A solidified material of phosphonium-modified styrene-based unsaturated resin and a preparation method thereof

Abstract

The present application relates to a cured product of a phosphonium-modified styrene-based unsaturated resin and a preparation method thereof. The cured product is a cross-linked polymer of a phosphonium-modified styrene-based unsaturated resin and a free radical polymerization monomer; wherein the phosphonium-modified styrene-based unsaturated resin is obtained by a quaternary phosphonium reaction between a phosphorus-containing unsaturated resin and 4-vinylbenzyl halide. The cured product has good flame retardant properties.

Description

Technical Field

[0001] The present application relates to the field of flame retardant materials, and in particular to a cured product of a phosphonium-modified styrene-based unsaturated resin and a preparation method thereof. Background Art

[0002] As a high-strength thermosetting resin, epoxy resin has excellent bonding properties, wear resistance, mechanical properties, electrical insulation properties, chemical stability, high and low temperature resistance, low shrinkage, easy processing and low cost, etc. It has been widely used in adhesives, electronic instruments, aerospace, coatings, electronic and electrical insulation materials, and advanced composite materials. After curing, epoxy resin has a high cross-linking density, large internal stress, brittleness, poor impact resistance, crack resistance, and poor moisture and heat resistance, which greatly limits its application in certain technical fields. Therefore, it is very necessary to study the modification of epoxy resin.

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

[0004] On one hand, the present application provides a cured product of a phosphonium-modified styrene-based unsaturated resin, which has good flame retardant and antibacterial properties.

[0005] The cured product of the phosphonium-modified styrene-based unsaturated resin provided in the present application is a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and a free radical polymerization monomer; wherein the phosphonium-modified styrene-based unsaturated resin is obtained by a quaternary phosphonium reaction between a phosphorus-containing unsaturated resin and 4-vinylbenzyl halide.

[0006] In one embodiment, the free radical polymerization monomer is any one or more of styrene, N-vinyl pyrrolidone, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile.

[0007] In one embodiment, the 4-vinylbenzyl halide is 4-vinylbenzyl chloride and 4-vinylbenzyl bromide.

[0008] In one embodiment, the mass ratio of the phosphonium styrene-modified unsaturated resin to the free radical polymerization monomer is 1:(1-3).

[0009] In another aspect, the present application provides a method for preparing a cured product of a phosphonium-modified styrene-based unsaturated resin, comprising:

[0010] The phosphorus-containing unsaturated resin in the first solvent is reacted with 4-vinylbenzyl halide at 60-120° C. to precipitate the reaction product to obtain a phosphonium-modified styrene-based unsaturated resin;

[0011] The phosphonium-modified styrene-based unsaturated resin, free radical polymerization monomer and initiator are mixed and cured to obtain a cured product of the phosphonium-modified styrene-based unsaturated resin.

[0012] In one embodiment, the molar ratio of the phosphine groups of the phosphorus-containing unsaturated resin to the halobenzyl groups of 4-vinylbenzyl halide is 1:(1-3).

[0013] In one embodiment, the 4-vinylbenzyl halide is 4-vinylbenzyl chloride and 4-vinylbenzyl bromide.

[0014] In one embodiment, the free radical polymerization monomer is any one or more of styrene, N-vinyl pyrrolidone, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile.

[0015] In one embodiment, the first solvent is any one or more of chloroform, tetrahydrofuran, 4-methyltetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0016] In one embodiment, the initiator is any one or more of azobisisobutyronitrile, azobisisoheptanenitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide paste, dibenzoyl peroxide, diisopropylbenzene peroxide, benzoin dimethyl ether, benzoin diethyl ether, diacetophenone, benzoin derivatives, benzyl ketal derivatives, α-hydroxyalkyl phenones, α-aminoalkyl phenones, acylphosphine oxides, esterified oxime ketone compounds, aromatic peroxyester compounds, dialkoxyacetophenones, phenylacetoacetate or diacetophenones.

[0017] The cured product of the phosphonium-modified styrene-based unsaturated resin of the present application has good flame retardant and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the unsaturated resin prepared in Example 1 is shown.

[0019] Figure 2The hydrogen nuclear magnetic resonance spectrum of the phosphorus-containing unsaturated resin prepared in Example 1 is shown.

[0020] Figure 3 The hydrogen nuclear magnetic resonance spectrum of the phosphonium-modified styrene-based unsaturated resin prepared in Example 1 is shown.

[0021] Figure 4 The physical picture of the cross-linked polymer of phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate prepared in Example 1 is shown. DETAILED DESCRIPTION

[0022] On one hand, the present application provides a cured product of a phosphonium-modified styrene-based unsaturated resin, which has good flame retardant and antibacterial properties.

[0023] The cured product of the phosphonium-modified styrene-based unsaturated resin provided in the present application is a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and a free radical polymerization monomer; wherein the phosphonium-modified styrene-based unsaturated resin is obtained by a quaternary phosphonium reaction between a phosphorus-containing unsaturated resin and 4-vinylbenzyl halide.

[0024] Phosphorus is an element that can easily form compounds. The POC bond or PC bond has good stability. The phosphorus-based flame retardant system can increase the carbonization rate of materials, especially oxygen-containing polymers, during combustion. The resulting carbon layer can resist oxidation. At the same time, since phosphoric acid can cover the carbon layer, it can prevent ignition.

[0025] The world of microorganisms is complex and diverse, and there are many harmful species that pose a serious threat to human health. Every year, countless people and animals lose their lives due to infectious diseases caused by microorganisms such as bacteria, viruses and fungi. Phosphorus and nitrogen belong to the same main group of the periodic table, and they share several similar properties. Compared with nitrogen atoms, phosphorus atoms have a larger radius and lower electronegativity, which makes quaternary phosphonium salts exhibit weaker association ability. This characteristic promotes the quaternary phosphonium salt group to attach to the phospholipid bilayer membrane of microorganisms by electrostatic attraction, thereby destroying its structural integrity, causing the leakage of intracellular substances, and effectively inhibiting the growth and replication of microorganisms. Quaternary phosphonium esters are lipid compounds containing quaternary phosphonium groups. The quaternary phosphonium salt structure in the material can give the material a broad-spectrum antibacterial activity, and the ester bond can give the material better hydrolysis performance. This composite property can play an important role in the field of biodegradability.

[0026] In one embodiment, the free radical polymerization monomer is any one or more of styrene, N-vinyl pyrrolidone, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile.

[0027] In one embodiment, the 4-vinylbenzyl halide is 4-vinylbenzyl chloride and 4-vinylbenzyl bromide.

[0028] In one embodiment, the mass ratio of the phosphonium styrene-modified unsaturated resin to the free radical polymerization monomer is 1:(1-3).

[0029] In another aspect, the present application provides a method for preparing a cured product of a phosphonium-modified styrene-based unsaturated resin, comprising:

[0030] The phosphorus-containing unsaturated resin in the first solvent is reacted with 4-vinylbenzyl halide at 60-120° C. to precipitate the reaction product to obtain a phosphonium-modified styrene-based unsaturated resin;

[0031] The phosphonium-modified styrene-based unsaturated resin, free radical polymerization monomer and initiator are mixed and cured to obtain a cured product of the phosphonium-modified styrene-based unsaturated resin.

[0032] In one embodiment, the molar ratio of the phosphine groups of the phosphorus-containing unsaturated resin to the halobenzyl groups of 4-vinylbenzyl halide is 1:(1-3).

[0033] In one embodiment, the 4-vinylbenzyl halide is 4-vinylbenzyl chloride and 4-vinylbenzyl bromide.

[0034] In one embodiment, the free radical polymerization monomer is any one or more of styrene, N-vinyl pyrrolidone, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile.

[0035] In one embodiment, the first solvent is any one or more of chloroform, tetrahydrofuran, 4-methyltetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0036] In one embodiment, the initiator is any one or more of azobisisobutyronitrile, azobisisoheptanenitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide paste, dibenzoyl peroxide, diisopropylbenzene peroxide, benzoin dimethyl ether, benzoin diethyl ether, diacetophenone, benzoin derivatives, benzyl ketal derivatives, α-hydroxyalkyl phenones, α-aminoalkyl phenones, acylphosphine oxides, esterified oxime ketone compounds, aromatic peroxyester compounds, dialkoxyacetophenones, phenylacetoacetate or diacetophenones.

[0037] In one embodiment, the amount of the initiator is 0.1 wt%-2 wt%.

[0038] In one embodiment, the phosphorus-containing unsaturated resin is obtained by addition reaction of an unsaturated resin with an organic phosphine compound.

[0039] In one embodiment, the organic phosphine compound is diphenylphosphine. As one of the sources of quaternary phosphonium salt structure, diphenylphosphine can be used as a phosphorus source to provide flame retardant properties, thereby improving the flame retardancy of epoxy resin.

[0040] In one embodiment, the unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 60-100° C. in an inert atmosphere in the presence of an inhibitor until the acid value is less than 20 mg KOH / g.

[0041] In one embodiment, the molar ratio of the epoxy resin to the acrylic acid is 1:(2-7), and the amount of the polymerization inhibitor is 0.75 wt%-1.5 wt%.

[0042] In one embodiment, the 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, and ethylene glycol diglycidyl ether.

[0043] In one embodiment, the polymerization inhibitor is any one or more of hydroquinone, 4-methoxyphenol, 2,5-dimethylhydroquinone, and 2,6-di-tert-butyl-p-quinone.

[0044] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail 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. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0045] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0046] Example 1

[0047] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (3.7 g), and inhibitor hydroquinone (0.10 g) were reacted at a reaction temperature of 60°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkaline washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin. Figure 1 shows the hydrogen nuclear magnetic resonance spectrum of the unsaturated resin;

[0048] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.37 g) at 45°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin. Figure 2 shows the hydrogen nuclear magnetic resonance spectrum of the phosphorus-containing unsaturated resin;

[0049] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.31 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin. Figure 3 The hydrogen nuclear magnetic resonance spectrum of the phosphonium-modified styrene-based unsaturated resin is shown;

[0050] The phosphonium-modified styrene-based unsaturated resin (5 g), hydroxyethyl acrylate (5 g), and benzoin dimethyl ether (10 mg) were mixed evenly, transferred to a mold, and cured under ultraviolet irradiation for 5 minutes to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate. Figure 4 A physical picture of a cross-linked polymer of a phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate is shown.

[0051] Example 2

[0052] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (13 g), and polymerization inhibitor 4-methoxyphenol (0.21 g) were reacted at a reaction temperature of 100°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Dichloromethane was added to completely dissolve the product, and the reaction solution was alkali washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0053] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.93 g) at 85°C for 1 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0054] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl bromide (0.59 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 100°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0055] The phosphonium-modified styrene-based unsaturated resin (5 g), hydroxyethyl methacrylate (5 g), and azobisisobutyronitrile (0.2 g) were mixed evenly, transferred to a mold, and cured at 45° C. for 24 h to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0056] Example 3

[0057] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (4.4 g), and polymerization inhibitor 4-methoxyphenol (0.15 g) were reacted at a reaction temperature of 70°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkali washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0058] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 40°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0059] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0060] The phosphonium-modified styrene-based unsaturated resin (5 g), hydroxypropyl acrylate (5 g), and benzoin diethyl ether (0.1 g) were mixed evenly, transferred to a mold, and cured under ultraviolet irradiation for 5 minutes to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0061] Example 4

[0062] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (4.4 g), and polymerization inhibitor 2,5-dimethylhydroquinone (0.15 g) were reacted at a reaction temperature of 70°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Dichloromethane was added to completely dissolve the product, and the reaction solution was alkaline washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0063] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 40°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0064] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0065] The phosphonium-modified styrene-based unsaturated resin (5 g), styrene (5 g), and diphenylacetophenone (0.2 g) were mixed evenly, transferred to a mold, and cured under ultraviolet irradiation for 10 minutes to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0066] Example 5

[0067] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor 2,6-di-tert-butyl-p-benzophenol (0.15 g) were reacted at a reaction temperature of 70°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Toluene was added and heated to completely dissolve the product. The reaction solution was alkali washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0068] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 40°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0069] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at 80°C for 24 hours. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0070] Phosphonium-modified styrene-based unsaturated resin (5 g), N-vinyl pyrrolidone (5 g), and dibenzoyl peroxide (0.2 g) were mixed evenly, transferred to a mold, and cured at 100° C. for 1 h to obtain a cross-linked polymer of phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0071] Example 6

[0072] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.15 g) were reacted at a reaction temperature of 70°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkaline washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0073] Under nitrogen atmosphere, the unsaturated resin (0.54 g) in tetrahydrofuran (10 mL) was reacted with diphenylphosphine (0.47 g) at 80°C for 1 h. After the reaction, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 50°C to obtain a solid phosphorus-containing unsaturated resin;

[0074] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0075] Phosphonium-modified styrene-based unsaturated resin (5 g), vinyl acetate (5 g), and dibenzoyl peroxide (0.2 g) were mixed evenly, transferred to a mold, and cured at 100° C. for 1 h to obtain a cross-linked polymer of phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0076] Example 7

[0077] Under nitrogen atmosphere, bisphenol A diglycidyl ether (10g), acrylic acid (4.4g), and inhibitor hydroquinone (0.15g) were reacted at a reaction temperature of 110°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkali washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0078] Under nitrogen atmosphere, unsaturated resin (0.48 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 40°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0079] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0080] The phosphonium-modified styrene-based unsaturated resin (5 g), acrylonitrile (5 g), and benzoin diethyl ether (0.2 g) were mixed evenly, transferred to a mold, and cured under ultraviolet irradiation for 5 minutes to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0081] Example 8

[0082] Under nitrogen atmosphere, bisphenol F diglycidyl ether (8.0 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.062 g) were reacted at a reaction temperature of 110°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkali washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0083] Under nitrogen atmosphere, unsaturated resin (0.46 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 40°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0084] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0085] The phosphonium-modified styrene-based unsaturated resin (5 g), hydroxyethyl acrylate (5 g), and dibenzoyl peroxide (0.2 g) were mixed evenly, transferred to a mold, and cured at 100° C. for 1 h to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0086] Example 9

[0087] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.15 g) were reacted at a reaction temperature of 70°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkaline washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0088] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 40°C for 24 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin;

[0089] The phosphorus-containing unsaturated resin (0.91 g) in chloroform (10 mL) was reacted with 4-vinylbenzyl chloride (0.46 g) at 60°C for 24 hours. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0090] The phosphonium-modified styrene-based unsaturated resin (5 g), hydroxyethyl acrylate (5 g), and diisopropylbenzene peroxide (0.2 g) were mixed evenly, transferred to a mold, and cured at 100° C. for 1 h to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0091] Example 10

[0092] In a nitrogen atmosphere, epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.15 g) were reacted at a reaction temperature of 100°C. During the reaction, samples were taken to track the acid value until the acid value was less than 20 mg KOH / g, and the reaction was terminated. Chloroform was added to completely dissolve the product, and the reaction solution was alkali washed and vacuum distilled to remove the solvent and water therein to obtain the product unsaturated resin;

[0093] Under nitrogen atmosphere, unsaturated resin (0.54 g) in chloroform (10 mL) was reacted with diphenylphosphine (0.47 g) at 85°C for 1 h. After the reaction, precipitation was performed with anhydrous ether, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a phosphorus-containing unsaturated resin in solid form;

[0094] The phosphorus-containing unsaturated resin (0.91 g) in N,N-dimethylformamide (10 mL) was reacted with 4-vinylbenzyl bromide (0.59 g) at a reaction temperature of 120°C for 1 hour. After the reaction was completed, cold anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 80°C to obtain a phosphonium-modified styrene-based unsaturated resin;

[0095] The phosphonium-modified styrene-based unsaturated resin (5 g), hydroxyethyl acrylate (5 g), and benzoin dimethyl ether (0.2 g) were mixed evenly, transferred to a mold, and cured under ultraviolet irradiation for 5 minutes to obtain a cross-linked polymer of the phosphonium-modified styrene-based unsaturated resin and hydroxyethyl acrylate.

[0096] Flame retardant performance test

[0097] In order to verify the flame retardant performance, the intrinsic flame retardant / antibacterial organophosphine-modified vinyl epoxy resin prepared in Examples 1-10 was subjected to UL-94 test. The results are shown in Table 1.

[0098] Table 1

[0099]

[0100] Note: Definition of V-0 level: The material is exposed to a flame for 10 seconds twice, the burning time each time does not exceed 10 seconds, the total burning time does not exceed 50 seconds, and there is no dripping of burning materials during the test or the dripping materials cannot ignite the absorbent cotton.

[0101] From the test results in Table 1, it can be seen that the UL-94 of the cured products of the organic phosphine-modified vinyl epoxy resin and the polyhalogenated compound prepared in Examples 1-10 is V-0.

[0102] 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 causing conflicts. 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 substitutions, improvements, etc. made within the spirit and principles of this application should be included in the scope of protection of this application.

Claims

1. A cured product of a phosphonium-modified styrene-based unsaturated resin, characterized in that: The solidified material is a cross-linked polymer of a phosphonated styrene-modified unsaturated resin and a free radical polymerization monomer; wherein the phosphonated styrene-modified unsaturated resin is obtained by a quaternary phosphonation reaction between a phosphorus-containing unsaturated resin and 4-vinylbenzyl halide; the phosphorus-containing unsaturated resin is obtained by an addition reaction between an unsaturated resin and an organic phosphine compound; the organic phosphine compound is diphenylphosphine; the unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 60-100° C. in an inert atmosphere in the presence of an inhibitor until the acid value is less than 20 mg KOH / g.

2. The cured product according to claim 1, characterized in that The free radical polymerization monomer is any one or any combination of styrene, N-vinyl pyrrolidone, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile.

3. The cured product according to claim 1, characterized in that The 4-vinylbenzyl halide is 4-vinylbenzyl chloride and 4-vinylbenzyl bromide.

4. The cured product according to claim 1, characterized in that The mass ratio of the phosphonium styrene-modified unsaturated resin to the free radical polymerization monomer is 1:(1-3).

5. A method for preparing a cured product of a phosphonium-modified styrene-based unsaturated resin, comprising: The phosphorus-containing unsaturated resin in the first solvent is reacted with 4-vinylbenzyl halide at 60-120° C. to precipitate the reaction product to obtain a phosphonium-modified styrene-based unsaturated resin; The phosphonium-modified styrene-based unsaturated resin, a free radical polymerization monomer, and an initiator are mixed and cured to obtain a cured product of the phosphonium-modified styrene-based unsaturated resin; The phosphorus-containing unsaturated resin is obtained by addition reaction of an unsaturated resin with an organic phosphine compound; the organic phosphine compound is diphenylphosphine; the unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 60-100° C. in an inert atmosphere in the presence of an inhibitor until the acid value is less than 20 mg KOH / g.

6. The method according to claim 5, characterized in that The molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the halogenated benzyl group of 4-vinylbenzyl halide is 1:(1-3).

7. The method according to claim 5, characterized in that The 4-vinylbenzyl halide is 4-vinylbenzyl chloride and 4-vinylbenzyl bromide.

8. The method according to claim 5, characterized in that The free radical polymerization monomer is any one or any combination of styrene, N-vinyl pyrrolidone, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, and acrylonitrile.

9. The method according to claim 5, characterized in that The first solvent is any one or any combination of chloroform, tetrahydrofuran, 4-methyltetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

10. The method according to claim 5, characterized in that The initiator is any one or more of azobisisobutyronitrile, azobisisoheptylnitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide paste, dibenzoyl peroxide, diisopropylbenzene peroxide, diacetophenone, benzoin derivatives, benzyl ketal derivatives, α-hydroxyalkyl phenone, α-aminoalkyl phenone, acylphosphine oxide, esterified oxime ketone compound, aromatic peroxyester compound, dialkoxyacetophenone, and phenylacetoacetate.

11. The method according to claim 10, characterized in that The initiator is benzoin dimethyl ether or benzoin diethyl ether.

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