Solidified product of organic phosphine-modified unsaturated resin and polyhalogenated compound and preparation method thereof

Abstract

The present application relates to a solidified product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound and a preparation method thereof. The solidified product is a solidified product having a cross-linked structure formed by a quaternary phosphonation reaction between a phosphorus-containing unsaturated resin and a polyhalogenated compound, and has good flame retardant properties.

Description

Technical Field

[0001] The present application relates to a solidified product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound and a preparation method thereof. Background Art

[0002] Epoxy resin has excellent physical and mechanical properties, electrical insulation, chemical resistance and bonding properties. It can be used as coatings, casting materials, molding materials, adhesives, and laminates in various fields of the national economy in the form of direct or indirect use. For example, epoxy resin is widely used in composite materials in aircraft and spacecraft, packaging materials for large-scale integrated circuits, insulation materials for copper-clad laminates, coatings for steel and wood, adhesives for mechanical and civil construction, and even coatings on the inner wall of food cans and metal anti-corrosion electrophoretic coatings.

[0003] A significant disadvantage of epoxy resin is its flammability. To enhance its flame retardancy, the industry currently generally uses halogen-containing flame-retardant epoxy resins. However, the use of halogen-based flame retardants has caused major concerns: they significantly weaken the UV resistance of the protected material and release a large amount of smoke, corrosive gases and harmful gases during combustion. In view of the need for environmental protection, the application of halogen-based flame retardants has been restricted to varying degrees. Therefore, the development of halogen-free epoxy resins has become the main development direction in this field. Summary of the invention

[0004] In view of the deficiencies in the prior art, one aspect of the present application provides a cured product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound.

[0005] The cured product provided in the present application is a cured product having a cross-linked structure formed by a quaternary phosphonium reaction between a phosphorus-containing unsaturated resin and a polyhalogenated compound.

[0006] In one embodiment, the polyhalogenated compound is obtained by reacting a polyhydroxy compound with a halogenated acid anhydride, and the molar ratio of the polyhydroxy compound to the halogenated acid anhydride is 1:(3-16).

[0007] In one embodiment, 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:(2-6).

[0008] In one embodiment, the polyhydroxy compound is any one or more of trimethylolethane, trimethylolpropane, 4,4',4''-methylenetriphenol, 1,1,1-tri(4-hydroxyphenyl)ethane, glycerol, dipropylene glycol, 1,2,6-hexanetriol, octantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,3,4-butanetetrol.

[0009] In one embodiment, the halogenated acid anhydride is any one or more of chloroacetic anhydride, chloropropionic anhydride, chlorobutyric anhydride, chlorovaleric anhydride, chlorohexanoic anhydride, chloroheptanoic anhydride, chlorooctanoic anhydride, chlorononanoic anhydride, chlorodecanoic anhydride, bromoacetic anhydride, bromopropionic anhydride, bromobutyric anhydride, bromovaleric anhydride, bromohexanoic anhydride, bromoheptanoic anhydride, bromooctanoic anhydride, bromononanoic anhydride, bromodecanic anhydride, iodoacetic anhydride, iodopropionic anhydride, iodobutyric anhydride, iodovaleric anhydride, iodohexanoic anhydride, iodoheptanoic anhydride, iodooctanoic anhydride, iodononanoic anhydride, and iododecanoic anhydride.

[0010] One aspect of the present application provides a method for preparing a cured product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound.

[0011] The method for preparing a solidified product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound provided by the present invention comprises:

[0012] Under an inert atmosphere, reacting the unsaturated resin in the first solvent with the organic phosphine compound at 50-90° C., precipitating the reaction product to obtain a phosphorus-containing unsaturated resin;

[0013] Under an inert atmosphere, reacting the polyhydroxy compound in the second solvent with a halogenated acid anhydride at 40-100° C. to obtain a polyhalogenated compound;

[0014] The phosphorus-containing unsaturated resin is mixed with the polyhalogenated compound, and then cured at 60-100° C. to obtain the cured product.

[0015] In one embodiment, the polyhydroxy compound is any one or more of trimethylolethane, trimethylolpropane, 4,4',4''-methylenetriphenol, 1,1,1-tri(4-hydroxyphenyl)ethane, glycerol, dipropylene glycol, 1,2,6-hexanetriol, octantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,3,4-butanetetrol.

[0016] In one embodiment, the halogenated acid anhydride is any one or more of chloroacetic anhydride, chloropropionic anhydride, chlorobutyric anhydride, chlorovaleric anhydride, chlorohexanoic anhydride, chloroheptanoic anhydride, chlorooctanoic anhydride, chlorononanoic anhydride, chlorodecanoic anhydride, bromoacetic anhydride, bromopropionic anhydride, bromobutyric anhydride, bromovaleric anhydride, bromohexanoic anhydride, bromoheptanoic anhydride, bromooctanoic anhydride, bromononanoic anhydride, bromodecanic anhydride, iodoacetic anhydride, iodopropionic anhydride, iodobutyric anhydride, iodovaleric anhydride, iodohexanoic anhydride, iodoheptanoic anhydride, iodooctanoic anhydride, iodononanoic anhydride, and iododecanoic anhydride.

[0017] In one embodiment, the molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the halomethyl group of the polyhalogenated compound is 1:(1-1.5); the molar ratio of the polyhydroxy compound to the halogenated acid anhydride is 1:(3-16); and the molar ratio of the unsaturated resin to the organic phosphine compound is 1:(2-6).

[0018] In one embodiment, the first solvent is any one or more of chloroform, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the second solvent is any one or more of dichloromethane, chloroform, tetrahydrofuran, and 2-methyltetrahydrofuran.

[0019] The cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound provided in the present application has good flame retardant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the unsaturated resin prepared in Example 1 is shown.

[0021] Figure 2 The hydrogen nuclear magnetic resonance spectrum of the phosphorus-containing unsaturated resin prepared in Example 1 is shown.

[0022] Figure 3 The hydrogen nuclear magnetic resonance spectrum of tris(hydroxymethyl)chloroacetate ethane prepared in Example 1 is shown.

[0023] Figure 4 The actual picture of the solidified product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound prepared in Example 1 is shown.

[0024] Figure 5 The actual picture of the solidified product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound prepared in Example 2 is shown. DETAILED DESCRIPTION

[0025] One aspect of the present application provides a cured product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound, wherein the cured product has good flame retardant properties.

[0026] The cured product provided in the present application is a cured product having a cross-linked structure formed by a quaternary phosphonium reaction between a phosphorus-containing unsaturated resin and a polyhalogenated compound.

[0027] Unsaturated resins contain hydroxyl groups and unsaturated double bonds, which can be modified by some functional groups to improve some properties. Organic phosphine compounds can react with vinyl groups and be introduced into the system to improve the flame retardant properties of the material. Polyhalogenated compounds can be used to cure epoxy resins with tertiary phosphine structures to form three-dimensional network structures, which can obtain polymer materials with excellent properties. Phosphorus elements have advantages in phosphorus-based flame retardant technology because they can easily form stable compounds with other elements (such as POC or PC bonds). This system can promote the formation of more carbon layers, especially oxygen-rich polymers, during combustion, and the generated carbon layers have good antioxidant properties. Since phosphoric acid can form a protective film on the surface of the carbon layer, this helps to prevent the spread of flames. In addition, people pay more and more attention to the protection of the ecological environment, and flame retardant materials must also be more green and environmentally friendly. Quaternary phosphonium esters are lipid compounds containing quaternary phosphonium groups. Their molecular structures contain electron-withdrawing groups, which reduce the charge density on the carbon atoms connected to the ester bond, which is conducive to the hydrolysis of the ester bond and can play an important role in the field of biodegradability.

[0028] In one embodiment, the polyhalogenated compound is obtained by reacting a polyhydroxy compound with a halogenated acid anhydride, and the molar ratio of the polyhydroxy compound to the halogenated acid anhydride is 1:(3-16).

[0029] In one embodiment, 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:(2-6).

[0030] In one embodiment, the polyhydroxy compound is any one or more of trimethylolethane, trimethylolpropane, 4,4',4''-methylenetriphenol, 1,1,1-tri(4-hydroxyphenyl)ethane, glycerol, dipropylene glycol, 1,2,6-hexanetriol, octantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,3,4-butanetetrol.

[0031] In one embodiment, the halogenated acid anhydride is any one or more of chloroacetic anhydride, chloropropionic anhydride, chlorobutyric anhydride, chlorovaleric anhydride, chlorohexanoic anhydride, chloroheptanoic anhydride, chlorooctanoic anhydride, chlorononanoic anhydride, chlorodecanoic anhydride, bromoacetic anhydride, bromopropionic anhydride, bromobutyric anhydride, bromovaleric anhydride, bromohexanoic anhydride, bromoheptanoic anhydride, bromooctanoic anhydride, bromononanoic anhydride, bromodecanic anhydride, iodoacetic anhydride, iodopropionic anhydride, iodobutyric anhydride, iodovaleric anhydride, iodohexanoic anhydride, iodoheptanoic anhydride, iodooctanoic anhydride, iodononanoic anhydride, and iododecanoic anhydride.

[0032] One aspect of the present application provides a method for preparing a cured product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound.

[0033] The method for preparing a solidified product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound provided by the present invention comprises:

[0034] Under an inert atmosphere, reacting the unsaturated resin in the first solvent with the organic phosphine compound at 50-90° C., precipitating the reaction product to obtain a phosphorus-containing unsaturated resin;

[0035] Under an inert atmosphere, reacting the polyhydroxy compound in the second solvent with a halogenated acid anhydride at 40-100° C. to obtain a polyhalogenated compound;

[0036] The phosphorus-containing unsaturated resin is mixed with the polyhalogenated compound, and then cured at 60-100° C. to obtain the cured product.

[0037] In one embodiment, the polyhydroxy compound is any one or more of trimethylolethane, trimethylolpropane, 4,4',4''-methylenetriphenol, 1,1,1-tri(4-hydroxyphenyl)ethane, glycerol, dipropylene glycol, 1,2,6-hexanetriol, octantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,3,4-butanetetrol.

[0038] In one embodiment, the halogenated acid anhydride is any one or more of chloroacetic anhydride, chloropropionic anhydride, chlorobutyric anhydride, chlorovaleric anhydride, chlorohexanoic anhydride, chloroheptanoic anhydride, chlorooctanoic anhydride, chlorononanoic anhydride, chlorodecanoic anhydride, bromoacetic anhydride, bromopropionic anhydride, bromobutyric anhydride, bromovaleric anhydride, bromohexanoic anhydride, bromoheptanoic anhydride, bromooctanoic anhydride, bromononanoic anhydride, bromodecanic anhydride, iodoacetic anhydride, iodopropionic anhydride, iodobutyric anhydride, iodovaleric anhydride, iodohexanoic anhydride, iodoheptanoic anhydride, iodooctanoic anhydride, iodononanoic anhydride, and iododecanoic anhydride.

[0039] In one embodiment, the molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the halomethyl group of the polyhalogenated compound is 1:(1-1.5); the molar ratio of the polyhydroxy compound to the halogenated acid anhydride is 1:(3-16); and the molar ratio of the unsaturated resin to the organic phosphine compound is 1:(2-6).

[0040] In one embodiment, the first solvent is any one or more of chloroform, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the second solvent is any one or more of dichloromethane, chloroform, tetrahydrofuran, and 2-methyltetrahydrofuran.

[0041] In one embodiment, the unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 65-105° C. in the presence of an inhibitor under an inert atmosphere to an acid value of less than 15 mg KOH / g.

[0042] In one embodiment, the molar ratio of the epoxy resin to the acrylic acid is 1:(2-6).

[0043] 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.

[0044] 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.

[0045] In one embodiment, the organic phosphine reagent is diphenylphosphine. Diphenylphosphine is an organic phosphine compound that can react with vinyl groups and be introduced into the system to improve the flame retardant properties of the material. In addition, the tertiary phosphine structure formed by the addition reaction has strong nucleophilicity and can easily form a quaternary phosphonium salt with a halogenated hydrocarbon.

[0046] 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.

[0047] 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.

[0048] Example 1

[0049] Epoxy resin E51 (10 g), acrylic acid (3.7 g), and inhibitor hydroquinone (0.069 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 65°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mg KOH / g, the reaction was terminated. Chloroform was added to completely dissolve the product. The reaction solution was washed with alkali and evaporated in vacuum to remove the solvent and water therein, and the product unsaturated resin was obtained. Figure 1 shows the hydrogen nuclear magnetic resonance spectrum of the unsaturated resin;

[0050] Under anaerobic conditions, unsaturated resin (0.54 g), diphenylphosphine (0.37 g) and chloroform (10 mL) were mixed and stirred at 50°C for 24 h. After the reaction, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30°C to obtain a solid phosphorus-containing unsaturated resin. Figure 2shows the hydrogen nuclear magnetic resonance spectrum of the phosphorus-containing unsaturated resin;

[0051] Under nitrogen atmosphere, trimethylolethane (1.20 g) in chloroform (15 mL) was reacted with chloroacetic anhydride (5.13 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(chloroacetic acid-hydroxymethyl) ester ethane. Figure 3 The hydrogen nuclear magnetic resonance spectrum of tris(hydroxymethyl)chloroacetate ethane is shown.

[0052] The phosphorus-containing unsaturated resin (0.45 g) and tris(chloroacetic acid-hydroxymethyl) ethane (0.12 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a solidified product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained. Figure 4 The figure shows the solid product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound.

[0053] Example 2

[0054] Epoxy resin E51 (10 g), acrylic acid (11 g), and polymerization inhibitor 2,5-dimethylhydroquinone (0.42 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 105°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mgKOH / g, the reaction was terminated. Chloroform was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein, and the product unsaturated resin was obtained;

[0055] Under anaerobic conditions, the unsaturated resin (0.54 g) was mixed with diphenylphosphine (1.12 g) and chloroform (10 mL), and stirred at 90° 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 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0056] Under nitrogen atmosphere, 4,4',4''-methylenetrisphenol (2.92 g) in chloroform (15 mL) was reacted with chloroacetic anhydride (27.4 g) at 100°C for 1 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain 4,4',4''-methylenetris(chloroacetic acid phenol) ester;

[0057] The phosphorus-containing unsaturated resin (0.45 g) and 4,4',4''-methylene tris(chloroacetate phenol) ester (0.26 g) were mixed evenly and cured at 100°C for 1 hour. After cooling to room temperature, a solidified product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained. Figure 5 The figure shows the solid product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound.

[0058] Example 3

[0059] Epoxy resin E51 (10 g), acrylic acid (4.4 g), and polymerization inhibitor 4-methoxyphenol (0.072 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mgKOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein, and the product unsaturated resin was obtained;

[0060] Under anaerobic conditions, the unsaturated resin (0.54 g) was mixed with diphenylphosphine (0.47 g) and chloroform (10 mL), and stirred at 50° C. for 24 h. After the reaction was completed, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0061] Under nitrogen atmosphere, trimethylolethane (1.20 g) in chloroform (15 mL) was reacted with bromoacetic anhydride (10.4 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(bromoacetic acid-hydroxymethyl) ester ethane;

[0062] (4) The phosphorus-containing unsaturated resin (0.45 g) and tris(bromoacetic acid-hydroxymethyl) ethane (0.24 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0063] Example 4

[0064] Epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.072 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mg KOH / g, the reaction was stopped. Dichloromethane was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein to obtain the product unsaturated resin;

[0065] Under nitrogen atmosphere, unsaturated resin (0.54 g) was mixed with diphenylphosphine (0.47 g) and chloroform (10 mL), and stirred at 50° C. for 24 h. After the reaction, anhydrous ether was used for precipitation, and the lower precipitate was collected, and then the precipitate was vacuum dried at 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0066] Under nitrogen atmosphere, trimethylolethane (1.20 g) in chloroform (15 mL) was reacted with iodoacetic anhydride (10.6 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(iodoacetic acid-hydroxymethyl) ester ethane;

[0067] The phosphorus-containing unsaturated resin (0.45 g) and tris(iodoacetic acid-hydroxymethyl) ethane (0.31 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0068] Example 5

[0069] Epoxy resin E51 (10 g), acrylic acid (4.4 g), and polymerization inhibitor 2,6-di-tert-butyl-p-benzophenol (0.072 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mg KOH / g, the reaction was stopped. Toluene was added and heated to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein to obtain the product unsaturated resin;

[0070] Under anaerobic conditions, the unsaturated resin (0.54 g) was mixed with diphenylphosphine (0.47 g) and chloroform (10 mL), and stirred at 50° C. for 24 h. After the reaction was completed, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0071] Under nitrogen atmosphere, trimethylolpropane (1.34 g) in chloroform (15 mL) was reacted with chloroacetic anhydride (5.47 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(chloroacetic acid-hydroxymethyl) ester ethane;

[0072] The phosphorus-containing unsaturated resin (0.45 g) and tris(chloroacetic acid-hydroxymethyl) propane (0.18 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0073] Example 6

[0074] Epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.072 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mg KOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein, and the product unsaturated resin was obtained;

[0075] Under anaerobic conditions, the unsaturated resin (0.54 g) was mixed with diphenylphosphine (0.47 g) and tetrahydrofuran (10 mL), and stirred at 80° C. for 1 h. After the reaction was completed, 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;

[0076] Under nitrogen atmosphere, glycerol (0.94 g) in chloroform (15 mL) was reacted with chloroacetic anhydride (5.47 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain glycerol-chloroacetate;

[0077] (4) The phosphorus-containing unsaturated resin (0.45 g) and glycerol monochloroacetate (0.16 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0078] Example 7

[0079] Bisphenol A diglycidyl ether (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.072 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mgKOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein, and the product unsaturated resin was obtained;

[0080] Under anaerobic conditions, the unsaturated resin (0.48 g) was mixed with diphenylphosphine (0.47 g) and chloroform (10 mL), and stirred at 50° C. for 24 h. After the reaction was completed, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0081] Under nitrogen atmosphere, trimethylolethane (1.20 g) in chloroform (15 mL) was reacted with chloroacetic anhydride (5.47 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(chloroacetic acid-hydroxymethyl) ester ethane;

[0082] The phosphorus-containing unsaturated resin (0.45 g) and tris(chloroacetic acid-hydroxymethyl)ethane (0.17 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0083] Example 8

[0084] Bisphenol F diglycidyl ether (8.0 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.062 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mgKOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein, and the product unsaturated resin was obtained;

[0085] Under anaerobic conditions, the unsaturated resin (0.46 g) was mixed with diphenylphosphine (0.47 g) and chloroform (10 mL), and stirred at 50° C. for 24 h. After the reaction was completed, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0086] Under nitrogen atmosphere, trimethylolethane (1.20 g) in chloroform (15 mL) was reacted with chloroacetic anhydride (5.47 g) at 40°C for 12 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(chloroacetic acid-hydroxymethyl) ester ethane;

[0087] The phosphorus-containing unsaturated resin (0.45 g) and tris(chloroacetic acid-hydroxymethyl)ethane (0.17 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0088] Example 9

[0089] Epoxy resin E51 (10 g), acrylic acid (4.4 g), and inhibitor hydroquinone (0.072 g) were reacted under mechanical stirring and anaerobic conditions. The reaction temperature was 90°C. During the reaction, samples were taken to track the acid value. When the acid value was less than 15 mg KOH / g, the reaction was stopped. Chloroform was added to completely dissolve the product. The reaction solution was alkali washed and vacuum evaporated to remove the solvent and water therein, and the product unsaturated resin was obtained;

[0090] Under anaerobic conditions, the unsaturated resin (0.54 g) was mixed with diphenylphosphine (0.47 g) and chloroform (10 mL), and stirred at 50° C. for 24 h. After the reaction was completed, anhydrous ether was used for precipitation, the lower precipitate was collected, and then the precipitate was vacuum dried at 30° C. to obtain a solid phosphorus-containing unsaturated resin;

[0091] Under nitrogen atmosphere, trimethylolethane (1.20 g) in tetrahydrofuran (15 mL) was reacted with chloroacetic anhydride (5.47 g) at 80°C for 1 h. After the reaction, the product was washed with alkali and evaporated in vacuo to obtain tris(chloroacetic acid-hydroxymethyl) ester ethane;

[0092] The phosphorus-containing unsaturated resin (0.45 g) and tris(chloroacetic acid-hydroxymethyl)ethane (0.17 g) were mixed evenly and cured at 60° C. for 12 h. After cooling to room temperature, a cured product of the organic phosphine-modified unsaturated resin and the polyhalogenated compound was obtained.

[0093] Flame retardant performance test

[0094] In order to verify the flame retardant performance, the cured products of the organic phosphine-modified unsaturated resin and the polyhalogenated compound prepared in Examples 1-9 were subjected to UL-94 test.

[0095] Table 1

[0096]

[0097] Note: Definition of V-0 level: When the material is exposed to a flame for 10 seconds twice, and 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.

[0098] From the test results in Table 1, it can be seen that the UL-94 of the cured products of the organic phosphine-modified unsaturated resin and the polyhalogenated compound prepared in Examples 1-9 is V-0.

[0099] 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 an organic phosphine-modified unsaturated resin and a polyhalogenated compound, characterized in that: The solidified material is a solidified material with a cross-linked structure formed by a quaternary phosphonium reaction between a phosphorus-containing unsaturated resin and a polyhalogenated compound; Wherein, the polyhalogenated compound is obtained by reacting a polyhydroxy compound with a halogenated acid anhydride, and the molar ratio of the polyhydroxy compound to the halogenated acid anhydride is 1:(3-16); The polyhydroxy compound is any one or more of trimethylolethane, trimethylolpropane, 4,4',4''-methylenetriphenol, 1,1,1-tris(4-hydroxyphenyl)ethane, glycerol, dipropylene glycol, 1,2,6-hexanetriol, octantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,3,4-butanetetrol; The phosphorus-containing unsaturated resin is obtained by reacting an unsaturated resin with an organic phosphine compound, wherein the molar ratio of the unsaturated resin to the organic phosphine compound is 1:(2-6); the organic phosphine compound is diphenylphosphine; The unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 65-105° C. in an inert atmosphere in the presence of an inhibitor until the acid value is less than 15 mg KOH / g.

2. The cured product according to claim 1, characterized in that The halogenated acid anhydride is any one or more of chloroacetic anhydride, chloropropionic anhydride, chlorobutyric anhydride, chlorovaleric anhydride, chlorohexanoic anhydride, chloroheptanoic anhydride, chlorooctanoic anhydride, chlorononanoic anhydride, chlorodecanoic anhydride, bromoacetic anhydride, bromopropionic anhydride, bromobutyric anhydride, bromovaleric anhydride, bromohexanoic anhydride, bromoheptanoic anhydride, bromooctanoic anhydride, bromononanoic anhydride, bromodecanic anhydride, iodoacetic anhydride, iodopropionic anhydride, iodobutyric anhydride, iodovaleric anhydride, iodohexanoic anhydride, iodoheptanoic anhydride, iodooctanoic anhydride, iodononanoic anhydride and iododecanoic anhydride.

3. A method for preparing a solidified product of an organic phosphine-modified unsaturated resin and a polyhalogenated compound, comprising: Under an inert atmosphere, reacting the unsaturated resin in the first solvent with the organic phosphine compound at 50-90° C., precipitating the reaction product to obtain a phosphorus-containing unsaturated resin; Under an inert atmosphere, reacting the polyhydroxy compound in the second solvent with a halogenated acid anhydride at 40-100° C. to obtain a polyhalogenated compound; The phosphorus-containing unsaturated resin is mixed with the polyhalogenated compound, and then cured at 60-100° C. to obtain the cured product; Wherein, the polyhydroxy compound is any one or more of trimethylolethane, trimethylolpropane, 4,4',4''-methylenetriphenol, 1,1,1-tris(4-hydroxyphenyl)ethane, propylene glycol, dipropylene glycol, 1,2,6-hexanetriol, octantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,3,4-butanetetrol; The phosphorus-containing unsaturated resin is obtained by reacting an unsaturated resin with an organic phosphine compound, wherein the molar ratio of the unsaturated resin to the organic phosphine compound is 1:(2-6); the organic phosphine compound is diphenylphosphine; The unsaturated resin is obtained by reacting an epoxy resin with acrylic acid at 65-105° C. in an inert atmosphere in the presence of an inhibitor until the acid value is less than 15 mg KOH / g.

4. The method according to claim 3, characterized in that The halogenated acid anhydride is any one or more of chloroacetic anhydride, chloropropionic anhydride, chlorobutyric anhydride, chlorovaleric anhydride, chlorohexanoic anhydride, chloroheptanoic anhydride, chlorooctanoic anhydride, chlorononanoic anhydride, chlorodecanoic anhydride, bromoacetic anhydride, bromopropionic anhydride, bromobutyric anhydride, bromovaleric anhydride, bromohexanoic anhydride, bromoheptanoic anhydride, bromooctanoic anhydride, bromononanoic anhydride, bromodecanic anhydride, iodoacetic anhydride, iodopropionic anhydride, iodobutyric anhydride, iodovaleric anhydride, iodohexanoic anhydride, iodoheptanoic anhydride, iodooctanoic anhydride, iodononanoic anhydride and iododecanoic anhydride.

5. The method according to claim 3, characterized in that: The molar ratio of the phosphine group of the phosphorus-containing unsaturated resin to the halomethyl group of the polyhalogenated compound is 1:(1-1.5); the molar ratio of the polyhydroxy compound to the halogenated acid anhydride is 1:(3-16).

6. The method according to claim 3, characterized in that: The first solvent is any one or more of chloroform, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the second solvent is any one or more of dichloromethane, chloroform, tetrahydrofuran, and 2-methyltetrahydrofuran.

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