Hydrated boric acid ester micromolecule with boron-nitrogen coordination bond, derivative resin material and preparation method of hydrated boric acid ester micromolecule and derivative resin material

Abstract

The invention relates to a hydrated borate micromolecule with a boron-nitrogen coordination bond, a derivative resin material and a preparation method of the hydrated borate micromolecule. The preparation method comprises the following steps: S1, synthesizing boron-nitrogen coordination micromolecules: dissolving and reacting boric acid, a derivative thereof and a polyfunctional group amine compound at room temperature through a solution reaction to obtain the boron-nitrogen coordination micromolecules; the borate micromolecule NCBW-X with intramolecular boron and nitrogen coordination is formed; s2, the NCBW-X micromolecule can be used for curing epoxy resin and synthesizing materials such as phenolic resin through end-NH2 and end-OH on two sides, the NCBW-X improves the mechanical property of each system through a rigid eight-membered ring, boron-nitrogen coordination of the NCBW-X can generate hydration, the environmental endurance is improved on the premise of retaining the original dynamic nature of boric acid ester of the NCBW-X, and the service life of the NCBW-X micromolecule is prolonged. Meanwhile, due to the dynamic reversibility of the NCBW-X, the NCBW-X is used for curing epoxy resin, and materials such as phenolic resin and the like are improved to a certain extent in the aspects of self-repairing and recycling.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer material synthesis and application, and in particular to the development of novel boron-nitrogen coordinated borate ester small molecules and their applications in dynamic polymer networks. The present invention relates to a hydrated borate ester small molecule with a boron-nitrogen coordination bond and a derivative resin material and a preparation method thereof, and in particular to a hydrated borate ester small molecule with a boron-nitrogen coordination bond that can be used for epoxy resin and phenolic resin materials and a preparation method and application thereof. The present invention describes in detail how to successfully apply the small molecule to the curing treatment of epoxy resin and the synthesis process of phenolic resin to improve the repair ability, reconstruction and environmental adaptability of these materials. Background Art

[0002] Epoxy resins and phenolic resins are widely used in industry due to their excellent mechanical properties, chemical resistance and processing convenience. However, common disadvantages of these materials include difficulty in repair and recycling, which limits their further application in some fields. In recent years, the introduction of dynamic chemical bonds has provided a new solution to improve the self-healing ability and recyclability of these materials.

[0003] Boron-nitrogen coordination bonds are particularly suitable for constructing dynamic polymer networks due to their reversibility and strong controllability. Through the dynamic breaking and recombination of boron-nitrogen coordination bonds, the self-repair and multiple recycling of materials can be achieved, significantly enhancing the life cycle of the material and its environmental adaptability.

[0004] In the prior art, boron-nitrogen coordination bonds have been applied to the design of some polymers, but most of these applications focus on their use in a single material system. Therefore, developing a universal boron-nitrogen coordination small molecule and widely applying it to a variety of polymer materials is of great significance for improving material performance and broadening the scope of application. Especially in the fields of epoxy resin curing and phenolic resin synthesis, by introducing boron-nitrogen coordination small molecules, not only can the mechanical properties of the material be improved, but also the material can be given excellent dynamic reversible properties, thereby showing greater potential in self-repair, sustainable development and green manufacturing. In this way, the limitations of existing polymer materials in durability, repair ability and environmental friendliness can be effectively solved, while promoting polymer science to develop in a more efficient and environmentally friendly direction. Summary of the invention

[0005] In view of this, in order to solve the above-mentioned shortcomings of epoxy resins and phenolic resins that are difficult to repair and recycle, which limits their further application in certain fields, the present invention provides a hydrated borate small molecule with a boron-nitrogen coordination bond and a derivative resin material and a preparation method thereof. The hydrated borate small molecule with a boron-nitrogen coordination bond is bonded by a boron-nitrogen coordination bond and can be used in a derivative resin material of epoxy resin and phenolic resin materials.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] A hydrated borate ester small molecule having a boron-nitrogen coordination bond, the small molecule chemical structure general formula is:

[0008]

[0009] The synthetic route is:

[0010]

[0011] Among them, R 1 is a substituent selected from any one of the electron donating groups such as hydrogen (-H), ortho-hydroxyl (m-OH), para-hydroxyl (p-OH), ortho-amino (m-NH2) and para-amino (p-NH2), R 2 It represents a substituent, which is a carbon chain or carbon chains of different lengths terminated with amino (-NH2), hydroxyl (-OH), alkenyl, alkynyl, carboxyl or the like, and n represents a plurality of borate ester groups coordinated with boron and nitrogen.

[0012] Furthermore, boric acid and its derivatives are dissolved and reacted with multifunctional amine compounds at room temperature through a solution reaction to form a boron-nitrogen coordinated small molecule NCBW-X, wherein NCBW-X has an eight-membered ring structure, wherein the boron-nitrogen coordination causes the eight-membered ring to split into a five-membered ring, so that its rigid eight-membered ring can exist stably.

[0013] In the hydrated borate ester small molecule having a boron-nitrogen coordination bond,

[0014] 1) The general chemical structure formula of boric acid and its derivatives is as follows:

[0015]

[0016] Where R 1 It is represented by a substituent, selected from any one of the electron donating groups such as hydrogen (-H), ortho-hydroxyl (m-OH), para-hydroxyl (p-OH), ortho-amino (m-NH2) and para-amino (p-NH2), wherein n represents a plurality of boronic acid groups; its main examples are as follows:

[0017]

[0018] 2) The general chemical structure formula of multifunctional amine compounds is as follows:

[0019]

[0020] Where R 2It is represented by a substituent, which is a carbon chain or carbon chains of different lengths terminated by amino (-NH2), hydroxyl (-OH), alkenyl, alkynyl, carboxyl, etc.; its main examples are as follows:

[0021]

[0022] 3) The formed boron-nitrogen coordinated small molecule NCBW-X has the following general chemical structure:

[0023]

[0024] Where R 1 and R 2 The groups represented are the same as 1) and 2), and n represents multiple borate groups containing boron-nitrogen coordination. The main examples are as follows:

[0025]

[0026] Furthermore, when n≥2, the rigid eight-membered ring forms a coordination system when it meets water, thereby improving the hydrolysis resistance of the borate ester; the rigid eight-membered ring in the material will form a stable BO coordination system when it meets water, making it exhibit higher chemical stability under hydrolysis conditions.

[0027] Furthermore, boric acid and its derivatives are all boric acids with aromatic rings (such as benzene ring, biphenyl, thiophene, pyridine, pyrazole, carbazole, etc.), wherein m, p represents -OH or -NH2 located at the ortho or para position of the aromatic ring, and the solvent used for the solution reaction is one of methanol or ethanol, wherein NCBW-X (X = 1, 2, 3...).

[0028] The method for preparing the hydrated borate ester small molecule derivative resin material having a boron-nitrogen coordination bond is characterized by comprising the following steps:

[0029] S1. Synthesis of boron-nitrogen coordinated small molecules: Boric acid and its derivatives are dissolved and reacted with multifunctional amine compounds at room temperature by solution reaction to form a boron-nitrogen coordinated small molecule NCBW-X (X=1, 2, 3...) with an eight-membered ring structure, wherein the boron-nitrogen coordination causes the eight-membered ring to split into two five-membered rings, so that the rigid eight-membered ring can exist stably;

[0030] S2. Synthetic resin material: Under nitrogen protection, the boron-nitrogen coordinated small molecule NCBW-X is mixed with a resin material precursor and an organic solvent in a mass ratio of 1:0.5 to 2:1, the mixture is heated to 70-120°C under vacuum or normal pressure, and stirred to promote the reaction between NCBW-X and the resin material precursor; a curing agent is added, the mass ratio of the curing agent to the resin material precursor is 0.1 to 0.5:1, and stirring is continued at 80-160°C until the reaction is complete; finally, the reaction mixture is poured into a mold, and cured in an oven at 70°C to 120°C for 6-48 hours to obtain a derivative resin material with improved performance.

[0031] Furthermore, the resin material precursor is one of epoxy resin or phenolic resin, the organic solvent is one of dimethyl sulfoxide (DMSO), acetone, formaldehyde or toluene, and when the resin material precursor is epoxy resin, the curing agent is an amine curing agent, and the amine curing agent is one of meta-phenylenediamine, dimethyl aliphatic amine (DMEA), and diethanolamine (DEA); when the resin material precursor is phenolic resin, the curing agent is an anhydride or aldehyde curing agent, and the anhydride curing agent is one of phthalic anhydride (PA) and methyltetrahydrophthalic anhydride (MTHPA), and the aldehyde curing agent is one of melamine-formaldehyde resin and urea-formaldehyde resin.

[0032] Furthermore, the epoxy resin was cured using a hydrated borate small molecule NCBW-X having a boron-nitrogen coordination bond. The specific steps included: under nitrogen protection, 10.2 mmol NCBW-X was weighed and placed in a 50 mL centrifuge tube, 5.0 mL dimethyl sulfoxide (DMSO) was added and mixed evenly at normal pressure, and then 10.2 mmol epoxy resin was added and heated to 80°C, and stirred to promote the reaction between NCBW-X and the epoxy resin; then a curing agent, m-phenylenediamine, was added, and stirring was continued at 100°C until the reaction was complete, and finally the solution was poured into a polytetrafluoroethylene mold, placed in a vacuum oven, heated to 120°C, reacted for 8 hours, and taken out to obtain a cured epoxy resin containing a boron-nitrogen coordination bond.

[0033] Furthermore, a hydrated borate small molecule NCBW-X having a boron-nitrogen coordination bond was used to cure a boron-modified phenolic resin, and the phenolic resin was selected from a resol phenolic resin. The specific steps included: weighing 10.2 mmol of the resol phenolic resin and putting it into a beaker, adding 30 ml of formaldehyde solvent and 10.2 mmol of NCBW-X, heating to 100°C at normal pressure, and stirring to promote the reaction between NCBW-X and the resol phenolic resin; then adding a curing agent urea-formaldehyde resin and stirring and curing at 120°C, and finally pouring the solution into a polytetrafluoroethylene mold, putting it into a vacuum oven, heating it to 120°C, reacting it for 8 hours, and taking it out to obtain a boron-modified phenolic resin containing a boron-nitrogen coordination bond.

[0034] The cured epoxy resin material is prepared by the method for preparing the derivative resin material.

[0035] The boron-modified phenolic resin material is prepared by the method for preparing the derivative resin material.

[0036] The beneficial effects of the present invention are:

[0037] 1. The present invention discloses a hydrated borate ester small molecule with a boron-nitrogen coordination bond. Boric acid and its derivatives are dissolved and reacted with multifunctional amine compounds at room temperature through a solution reaction to form a boron-nitrogen coordination small molecule NCBW-X. When selecting boric acid and its derivatives, boric acid and derivatives with aromatic ring structures are selected, which is conducive to the construction of high-strength small molecules, such as phenylboronic acid, biphenylboronic acid, thiopheneboronic acid, pyridineboronic acid, pyrazoleboronic acid, carbazoleboronic acid, etc. The characteristics of these boric acid derivatives are that the functional groups on the aromatic ring (such as hydroxyl-OH or amino-NH2) are located in the ortho or para position of the ring; the selection of multifunctional amine compounds, such as N,N-di(2-hydroxyethyl)amine derivatives; the nitrogen atom (N) connects two 2-hydroxyethyl (-CH2CH2OH) groups. R 2 Represents a variable substituent, which can be one of the following two forms: a substituent having a (-CH2)m structural unit and a hydroxyl group (-OH) at the terminal; a substituent having a (-CH2)m structural unit and an amino group (-NH2) at the terminal.

[0038] In addition, the boron-nitrogen coordination small molecules of the present invention can not only be used for traditional polymer material modification to improve the mechanical properties and heat resistance of the materials, but also can enhance the durability and safety of the materials by introducing self-repairing functions. This self-repairing function enables the material to restore its original performance under appropriate stimulation after being physically or chemically damaged, which has great economic value and social significance for reducing maintenance costs and extending the life of the material. These characteristics of the boron-nitrogen coordination small molecules enable it to show a wide range of application prospects in multiple fields. In epoxy resins and phenolic resins, boron-nitrogen coordination small molecules are not only used as curing agents, but also provide higher crosslinking density and thermal stability through their unique chemical structure.

[0039] 2. The epoxy resin material composite material disclosed in the present invention uses NCBW-X as a functional additive, and by introducing boron-nitrogen coordination bonds into the epoxy resin matrix, a significant performance improvement of the material is achieved. In the preparation process of the present invention, NCBW-X and epoxy resin form a stable cross-linked network structure through chemical reaction, giving the material excellent mechanical properties and thermal stability. In the present invention, the boron-nitrogen coordination bonds in the NCBW-X small molecules not only provide supramolecular effects, but also form stable physical cross-linking points in the epoxy resin matrix. The formation of this cross-linked structure significantly improves the mechanical strength and modulus of the composite material, especially under high stress conditions, the material exhibits higher tensile strength and fracture toughness. In addition, the dynamic reversibility of the boron-nitrogen coordination bonds enables the material to absorb and disperse energy by breaking and reorganizing the bonds when it is mechanically damaged, thereby greatly improving the impact resistance and fatigue resistance of the material. The epoxy resin composite material in the present invention also exhibits excellent thermal stability and dimensional stability. The introduction of the boron-nitrogen coordination structure helps to reduce the shrinkage of the material during the curing process and reduces the residual stress of the product, thereby significantly improving the durability and dimensional stability of the material in a high temperature environment. This makes the material particularly suitable for application fields such as electronic packaging and structural bonding that work in high temperature and high humidity environments. By adjusting the content of NCBW-X and the ratio of epoxy resin, the present invention can significantly improve the hardness and wear resistance of the material while maintaining the good toughness of the material. In addition, due to the special molecular structure of NCBW-X, the epoxy resin composite material of the present invention also has a significant improvement in chemical stability, showing good tolerance to various chemical reagents, thereby expanding its application range in corrosive environments. In short, the epoxy resin composite material of the present invention effectively solves the deficiencies of traditional epoxy resin materials in mechanical properties and thermal stability by introducing NCBW-X, and has broad application prospects and significant technical advantages. Other advantages, objectives and features of the present invention will be further elaborated in the subsequent description, and will be obvious to those skilled in the art based on the following investigation and research, or can be inspired by the practice of the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the following description.

[0040] 3. The boron-modified phenolic resin composite material disclosed in the present invention effectively enhances the thermal stability and mechanical strength of the phenolic resin by introducing NCBW-X as a boron modifier. Under high temperature conditions, traditional phenolic resins may experience performance degradation, while boron-modified phenolic resins show superior thermal stability and can withstand higher temperatures without significant degradation or failure. In addition, the introduction of the boron element promotes a more complex cross-linking reaction inside the material, thereby improving the overall mechanical strength of the material, enabling it to carry a larger load, and is suitable for application scenarios requiring higher mechanical strength. Secondly, during the preparation process of the present invention, by using formaldehyde solution as a solvent, it is ensured that NCBW-X can be evenly dispersed throughout the phenolic resin matrix. This uniform dispersion is the key to optimizing the performance of the composite material, and it can ensure that each part can equally benefit from the advantages of boron modification, so that the performance of the entire material system is balanced and predictable. In addition, the vacuum curing technology used in the present invention further improves the quality and performance of the composite material. Curing under vacuum conditions can effectively eliminate bubbles and other impurities, which not only improves the appearance and smoothness of the material, but also avoids the internal stress concentration caused by bubbles, thereby improving the structural integrity of the material and the reliability of long-term use. Since boron-modified phenolic resin has better chemical and thermal stability, the application potential of this material in high temperature and corrosive environments is significantly improved, especially in the fields of aviation, aerospace, automobiles and advanced building materials. The development of this new composite material not only provides a new material with superior performance, but also may lead the innovation of material technology in related industries.

[0041] Other advantages, objectives and features of the present invention will be described in the following description to some extent, and to some extent, will be obvious to those skilled in the art based on the following examination and study, or can be taught from the practice of the present invention. The objectives and other advantages of the present invention can be realized and obtained through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be described in detail below in conjunction with the accompanying drawings, wherein:

[0043] Figure 1 The synthetic route of the boron-nitrogen coordinated small molecule in the embodiment of the present invention is shown in FIG.

[0044] Figure 2 The structural formula of the boron-nitrogen coordinated small molecule NCBW-X is shown. Its synthesis method comes from Figure 1 ;

[0045] Figure 3 is the boron-nitrogen coordinated small molecule NCBW-1 in Example 1 of the present invention 1 H-NMR and 13C-NMR spectrum, where Figure 3 (a) is the boron-nitrogen coordinated small molecule NCBW-1 1 H-NMR spectrum, Figure 3 (b) is the boron-nitrogen coordinated small molecule NCBW-1 13 C-NMR spectrum;

[0046] Figure 4 is the boron-nitrogen coordinated small molecule NCBW-2 in Example 2 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Figure 4 (a) is the boron-nitrogen coordinated small molecule NCBW-2 1 H-NMR spectrum, Figure 4 (b) is the boron-nitrogen coordinated small molecule NCBW-2 13 C-NMR spectrum;

[0047] Figure 5 is the boron-nitrogen coordinated small molecule NCBW-3 in Example 3 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Figure 5 (a) is the boron-nitrogen coordinated small molecule NCBW-3 1 H-NMR spectrum, Figure 5 (b) is the boron-nitrogen coordinated small molecule NCBW-3 13 C-NMR spectrum;

[0048] Figure 6 is the boron-nitrogen coordinated small molecule NCBW-4 in Example 4 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Figure 6 (a) is the boron-nitrogen coordinated small molecule NCBW-4 1 H-NMR spectrum, Figure 6 (b) is the boron-nitrogen coordinated small molecule NCBW-4 13 C-NMR spectrum;

[0049] Figure 7 is the boron-nitrogen coordinated small molecule NCBW-5 in Example 5 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Figure 7 (a) is the boron-nitrogen coordinated small molecule NCBW-5 1 H-NMR spectrum, Figure 7 (b) is the boron-nitrogen coordinated small molecule NCBW-5 13 C-NMR spectrum;

[0050] Figure 8 is the boron-nitrogen coordinated small molecule NCBW-9 in Example 9 of the present invention1 H-NMR and 13 C-NMR spectrum, where Figure 8 (a) is the boron-nitrogen coordinated small molecule NCBW-9 1 H-NMR spectrum, Figure 8 (b) is the boron-nitrogen coordinated small molecule NCBW-9 13 C-NMR spectrum;

[0051] Fig. 9 is the boron-nitrogen coordinated small molecule NCBW-15 in Example 15 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Fig. 9 (a) is the boron-nitrogen coordinated small molecule NCBW-15 1 H-NMR spectrum, Fig. 9 (b) is the boron-nitrogen coordinated small molecule NCBW-15 13 C-NMR spectrum;

[0052] Fig.10 is the boron-nitrogen coordinated small molecule NCBW-18 in Example 18 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Fig.10 (a) is the boron-nitrogen coordinated small molecule NCBW-18 1 H-NMR spectrum, Fig.10 (b) is the boron-nitrogen coordinated small molecule NCBW-18 13 C-NMR spectrum;

[0053] Fig.11 is the boron-nitrogen coordinated small molecule NCBW-21 in Example 21 of the present invention 1 H-NMR and 13 C-NMR spectrum, where Fig.11 (a) is the boron-nitrogen coordinated small molecule NCBW-21 1 H-NMR spectrum, Fig.11 (b) is the boron-nitrogen coordinated small molecule NCBW-21 13 C-NMR spectrum;

[0054] Fig.12 FTIR graph of the epoxy resin material (E51-NCBW-9) with synergistic effects of hydrogen bonds and coordination bonds in an embodiment of the present invention;

[0055] Fig.13 FTIR graph of the boron-modified phenolic resin material (PF-NCBW-12) in the embodiment of the present invention. DETAILED DESCRIPTION

[0056] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0057] Traditional epoxy resins, phenolic resins and derivative resin materials are widely used in industry and daily life. Due to their excellent mechanical properties, chemical resistance and processing convenience, they have become important materials in many fields. However, with the continuous improvement of the requirements for high-performance materials, the shortcomings of traditional materials in terms of durability, repair ability, sustainability, etc. have gradually become apparent. For example, epoxy resins and phenolic resins are difficult to recycle and reuse due to the high degree of cross-linking of their molecular structures after curing. Once these materials suffer physical or chemical damage, the repair process usually requires additional energy or additives, which significantly increases the cost and process complexity.

[0058] In recent years, the introduction of dynamic chemical bonds has provided a new solution for improving the self-healing ability and recyclability of these polymer materials. Dynamic chemical bonds include reversible covalent bonds and non-covalent bonds, such as hydrogen bonds, coordination bonds, borate bonds, imine bonds, etc. These bonds can be reversibly broken and reorganized under external stimuli, thus playing a key role in the repair and recycling of materials. In particular, boron-nitrogen coordination bonds have become an ideal choice for constructing dynamic polymer networks due to their unique reversibility and regulation capabilities.

[0059] Boric acid ester small molecules are a special type of compound that is generated by the reaction of boronic acid groups and multifunctional amine compounds. These small molecules can form stable boron-nitrogen coordination bonds with nitrogen-containing compounds (such as amines, amides, etc.). This coordination bond is reversible and can break and reform when subjected to specific stimuli (such as heat, chemical, mechanical action, etc.). Therefore, the boron-nitrogen coordination bond can not only improve the mechanical properties of the material, but also give it dynamic reversibility, allowing the material to self-repair when damaged and have the potential for multiple cycles.

[0060] The present invention aims to improve the mechanical strength, self-repairing ability and environmental adaptability of epoxy resin and phenolic resin materials and derivative resin materials by synthesizing small molecules containing boron and nitrogen coordination (i.e., NCBW-X) and applying them to these materials. By introducing boron and nitrogen coordination bonds, the material of the present invention has excellent mechanical properties, such as high tensile strength, high elongation at break and good tear resistance. At the same time, the material can achieve effective self-repair after being damaged through dynamic fracture and recombination of boron and nitrogen bonds. In addition, the material of the present invention exhibits excellent chemical stability in environments such as solvents and has good solvent tolerance.

[0061] Figure 1 The synthetic route of the boron-nitrogen coordinated small molecule in Examples 1 to 45 is shown;

[0062] Figure 2 1 is the structural formula of the boron-nitrogen coordinated small molecule NCBW-X synthesized corresponding to Example 1 to Example 45.

[0063] Embodiment 1

[0064]

[0065] Synthesis of hydrated borate small molecule NCBW-1 containing boron-nitrogen coordination bonds: 1,4-phenylenediboronic acid (10 g, 0.06 mol) and triethanolamine (17.88 g, 0.12 mol) were dissolved in methanol (about 75 ml) at room temperature. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 1,4-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure gave a white solid product with a yield of 95%, such as Figure 3 shown.

[0066] Embodiment 2

[0067]

[0068] Synthesis of hydrated borate small molecule NCBW-2 containing boron-nitrogen coordination bonds: 1,4-phenylenediboronic acid (10 g, 0.06 mol) and diethanolamine (12.61 g, 0.12 mol) were dissolved in ethanol (about 70 ml) at room temperature. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the ethanol solution of 1,4-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with ethanol two to three times. This procedure obtained a white solid product with a yield of 94%, such as Figure 4 shown.

[0069] Embodiment 3

[0070]

[0071] Synthesis of hydrated borate small molecule NCBW-3 containing boron-nitrogen coordination bonds: 1,4-phenylenediboronic acid (10 g, 0.06 mol) and N-(3-aminopropyl)diethanolamine (19.44 g, 0.12 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 1,4-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained a 96% yield of an off-white solid product, such as Figure 5 shown.

[0072] Embodiment 4

[0073]

[0074] Synthesis of hydrated borate small molecule NCBW-4 containing boron-nitrogen coordination bonds: 1,4-phenylenediboronic acid (10 g, 0.06 mol) and N-ethyldiethanolamine (15.98 g, 0.12 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the solution of N-ethyldiethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 1,4-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained a 96% yield of an off-white solid product, such as Figure 6 shown.

[0075] Embodiment 5

[0076]

[0077] Synthesis of hydrated borate small molecule NCBW-5 containing boron-nitrogen coordination bonds: 1,4-phenylenediboronic acid (10 g, 0.06 mol) and N-butyldiethanolamine (19.34 g, 0.12 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the solution of N-butyldiethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 1,4-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained a 94% yield of an off-white solid product, such as Figure 7 shown.

[0078] Embodiment 6

[0079]

[0080] Synthesis of hydrated borate small molecule NCBW-6 containing boron-nitrogen coordination bonds: 4-aminophenylboronic acid (10 g, 0.07 mol) and triethanolamine (10.44 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50°C. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 4-aminophenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray solid product with a yield of 90%.

[0081] Embodiment 7

[0082]

[0083] Synthesis of hydrated borate small molecule NCBW-7 containing boron-nitrogen coordination bonds: 4-aminophenylboronic acid (10 g, 0.07 mol) and diethanolamine (7.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50°C. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 4-aminophenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 96%.

[0084] Embodiment 8

[0085]

[0086] Synthesis of hydrated borate ester small molecule NCBW-8 containing boron-nitrogen coordination bonds: 4-aminophenylboronic acid (10 g, 0.07 mol) and N-(3-aminopropyl)diethanolamine (11.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50°C. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 4-aminophenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 91%.

[0087] Embodiment 9

[0088]

[0089] Synthesis of hydrated borate small molecule NCBW-9 containing boron-nitrogen coordination bonds: 4-hydroxyphenylboronic acid (10 g, 0.07 mol) and triethanolamine (10.44 g, 0.07 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 4-hydroxyphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained a 96% yield of an off-white solid product, such as Figure 8 shown.

[0090] Embodiment 10

[0091]

[0092] Synthesis of hydrated borate ester small molecule NCBW-10 containing boron-nitrogen coordination bond: 4-hydroxyphenylboronic acid (10 g, 0.07 mol) and diethanolamine (7.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 4-hydroxyphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 91%.

[0093] Embodiment 11

[0094]

[0095] Synthesis of hydrated borate ester small molecule NCBW-11 containing boron-nitrogen coordination bonds: 4-hydroxyphenylboronic acid (10 g, 0.07 mol) and N-(3-aminopropyl)diethanolamine (11.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 4-hydroxyphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes, and no further heating was required. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 91%.

[0096] Embodiment 12

[0097]

[0098] Synthesis of hydrated borate small molecule NCBW-12 containing boron-nitrogen coordination bonds: 3-hydroxyphenylboronic acid (10 g, 0.07 mol) and triethanolamine (10.44 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50 ° C. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-hydroxyphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 96%.

[0099] Embodiment 13

[0100]

[0101] Synthesis of hydrated borate ester small molecule NCBW-13 containing boron-nitrogen coordination bonds: 3-hydroxyphenylboronic acid (10 g, 0.07 mol) and diethanolamine (7.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50°C. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-hydroxyphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 91%.

[0102] Embodiment 14

[0103]

[0104] Synthesis of hydrated borate small molecule NCBW-14 containing boron-nitrogen coordination bonds: 3-hydroxyphenylboronic acid (10 g, 0.07 mol) and N-(3-aminopropyl)diethanolamine (11.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50°C. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. The methanol solution of 3-hydroxyphenylboronic acid was then added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure gave a gray-white solid product with a yield of 91%.

[0105] Embodiment 15

[0106]

[0107] Synthesis of hydrated borate ester small molecule NCBW-15 containing boron-nitrogen coordination bonds: 3-aminophenylboronic acid (10 g, 0.07 mol) and triethanolamine (10.44 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 40°C. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-aminophenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure gave a gray-white solid product with a yield of 92%, such as Fig. 9 shown.

[0108] Embodiment 16

[0109]

[0110] Synthesis of hydrated borate small molecule NCBW-16 containing boron-nitrogen coordination bonds: 3-aminophenylboronic acid (10 g, 0.07 mol) and diethanolamine (7.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 40°C. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-aminophenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 91%.

[0111] Embodiment 17

[0112]

[0113] Synthesis of hydrated borate small molecule NCBW-17 containing boron-nitrogen coordination bonds: 3-aminophenylboronic acid (10 g, 0.07 mol) and N-(3-aminopropyl)diethanolamine (11.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 50°C. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. The methanol solution of 3-aminophenylboronic acid was then added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure gave an off-white solid product with a yield of 88%.

[0114] Embodiment 18

[0115]

[0116] Synthesis of hydrated borate ester small molecule NCBW-18 containing boron-nitrogen coordination bonds: At 40°C, 2,5-diboric acid thiophene (10g, 0.06mol) and triethanolamine (17.90g, 0.12mol) were dissolved in methanol (about 100ml) respectively. Subsequently, the triethanolamine solution was transferred to a 250ml single-necked flask. Then the methanol solution of 2,5-diboric acid thiophene was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained an off-white solid product with a yield of 89%, such as Fig.10 shown.

[0117] Embodiment 19

[0118]

[0119] Synthesis of hydrated borate ester small molecule NCBW-19 containing boron-nitrogen coordination bonds: 2,5-diboronic acid thiophene (10 g, 0.06 mol) and diethanolamine (12.62 g, 0.12 mol) were dissolved in methanol (about 100 ml) at 40 ° C. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 2,5-diboronic acid thiophene was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained an off-white solid product with a yield of 86%.

[0120] Embodiment 20

[0121]

[0122] Synthesis of hydrated borate ester small molecule NCBW-20 containing boron-nitrogen coordination bond: 2,5-diboronic acid thiophene (10 g, 0.06 mol) and N-(3-aminopropyl) diethanolamine (19.47 g, 0.12 mol) were dissolved in methanol (about 100 ml) at 40 ° C. Subsequently, the solution of N-(3-aminopropyl) diethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 2,5-diboronic acid thiophene was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained an off-white solid product with a yield of 88%.

[0123] Embodiment 21

[0124]

[0125] Synthesis of hydrated borate small molecule NCBW-21 containing boron-nitrogen coordination bonds: 4,4'-biphenyldiboronic acid (10g, 0.04mol) and triethanolamine (11.94g, 0.08mol) were dissolved in methanol (about 100ml) at 50°C. Subsequently, the triethanolamine solution was transferred to a 250ml single-necked flask. Then the methanol solution of 4,4'-biphenyldiboronic acid was added dropwise. A white precipitate began to form within 1 minute after the addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with methanol two to three times. This procedure obtained a 93% yield of an off-white solid product, such as Fig.11 shown.

[0126] Embodiment 22

[0127]

[0128] Synthesis of hydrated borate small molecule NCBW-22 containing boron-nitrogen coordination bonds: 4,4'-biphenyldiboronic acid (10g, 0.04mol) and diethanolamine (8.41g, 0.08mol) were dissolved in ethanol (about 100ml) at 50°C. Subsequently, the diethanolamine solution was transferred to a 250ml single-necked flask. Then the methanol solution of 4,4'-biphenyldiboronic acid was added dropwise. A white precipitate began to form within 1 minute after addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with ethanol two to three times. This procedure obtained a gray-white solid product with a yield of 94%.

[0129] Embodiment 23

[0130]

[0131] Synthesis of hydrated borate ester small molecule NCBW-23 containing boron-nitrogen coordination bond: 4,4'-biphenyl diboronic acid (10g, 0.04mol) and N-(3-aminopropyl) diethanolamine (12.98g, 0.08mol) were dissolved in methanol (about 100ml) at 50°C. Subsequently, the solution of N-(3-aminopropyl) diethanolamine was transferred to a 250ml single-necked flask. Then the methanol solution of 4,4'-biphenyl diboronic acid was added dropwise. A white precipitate began to form within 10 minutes after addition. The reaction stopped after 15 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained a gray-white solid product with a yield of 93%.

[0132] Embodiment 24

[0133]

[0134] Synthesis of hydrated borate small molecule NCBW-24 containing boron-nitrogen coordination bonds: 3-hydroxymethylphenylboronic acid (10 g, 0.07 mol) and triethanolamine (10.44 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 60 ° C. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-hydroxymethylphenylboronic acid was added dropwise. A white precipitate began to form within 10 minutes after addition. The reaction stopped after 15 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained an off-white solid product with a yield of 88%.

[0135] Embodiment 25

[0136]

[0137] Synthesis of hydrated borate ester small molecule NCBW-25 containing boron-nitrogen coordination bond: 3-hydroxymethylphenylboronic acid (10 g, 0.07 mol) and diethanolamine (7.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 60 ° C. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-hydroxymethylphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained an off-white solid product with a yield of 83%.

[0138] Embodiment 26

[0139]

[0140] Synthesis of hydrated borate ester small molecule NCBW-26 containing boron-nitrogen coordination bond: 3-hydroxymethylphenylboronic acid (10 g, 0.07 mol) and N-(3-aminopropyl)diethanolamine (11.36 g, 0.07 mol) were dissolved in methanol (about 100 ml) at 60°C. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 3-hydroxymethylphenylboronic acid was added dropwise. A white precipitate began to form within 1 minute after addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure obtained an off-white solid product with a yield of 82%.

[0141] Embodiment 27

[0142]

[0143] Synthesis of hydrated boronate small molecule NCBW-27 containing boron-nitrogen coordination bonds: 1,3-phenylenediboronic acid (10 g, 0.06 mol) and triethanolamine (17.88 g, 0.12 mol) were dissolved in methanol (about 75 ml) at room temperature. Subsequently, the triethanolamine solution was transferred to a 250 ml single-necked flask. Then the methanol solution of 1,3-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure gave a white solid product with a yield of 93%.

[0144] Embodiment 28

[0145]

[0146] Synthesis of hydrated borate ester small molecule NCBW-28 containing boron-nitrogen coordination bond: 1,3-phenylenediboronic acid (10 g, 0.06 mol) and diethanolamine (12.61 g, 0.12 mol) were dissolved in ethanol (about 70 ml) at room temperature. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then the ethanol solution of 1,3-phenylenediboronic acid was added dropwise. A white precipitate began to form within 1 minute after addition. The reaction stopped after 5 minutes without further heating. Finally, the precipitate was filtered and washed with ethanol two to three times. This procedure obtained a white solid product with a yield of 92%.

[0147] Embodiment 29

[0148]

[0149] Synthesis of the hydrated boronate ester small molecule NCBW-29 containing a boron-nitrogen coordination bond: 1,3-phenylenediboronic acid (10 g, 0.06 mol) and N-(3-aminopropyl)diethanolamine (19.44 g, 0.12 mol) were dissolved in methanol (about 100 ml) at room temperature. Subsequently, the solution of N-(3-aminopropyl)diethanolamine was transferred to a 250 ml single-necked flask. Then the methanol solution of 1,3-phenylenediboronic acid was added dropwise. A white precipitate began to form within 5 minutes after the addition. The reaction stopped after 15 minutes without further heating. Finally, the precipitate was filtered and washed two to three times with methanol. This procedure gave a 90% yield of an off-white solid product.

[0150] Embodiment 30

[0151] Accurately weigh 2.56 g of NCBW-9 (10.2 mmol) and transfer it to a 50 ml centrifuge tube, followed by the addition of 5.0 ml of dimethyl sulfoxide (DMSO) as a solvent. Use a glass rod to stir thoroughly to ensure that NCBW-9 is completely dissolved to form a uniform solution. Next, slowly add 2.0 g of E-51 epoxy resin (10.2 mmol) and continue stirring until the mixture is uniform and free of bubbles. Pour the resulting reaction mixture into a pre-prepared polytetrafluoroethylene mold and place the mold in a vacuum oven preheated to 150°C for 5 hours to complete the curing process. Recorded as E51-NCBW-9, as Fig.12 As shown, the peak at 1368 cm-1 corresponds to the stretching vibration of the BO bond, and the vibration of the BN coordination is between 689 and 860 cm-1.

[0152] Embodiment 31

[0153] 2.56 g of NCBW-12 (10.2 mmol) was accurately weighed and transferred to a 100 ml flask. Subsequently, 30 ml of formaldehyde solution was added to the flask and stirred thoroughly with a glass rod to ensure that the NCBW-12 was completely dispersed to form a uniform solution. Next, an equal number of moles of resol phenolic resin was slowly added and stirred continuously until the mixture was uniform and free of bubbles. Thereafter, the mixture was poured into a pre-prepared polytetrafluoroethylene mold and the mold was placed in a vacuum oven preheated to 120 ° C and heated for 5 hours to complete the curing process. It was recorded as PF-NCBW-12, as Fig.13 As shown, the peak at 1100 cm-1 corresponds to the vibration of the CN bond, the peak at 1368 cm-1 corresponds to the stretching vibration of the BO bond, and the vibration of the BN coordination is between 689 and 860 cm-1.

[0154] Comparative Example

[0155]

[0156] Boric acid compounds without conjugated systems cannot form boric acid esters with boron-nitrogen coordination. For example, cyclohexylboronic acid (10 g, 0.078 mol) and diethanolamine (16.4 g, 0.156 mol) were dissolved in ethanol (about 70 ml) at room temperature. Subsequently, the diethanolamine solution was transferred to a 250 ml single-necked flask. Then, the ethanol solution of cyclohexylboronic acid was added dropwise. No reactant was generated after the addition. (Rigid planar structure, aliphatic ring conformation is changeable).

[0157] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution, which should be included in the scope of the claims of the present invention.

Claims

1. A hydrated borate ester small molecule having a boron-nitrogen coordination bond, characterized in that: The general formula of the small molecule chemical structure is: The synthetic route is: Among them, R 1 It is represented by a substituent, selected from any one of the electron donating groups such as hydrogen (-H), ortho-hydroxyl (m-OH), para-hydroxyl (p-OH), ortho-amino (m-NH2) and para-amino (p-NH2), R 2 It represents a substituent, which is a carbon chain or carbon chains of different lengths terminated with an amino group (-NH2), a hydroxyl group (-OH), an alkenyl group, an alkynyl group, or a carboxyl group, and n represents a plurality of borate ester groups coordinated with boron and nitrogen.

2. The hydrated borate ester small molecule having a boron-nitrogen coordination bond according to claim 1, characterized in that: Boric acid and its derivatives are dissolved and reacted with multifunctional amine compounds at room temperature through solution reaction to form a boron-nitrogen coordinated small molecule NCBW-X, wherein NCBW-X has an eight-membered ring structure, wherein the boron-nitrogen coordination causes the eight-membered ring to split into a five-membered ring, so that its rigid eight-membered ring can exist stably.

3. The hydrated borate ester small molecule having a boron-nitrogen coordination bond as claimed in claim 2, characterized in that: When n≥2, the rigid eight-membered ring forms a coordination system when it meets water, which improves the hydrolysis resistance of the borate ester; the rigid eight-membered ring in the material will form a stable BO coordination system when it meets water, making it exhibit higher chemical stability under hydrolysis conditions.

4. The hydrated borate ester small molecule having a boron-nitrogen coordination bond as claimed in claim 3, wherein the boric acid and its derivatives are all boric acids having an aromatic ring, wherein m, p represent -OH or -NH2 located at the ortho or para position of the aromatic ring, and the solvent used for the solution reaction is one of methanol or ethanol, wherein NCBW-X (X=1, 2, 3...).

5. A method for preparing a resin material derived from a hydrated borate ester small molecule having a boron-nitrogen coordination bond according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Synthesis of boron-nitrogen coordinated small molecules: Boric acid and its derivatives are dissolved and reacted with multifunctional amine compounds at room temperature through solution reaction to form a boron-nitrogen coordinated small molecule NCBW-X (X=1, 2, 3...) with an eight-membered ring structure, wherein the boron-nitrogen coordination causes the eight-membered ring to split into two five-membered rings, so that the rigid eight-membered ring can exist stably; S2. Synthetic resin material: Under nitrogen protection, the boron-nitrogen coordinated small molecule NCBW-X is mixed with the resin material precursor molecule and the organic solvent in a mass ratio of 1:0.5~2:1, the mixture is heated to 70-120°C under vacuum or normal pressure, and stirred to promote the reaction between NCBW-X and the resin material precursor; a curing agent is added, and the mass ratio of the curing agent to the resin material precursor is 0.1~0.5:1, and stirring is continued at 80-160°C until the reaction is complete; finally, the reaction mixture is poured into a mold, and cured in an oven at 70°C-120°C for 6-48 hours to obtain a derivative resin material with improved performance.

6. The method for preparing the resin material according to claim 5, characterized in that: The resin material precursor is one of epoxy resin or phenolic resin, the organic solvent is one of dimethyl sulfoxide (DMSO), acetone, formaldehyde or toluene, when the resin material precursor is epoxy resin, the curing agent is an amine curing agent, and the amine curing agent is one of meta-phenylenediamine, dimethyl aliphatic amine (DMEA), and diethanolamine (DEA); when the resin material precursor is phenolic resin, the curing agent is an anhydride or aldehyde curing agent, and the anhydride curing agent is one of phthalic anhydride (PA) and methyltetrahydrophthalic anhydride (MTHPA), and the aldehyde curing agent is one of melamine-formaldehyde resin and urea-formaldehyde resin.

7. The method for preparing a resin material according to claim 6, characterized in that: The epoxy resin was cured using a hydrated borate small molecule NCBW-X having a boron-nitrogen coordination bond. The specific steps included: under nitrogen protection, 10.2 mmol NCBW-X was weighed and placed in a 50 mL centrifuge tube, 5.0 mL dimethyl sulfoxide (DMSO) was added and mixed evenly at normal pressure, and then 10.2 mmol epoxy resin was added and heated to 80°C, and stirred to promote the reaction between NCBW-X and the epoxy resin; then a curing agent, m-phenylenediamine, was added, and stirring was continued at 100°C until the reaction was complete. Finally, the solution was poured into a polytetrafluoroethylene mold, placed in a vacuum oven, heated to 120°C, reacted for 8 h, and then taken out to obtain a cured epoxy resin containing a boron-nitrogen coordination bond.

8. The method for preparing a resin material according to claim 6, characterized in that: The boron-modified phenolic resin is cured using a hydrated borate ester small molecule NCBW-X having a boron-nitrogen coordination bond. The phenolic resin is a resol phenolic resin. The specific steps include: weighing 10.2 mmol of the resol phenolic resin and putting it into a beaker, adding 30 ml of formaldehyde solvent and 10.2 mmol of NCBW-X, heating to 100°C at normal pressure, and stirring to promote the reaction between NCBW-X and the resol phenolic resin; then adding a curing agent urea-formaldehyde resin and stirring and curing at 120°C, finally pouring the solution into a polytetrafluoroethylene mold, putting it into a vacuum oven, heating it to 120°C, reacting it for 8 hours, and taking it out to obtain a boron-modified phenolic resin containing a boron-nitrogen coordination bond.

9. A cured epoxy resin material prepared by the method for preparing a resin material according to claim 7.

10. The boron-modified phenolic resin material prepared by the method for preparing the resin material according to claim 8.

Images