Intrinsic flame-retardant / antibacterial organic phosphine modified unsaturated resin and preparation method thereof

Abstract

The invention relates to intrinsic flame-retardant / antibacterial organic phosphine modified unsaturated resin and a preparation method thereof. The organic phosphine modified unsaturated resin is a cured product which is formed by carrying out ring opening polymerization on phosphorus-containing unsaturated resin and polyfunctional epoxy resin and has a cross-linked structure, and has good flame-retardant and antibacterial properties.

Description

Technical Field

[0001] This application relates to the field of flame retardant / antibacterial materials, and particularly to an intrinsically flame retardant / antibacterial organophosphorus-modified unsaturated resin and a preparation method thereof. Background Art

[0002] The microbial system is complex, and in particular, some harmful microorganisms pose a great threat to human health. Every year, countless people and animals die from infectious diseases caused by bacterial, viral, and fungal infections. Phosphorus and nitrogen belong to the same main group and have some similar properties. Compared with nitrogen atoms, phosphorus has a larger atomic radius and a lower electronegativity. Therefore, quaternary phosphonium salts exhibit weak association, which is conducive to the attachment of quaternary phosphonium salt groups to the phospholipid bilayer of microorganisms through electrostatic interaction, destroying its structure, resulting in the leakage of cell contents, and thus inhibiting the growth and reproduction of microorganisms. In addition, antibacterial materials containing quaternary phosphonium salt structures have broad antibacterial spectrum and high antibacterial efficiency, and generally show excellent antibacterial properties, with great development potential in the field of cationic antibacterial.

[0003] The biggest drawback of epoxy resin is its flammability. In order to improve the flame retardancy of epoxy resin, the most widely used industrial method is to use halogen-containing flame retardant epoxy resin. However, when using halogen-based flame retardants, people have found that it has serious problems: it will seriously reduce the ultraviolet stability of the flame-retarded substrate, and produce more smoke, corrosive gases, and toxic gases during combustion. Due to environmental protection issues, the use of halogen-based flame retardants has been restricted to varying degrees, and halogen-free epoxy resin has become the main trend in the development and application of epoxy resin. Summary of the Invention

[0004] On the one hand, this application provides an organophosphorus-modified unsaturated resin, which has good flame retardant performance and antibacterial performance.

[0005] The organophosphorus-modified unsaturated resin provided by this application is a cured product with a cross-linked structure formed by ring-opening polymerization of a phosphorus-containing unsaturated resin and a polyfunctional epoxy resin.

[0006] In one embodiment, the polyfunctional epoxy resin is any one or several of bisphenol A epoxy resin, phenolic epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, triglycidyl p-aminophenol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, triglycidyl m-aminophenol, and triglycidyl aminomesitylene.

[0007] In one embodiment, the molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the epoxy group of the polyfunctional epoxy resin is 1:(1 - 1.2).

[0008] In one embodiment, the phosphorus-containing unsaturated resin is obtained by reacting an unsaturated resin with an organophosphorus compound, and the molar ratio of the unsaturated resin to the organophosphorus compound is 1:(2 - 5).

[0009] Another aspect of the present application provides a method for preparing an organophosphorus-modified unsaturated resin, comprising: Under an inert atmosphere, reacting the unsaturated resin in a first solvent with an organophosphorus compound at 40 - 80 °C, and precipitating the reaction product to obtain a phosphorus-containing unsaturated resin; Mixing the phosphorus-containing unsaturated resin with a polyfunctional epoxy resin, and then curing to obtain an organophosphorus-modified unsaturated resin.

[0010] In one embodiment, the molar ratio of the unsaturated resin to the organophosphorus compound is 1:(2 - 5).

[0011] In one embodiment, the molar ratio of the phosphorus groups of the phosphorus-containing unsaturated resin to the epoxy groups of the polyfunctional epoxy resin is 1:(1 - 1.2).

[0012] In one embodiment, the polyfunctional epoxy resin is any one or more of bisphenol A epoxy resin, phenolic epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, triglycidyl p-aminophenol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, triglycidyl m-aminophenol, and triglycidyl aminomesitol.

[0013] In one embodiment, the first solvent is any one or more of chloroform, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0014] In one embodiment, the curing is carried out at 40 - 80 °C for 1 - 24 h, then at 60 - 100 °C for 1 - 12 h, and finally at 80 - 120 °C for 1 - 6 h.

[0015] The organophosphorus-modified unsaturated resin provided by the present application has good flame retardancy and antibacterial properties. Description of the Drawings

[0016] Figure 1 Shows the nuclear magnetic resonance hydrogen spectrum of the unsaturated resin prepared in Example 1.

[0017] Figure 2 Shows the nuclear magnetic resonance hydrogen spectrum of the phosphorus-containing unsaturated resin prepared in Example 1.

[0018] Figure 3(a) shows a physical picture of the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin prepared in Example 1; Figure 3(b) shows a physical picture of the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin prepared in Example 2.

[0019] Figure 4(a) shows the antibacterial ability results of the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin prepared in Example 1 against Staphylococcus aureus; Figure 4(b) shows the antibacterial ability results of the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin prepared in Example 2 against Staphylococcus aureus. Detailed implementation manners

[0020] On the one hand, the present application provides an organophosphorus-modified unsaturated resin, which has good flame-retardant performance and antibacterial performance.

[0021] The organophosphorus-modified unsaturated resin provided by the present application is a cured product with a crosslinked structure formed by ring-opening polymerization of a phosphorus-containing unsaturated resin and a polyfunctional epoxy resin.

[0022] The unsaturated resin contains hydroxyl groups and unsaturated double bonds, and can be modified by some functional groups, thereby obtaining some performance improvements. Phosphorus is an element that is easy to form compounds, and the P-O-C bond or P-C bond has good stability. The phosphorus-based flame-retardant system can increase the carbonization rate of materials, especially oxygen-containing polymers during combustion. The obtained carbon layer can resist oxidation. At the same time, since phosphoric acid can cover the carbon layer, it can prevent ignition. Organophosphorus compounds can undergo an addition reaction with vinyl groups and be introduced into the system, improving the flame-retardant performance. By introducing a quaternary phosphonium salt structure into the system, the antibacterial performance is improved.

[0023] In one embodiment, the polyfunctional epoxy resin is any one or any combination of bisphenol A epoxy resin, phenolic epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, triglycidyl p-aminophenol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, triglycidyl m-aminophenol, and triglycidyl aminometacresol.

[0024] In one embodiment, the molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the epoxy group of the polyfunctional epoxy resin is 1:(1 - 1.2).

[0025] In one embodiment, the phosphorus-containing unsaturated resin is obtained by reacting an unsaturated resin with an organophosphorus compound, and the molar ratio of the unsaturated resin to the organophosphorus compound is 1:(2 - 5).

[0026] Another aspect of the present application provides a method for preparing an organophosphorus-modified unsaturated resin, comprising: Under an inert atmosphere, reacting an unsaturated resin in a first solvent with an organophosphorus compound at 40 - 80 °C, precipitating the reaction product to obtain a phosphorus-containing unsaturated resin; Mixing the phosphorus-containing unsaturated resin with a polyfunctional epoxy resin, and then curing to obtain an organophosphorus-modified unsaturated resin.

[0027] In one embodiment, the molar ratio of the unsaturated resin to the organophosphorus compound is 1:(2 - 5).

[0028] In one embodiment, the molar ratio of the phosphorus groups of the phosphorus-containing unsaturated resin to the epoxy groups of the polyfunctional epoxy resin is 1:(1 - 1.2).

[0029] In one embodiment, the polyfunctional epoxy resin is any one or several of bisphenol A epoxy resin, phenolic epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6 - hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, triglycidyl p - aminophenol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, triglycidyl m - aminophenol, and triglycidyl amino - m - cresol.

[0030] In one embodiment, the first solvent is any one or several of chloroform, dichloromethane, tetrahydrofuran, N,N - dimethylformamide, N,N - dimethylacetamide, and dimethyl sulfoxide.

[0031] In one embodiment, the curing is carried out by maintaining at 40 - 80 °C for 1 - 24 h, then at 60 - 100 °C for 1 - 12 h, and finally at 80 - 120 °C for 1 - 6 h.

[0032] In one embodiment, the unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 70 - 110 °C in the presence of an inhibitor under an inert atmosphere until the acid value is less than 10 mg KOH / g.

[0033] In one embodiment, the molar ratio of the epoxy resin to the acrylic acid is 1:(2 - 5).

[0034] In one embodiment, the epoxy resin is any one or several of bisphenol A epoxy resin, phenolic epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6 - hexanediol diglycidyl ether, and ethylene glycol diglycidyl ether.

[0035] In one embodiment, the inhibitor is any one or several of hydroquinone, 4-methoxyphenol, 2,5-dimethylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0036] In one embodiment, the organophosphorus compound is diphenylphosphine. Diphenylphosphine is an organophosphorus reagent that can undergo an addition reaction with vinyl groups and is introduced into the system to improve the flame retardancy of the material.

[0037] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the protection scope of the present invention.

[0038] In the following examples, the experimental methods are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.

[0039] Example 1 Under a nitrogen atmosphere, epoxy resin E51 (10 g) and acrylic acid (3.7 g) were reacted in the presence of the inhibitor hydroquinone (0.014 g). The reaction temperature was 70 °C, and the acid value was sampled and tracked during the reaction. The reaction was stopped when the acid value was less than 10 mg KOH / g. Chloroform was added to completely dissolve the product, and the reaction solution was washed with alkali and vacuum-evaporated to remove the solvent and water therein, obtaining the product unsaturated resin. Figure 1 The nuclear magnetic resonance hydrogen spectrum of the unsaturated resin is shown; Under a nitrogen atmosphere, the unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.37 g). The reaction temperature was 40 °C and maintained for 24 h. After the reaction, precipitation was carried out with anhydrous ether, and the lower-layer precipitate was collected. Then, the precipitate was vacuum-dried at 30 °C to obtain the phosphorus-containing unsaturated resin in solid form. Figure 2 The nuclear magnetic resonance hydrogen spectrum of the phosphorus-containing unsaturated resin is shown; After mixing the phosphorus-containing unsaturated resin (0.46 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold, vacuum-degassed, and gradually heated for curing and molding. The curing process was to maintain at 40 °C for 24 h, then at 60 °C for 12 h, and finally at 80 °C for 6 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0040] Example 2 In a nitrogen atmosphere, epoxy resin E51 (10 g) and acrylic acid (9.2 g) were reacted in the presence of the inhibitor hydroquinone (0.19 g). The reaction temperature was 110 °C. During the reaction, samples were taken to track the acid value. The reaction was stopped when the acid value was less than 10 mg KOH / g. Chloroform was added to completely dissolve the product, and the reaction solution was washed with alkali and vacuum-evaporated to remove the solvent and water therein, obtaining the product unsaturated resin; In a nitrogen atmosphere, the unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.93 g). The reaction temperature was 80 °C and it was maintained for 1 h. After the reaction was completed, precipitation was carried out with anhydrous ether, the lower-layer precipitate was collected, and then the precipitate was vacuum-dried at 30 °C to obtain the phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.46 g) and triglycidyl-p-aminophenol (0.18 g) evenly, it was transferred to a mold, vacuum-degassed, and gradually heated for curing and molding. The curing process was to maintain at 80 °C for 1 h, then at 100 °C for 1 h, and finally at 120 °C for 1 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0041] Example 3 In a nitrogen atmosphere, epoxy resin E51 (10 g) and acrylic acid (4.4 g) were reacted in the presence of the inhibitor 4-methoxyphenol (0.072 g). The reaction temperature was 110 °C. During the reaction, samples were taken to track the acid value. The reaction was stopped when the acid value was less than 10 mg KOH / g. Chloroform was added to completely dissolve the product, and the reaction solution was washed with alkali and vacuum-evaporated to remove the solvent and water therein, obtaining the product unsaturated resin; In a nitrogen atmosphere, the unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g). The reaction temperature was 40 °C and it was maintained for 24 h. After the reaction was completed, precipitation was carried out with anhydrous ether, the lower-layer precipitate was collected, and then the precipitate was vacuum-dried at 30 °C to obtain the phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.46 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold, vacuum-degassed, and then gradually heated for curing and molding. The curing process was to maintain at 40 °C for 24 h, then at 60 °C for 12 h, and finally at 80 °C for 6 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0042] Example 4 In a nitrogen atmosphere, epoxy resin E51 (10 g) and acrylic acid (4.4 g) were reacted in the presence of the inhibitor hydroquinone (0.072 g) at a reaction temperature of 70 °C. During the reaction process, samples were taken to track the acid value. When the acid value was less than 10 mg KOH / g, the reaction was stopped. Dichloromethane was added to completely dissolve the product, and the reaction solution was subjected to alkali washing and vacuum evaporation to remove the solvent and water therein, obtaining the product unsaturated resin; In a nitrogen atmosphere, the unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at a reaction temperature of 40 °C for 24 h. After the reaction was completed, precipitation was carried out with anhydrous ether, the lower-layer precipitate was collected, and then the precipitate was dried in vacuo at 30 °C to obtain the phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.46 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold. After vacuum degassing, the temperature was gradually increased for curing and molding. The curing process was to hold at 40 °C for 24 h, then hold at 60 °C for 12 h, and finally hold at 80 °C for 6 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0043] Example 5 In a nitrogen atmosphere, epoxy resin E51 (10 g) and acrylic acid (4.4 g) were reacted in the presence of the inhibitor hydroquinone (0.072 g) at a reaction temperature of 70 °C. During the reaction process, samples were taken to track the acid value. When the acid value was less than 10 mg KOH / g, the reaction was stopped. Toluene was added and heated to completely dissolve the product, and the reaction solution was subjected to alkali washing and vacuum evaporation to remove the solvent and water therein, obtaining the product unsaturated resin; In a nitrogen atmosphere, the unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at a reaction temperature of 40 °C for 24 h. After the reaction was completed, precipitation was carried out with anhydrous ether, the lower-layer precipitate was collected, and then the precipitate was dried in vacuo at 30 °C to obtain the phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.46 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold. After vacuum degassing, the temperature was gradually increased for curing and molding. The curing process was to hold at 40 °C for 24 h, then hold at 60 °C for 12 h, and finally hold at 80 °C for 6 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0044] Example 6 In a nitrogen atmosphere, epoxy resin E51 (10 g) and acrylic acid (4.4 g) were reacted in the presence of inhibitor hydroquinone (0.072 g). The reaction temperature was 70 °C. During the reaction, samples were taken to track the acid value. When the acid value was less than 10 mg KOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was washed with alkali and vacuum-evaporated to remove the solvent and water therein, obtaining the product unsaturated resin; In a nitrogen atmosphere, unsaturated resin (0.54 g) in tetrahydrofuran (10 mL) and diphenylphosphine (0.47 g) were reacted. The reaction temperature was 40 °C and maintained for 24 h. After the reaction, precipitation was carried out with anhydrous ether, and the lower-layer precipitate was collected. Then the precipitate was vacuum-dried at 50 °C to obtain the phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.46 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold. After vacuum degassing, the temperature was gradually increased for curing and molding. The curing process was to maintain at 40 °C for 24 h, then at 60 °C for 12 h, and finally at 80 °C for 6 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0045] Example 7 In a nitrogen atmosphere, bisphenol A diglycidyl ether (10 g) and acrylic acid (4.4 g) were reacted in the presence of inhibitor hydroquinone (0.072 g). The reaction temperature was 110 °C. During the reaction, samples were taken to track the acid value. When the acid value was less than 10 mg KOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was washed with alkali and vacuum-evaporated to remove the solvent and water therein, obtaining the product unsaturated resin; In a nitrogen atmosphere, unsaturated resin (0.48 g) in chloroform (10 mL) and diphenylphosphine (0.47 g) were reacted. The reaction temperature was 40 °C and maintained for 24 h. After the reaction, precipitation was carried out with anhydrous ether, and the lower-layer precipitate was collected. Then the precipitate was vacuum-dried at 30 °C to obtain the phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.43 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold. After vacuum degassing, the temperature was gradually increased for curing and molding. The curing process was to maintain at 40 °C for 24 h, then at 60 °C for 12 h, and finally at 80 °C for 6 h. After cooling to room temperature, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0046] Example 8 In a nitrogen atmosphere, bisphenol F diglycidyl ether (8.0 g) and acrylic acid (4.4 g) were reacted in the presence of the polymerization inhibitor hydroquinone (0.062 g). The reaction temperature was 110 °C. During the reaction, samples were taken to track the acid value. When the acid value was less than 10 mg KOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product, and the reaction solution was washed with alkali and vacuum-evaporated to remove the solvent and water therein, obtaining an unsaturated resin product; In a nitrogen atmosphere, the unsaturated resin (0.46 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g). The reaction temperature was 40 °C and it was maintained for 24 h. After the reaction was completed, precipitation was carried out with anhydrous ether, the lower-layer precipitate was collected, and then the precipitate was vacuum-dried at 30 °C to obtain a phosphorus-containing unsaturated resin in solid form; After mixing the phosphorus-containing unsaturated resin (0.41 g) and glycerol triglycidyl ether (0.17 g) evenly, it was transferred to a mold. After vacuum degassing, the temperature was gradually raised for curing and molding. The curing process was to maintain at 40 °C for 24 h, then at 60 °C for 12 h, and finally at 80 °C for 6 h. After cooling to room temperature, an intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin was obtained.

[0047] Flame retardancy test To verify the flame retardancy, the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resins prepared in Examples 1-8 were subjected to UL-94 tests.

[0048] Table 1

[0049] Note: Definition of V-0 level: When the material is exposed to a flame for 10 seconds twice, and the combustion time each time does not exceed 10 seconds, the total combustion time does not exceed 50 seconds, and there is no burning material dripping or the dripping material cannot ignite absorbent cotton during the test.

[0050] From the test results in Table 1, it can be seen that the UL-94 of the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resins prepared in Examples 1-8 are all V-0.

[0051] Antibacterial property test The antibacterial ability was evaluated by the live / dead bacteria fluorescence staining method, and Staphylococcus aureus was selected as the test strain. The bacterial solution was spread on an agar plate and incubated overnight at 37°C. Subsequently, a single colony was picked and inoculated into 40 ml of LB liquid medium, and incubated at 37°C for 8 - 12 h at a rotation speed of 200 rpm. Then the LB liquid medium was diluted to an appropriate bacterial concentration (OD = ~0.1 at an ultraviolet wavelength of 600 nm). The solidified sample was first soaked in PBS buffer solution and sterilized by irradiating with an ultraviolet lamp for a period of time. Then the solidified sample was placed into a 12-well plate containing 3 ml of bacterial solution and incubated at 37°C for 12 h. Finally, all samples were rinsed with PBS buffer to remove the non-adherent bacteria. The bacteria adhered to the sample surface were stained by dropping the diluted Live / Dead BackLight kit (ThermoFisher Scientific Inc., NY), and the staining of live and dead bacteria was observed with an inverted fluorescence microscope.

[0052] The number of live bacteria is denoted as N L , and the number of dead bacteria is denoted as N D , and the antibacterial ability R A is expressed according to the following formula.

[0053]

[0054] Figures 4(a) and 4(b) respectively show the antibacterial ability results of the intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resin prepared in Example 1 and Example 2 against Staphylococcus aureus. The light spots in the figures are the number of live bacteria, and the test shows that the antibacterial rates are 92.0% and 93.3% in sequence.

[0055] The intrinsically flame-retardant / antibacterial organophosphorus-modified unsaturated resins prepared in Examples 1 - 8 all have obvious antibacterial ability.

[0056] It should be noted that the technical solutions or technical features described in the above embodiments can be combined or supplemented with each other without conflict. The scope of protection of this application is not limited to the precise structures described in the above embodiments and shown in the drawings; all modifications, equivalent replacements, improvements, etc. made within the spirit and principle of this application shall be included within the scope of protection of this application.

Claims

1. An organic phosphine-modified unsaturated resin, characterized in that: The organic phosphine-modified unsaturated resin is a cured product with a cross-linked structure formed by ring-opening polymerization of a phosphorus-containing unsaturated resin and a multifunctional epoxy resin.

2. The organic phosphine-modified unsaturated resin according to claim 1, characterized in that: The multifunctional epoxy resin is any one or more of bisphenol A epoxy resin, novolac epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, triglycidyl p-aminophenol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, triglycidyl m-aminophenol, and triglycidyl amino m-cresol.

3. The organic phosphine-modified unsaturated resin according to claim 1, characterized in that: The molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the epoxy group of the multifunctional epoxy resin is 1:(1-1.2).

4. The organic phosphine-modified unsaturated resin according to claim 1, characterized in that: The phosphorus-containing unsaturated resin is obtained by reacting an unsaturated resin with an organic phosphine compound, and the molar ratio of the unsaturated resin to the organic phosphine compound is 1:(2-5).

5. A method for preparing an organic phosphine-modified unsaturated resin, comprising: Under an inert atmosphere, reacting the unsaturated resin in the first solvent with the organic phosphine compound at 40-80° C., precipitating the reaction product to obtain a phosphorus-containing unsaturated resin; The phosphorus-containing unsaturated resin is mixed with a multifunctional epoxy resin and then cured to obtain an organic phosphine-modified unsaturated resin.

6. The method according to claim 5, characterized in that The molar ratio of the unsaturated resin to the organic phosphine compound is 1:(2-5).

7. The method according to claim 5, characterized in that The molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the epoxy group of the multifunctional epoxy resin is 1:(1-1.2).

8. The method according to claim 5, characterized in that The multifunctional epoxy resin is any one or more of bisphenol A epoxy resin, novolac epoxy resin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, triglycidyl p-aminophenol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, triglycidyl m-aminophenol, and triglycidyl amino m-cresol.

9. The method according to claim 5, characterized in that The first solvent is any one or any combination of chloroform, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

10. The method according to claim 5, characterized in that The curing is carried out at 40-80°C for 1-24h, then at 60-100°C for 1-12h, and finally at 80-120°C for 1-6h.

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