were significantly improved. By introducing nitrogen-coordinated borate ester, the present invention bridged the silane chain and the carbon chain, improving the compatibility while also improving the self-healing efficiency and mechanical properties, which can well meet the application of the material in the field of electronic components.

[0135] In summary, the mechanism of the present invention is as follows: The binary epoxy monomer, monoamine monomer, diisocyanate monomer, diamine monomer, triamine monomer, and monoaldehyde monomer are selected in the present invention, which can not only form boron-nitrogen inner-coordinated dynamic borate ester bonds, greatly promote the exchange reaction between reversible dynamic borate ester bonds, and improve the repair efficiency, but also bridge the silane chain and the carbon chain through the borate ester bond, promoting the better compatibility of polar polymer chains and non-polar polymer chains, thereby endowing the material with the ability of room-temperature self-healing and recycling and reprocessing performance. Specifically, in the examples of the present invention, the epoxy group on the binary epoxy monomer first undergoes an epoxy ring-opening reaction with the amino group on the monoamine monomer to form multiple claw-shaped structures of diols in the middle of the prepared linear polymer chain; then a linear polyurea with phenylboronic acid branches is prepared by using the triamine monomer, monoaldehyde monomer, diisocyanate monomer, and diamine monomer; the linear polyurea is reacted with the linear polyol polymer to obtain a cross-linked polymer containing boron-nitrogen inner-coordinated borate ester bonds; due to the nitrogen-coordinated borate ester bonds and hydrogen bonds contained in this network, the polymer has excellent self-healing properties at room temperature.

[0136] In addition, it should be specifically noted that the core of the present invention lies in utilizing the chemical reaction between specific raw materials. The preparation materials, by weight percentage, consist of 10 - 30% of binary epoxy monomers, 1 - 5% of monoamine monomers, 10 - 20% of diisocyanate monomers, 30 - 70% of diamine monomers, 3 - 20% of triamine monomers, and 1 - 10% of monoaldehyde monomers. Among them, there are various optional raw materials for each type of monomer. Its preparation method includes steps such as the synthesis of linear polymer polyols and linear polymer polyureas, the synthesis of crosslinked polymers, and the curing of self - healing materials, which need to react under specific temperature and time conditions. This material bridges the silane chain and the carbon chain by introducing nitrogen - coordinated borate ester, making the compatibility between polar and non - polar chains better, enhancing and toughening the properties of the material, and being able to self - repair at room temperature. It can be applied to the field of electronic packaging, effectively protecting electronic components and improving the reliability and service life of electronic devices. Compared with the prior art, the present invention generates a borate ester bond with internal boron - nitrogen coordination through the reaction of linear polyurea with phenylboronic acid branches and linear polysiloxane containing a large number of hydroxyl groups, greatly improving the compatibility between the silane chain and the carbon chain. Moreover, by utilizing the reaction of isocyanate and diamine, good mechanical properties are provided for the material, and at room temperature, the borate ester bond can undergo an exchange reaction, providing good self - repair properties and service life for the material. It is particularly suitable for the field of electronic packaging and has broad market prospects.

[0137] The above - mentioned preferred embodiments of the present invention have been described in detail, 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 - mentioned embodiments. The above - mentioned 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 room temperature self-healing polymer blend material, characterized in that: The room temperature self-healing polymer blend material includes the following raw materials: polyol linear polymers and polyurea linear polymers; wherein the polyol linear polymers are prepared using divalent epoxy monomers and monovalent amine monomers as raw materials; and the polyurea linear polymers are prepared using divalent isocyanate monomers, divalent amine monomers, trivalent amine monomers and monovalent aldehyde monomers as raw materials.

2. The room temperature self-healing polymer blend material according to claim 1, characterized in that: The room temperature self-healing high molecular polymer blend material comprises the following raw materials calculated by weight percentage: 10-30% of divalent epoxy monomers, 1-5% of monovalent amine monomers, 10-20% of divalent isocyanate monomers, 30-70% of divalent amine monomers, 3-20% of trivalent amine monomers, and 1-10% of monovalent aldehyde monomers.

3. The room temperature self-healing polymer blend material according to claim 2, characterized in that: The binary epoxy monomer is selected from at least one of polydimethylsiloxane diglycidyl ether end-capping, 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, and polyethylene glycol diglycidyl ether.

4. The room temperature self-healing polymer blend material according to claim 3, characterized in that: The monoamine monomer is at least one of n-butylamine, n-pentylamine, n-hexylamine, 2-amino-2-methyl-1-propanol and 3-methyl-1-pentylamine.

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

7. The room temperature self-healing polymer blend material according to claim 6, characterized in that: The triamine monomer is at least one of trimethylolpropane tripropylene glycol ether (amino-terminated), melamine, and three-arm polyethylene glycol amino.

8. The room temperature self-healing polymer blend material according to claim 7, characterized in that: The monoaldehyde monomer is at least one of 2-formylphenylboronic acid, 3-formylphenylboronic acid, 4-formylphenylboronic acid and benzaldehyde.

9. A method for preparing a room temperature self-healing polymer blend material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) mixing the binary epoxy monomer and the monoamine monomer uniformly, reacting at 50° C.-100° C. for 6 h-12 h to obtain a polyol linear polymer; (2) uniformly mixing the monoaldehyde monomer and the triamine monomer, reacting them at 40-80° C. for 6 h-12 h, and then uniformly mixing them with the diisocyanate monomer and the diamine monomer, and reacting them at 30-80° C. for 3 h-10 h to obtain a polyurea linear polymer; (3) The linear polyol polymer in step (1) and the linear polyurea polymer in step (2) are uniformly mixed, reacted at 50° C.-100° C. to obtain a uniform cross-linked polymer, and then heated and cured to obtain the room temperature self-healing polymer blend material.

10. Use of the room temperature self-healing polymer blend material as claimed in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 in electronic packaging.

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