Flavonol hyperbranched flame retardant as well as preparation method and application thereof

Abstract

The invention relates to the technical field of flame-retardant materials, and particularly discloses a flavonol hyperbranched flame retardant and a preparation method and application thereof.The flavonol hyperbranched flame retardant has the structural formula shown in the formula I: # imgabs0 #, wavy lines in the structural formula are repeated units in the structure, and Rn (n = 1-7) in the formula I is hydroxyl. The flavonol hyperbranched flame retardant is formed through nucleophilic substitution reaction of the flavonol compound containing reactive hydrogen, the organic phosphorus organic silicon containing dichloro and the like, the flame retardant effect is improved, and meanwhile the effects of improving the mechanical property and reducing the smoke amount are achieved.

Description

Technical Field

[0001] The present application relates to the technical field of flame retardant materials, and in particular to a flavonol hyperbranched flame retardant and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a polymer, a type of polymer material with a cross-linked network structure. It is a condensation product of epichlorohydrin and bisphenol A or polyol. Due to the chemical activity of the epoxy group, it can be opened with a variety of compounds containing active hydrogen to form a network structure by curing and cross-linking, so it is a thermosetting resin. It has excellent dielectric properties, bonding properties, mechanical properties and thermal properties, and is widely used in the fields of machinery, electronics and aerospace in the form of coatings and composite materials. However, epoxy resin has defects: the limiting oxygen index of epoxy resin is low, only 19.8%, and it is a flammable material. It is extremely flammable and can burn in the air, which is easy to cause fire. It is accompanied by a large amount of toxic gases and black smoke when burning; it greatly limits its application field. In recent years, with the country's attention to fire hazards, the flammability of epoxy resin has largely limited its wide application. The flame retardant modification of epoxy resin usually adopts two strategies: introducing flame retardants and preparing flame retardant epoxy monomers. Although halogen-containing flame retardants have high flame retardant efficiency, they release a large amount of toxic gases during combustion, which harms the environment and human health. Therefore, improving the flame retardant properties of epoxy resins and developing bio-based halogen-free flame retardant epoxy resins are of great significance for saving resources, protecting the environment and expanding its application areas, and are key issues that need to be solved in the application of epoxy resins. Composite materials such as polycarbonate and polypropylene are widely used in various fields due to their advantages such as insulation, ductility, and easy processing and molding. However, polymer-based composite materials are extremely flammable, which brings great fire hazards to society. Therefore, the study of the flame retardant properties of polymer-based composite materials is one of the hot spots in scientific application research.

[0003] In terms of flame retardancy of composite materials, adding flame retardants is a low-cost and simple method. Biomass-derived phenolic and acid compounds usually have rich aromatic structures and high carbon-forming ability, such as eugenol, magnolol, vanillin, gallic acid, diphenolic acid, etc. Different biomass compounds have different types of substituents, and bio-based epoxy monomers with diverse structures and properties can be synthesized by molecular design. The main body of aliphatic epoxy resins is usually a long aliphatic chain structure, such as epoxy resins containing fatty acids, itaconic acid, sebacic acid, etc., which have low viscosity and good toughness. Through its active functional groups such as hydroxyl, carboxyl, carbon-carbon double bonds, etc., the flame retardant properties of aliphatic biomass epoxy compounds can be improved after introducing flame retardant elements such as phosphorus and nitrogen. For example, Chinese patent document CN202410851811.6, application date 20240628, named: A bio-based intumescent flame retardant and its preparation method and application, discloses a bio-based intumescent flame retardant that can significantly improve the flame retardant properties of epoxy resins. As a bio-based reactive flame retardant, it has little effect on the mechanical properties of composite materials. At the same time, most of the existing flame retardants need to be added to the composite materials in a certain amount to achieve the flame retardant effect, but when a large amount of flame retardant is added, the mechanical properties of the composite materials will also be reduced, limiting the application of flame retardant composite materials.

[0004] Therefore, a new flame retardant is needed to improve the flame retardancy of flame retardant composite materials, reduce the amount of smoke generated when the flame retardant composite materials are burned, and enhance the mechanical properties of the composite materials. Summary of the invention

[0005] The purpose of this application is to overcome the shortcomings of the prior art and provide a flavonol hyperbranched flame retardant and a preparation method and application thereof, so as to at least improve the flame retardant ability of the flame retardant composite material, reduce the amount of smoke generated by the flame retardant composite material during combustion, and enhance the mechanical properties of the composite material.

[0006] In order to solve the above problems, this application adopts the following technical solutions:

[0007] On the one hand, the present application provides a flavonol hyperbranched flame retardant, the structural formula of which is as follows:

[0008] Formula I:

[0009]

[0010] The wavy lines in the structural formula are repeating units in the structure.

[0011] Furthermore, R in Formula I n (n=1-7) is a hydroxyl group, and the R' includes a phosphophenyl ring group and a silylphenyl group.

[0012] On the other hand, the present application provides a method for preparing the above-mentioned flavonol hyperbranched flame retardant, comprising the following steps:

[0013] Mixing a flavonol compound, a solvent and triethylamine to obtain a solution I;

[0014] Add the dichlorinated organophosphorus organosilicon compound dropwise into the solution I, react for 2 h in a nitrogen atmosphere at 0-5° C., then heat to room temperature and continue to react for 6 h to obtain solution II;

[0015] The solution II is filtered, air-dried, washed, dried and ground, and then the solid is collected to obtain the flavonol hyperbranched flame retardant.

[0016] Through the above technical scheme, the present application forms the flavonol hyperbranched flame retardant by reacting the flavonol compounds containing active hydrogen with the dichlorinated organophosphorus organosilicon through nucleophilic substitution reaction, thereby achieving the effect of improving the flame retardant effect and reducing the amount of smoke and increasing its mechanical properties when preparing resin composite materials. Among them, the phosphate group provides an efficient gas phase flame retardant effect and promotes catalytic carbonization, and the flavonol structure provides a condensed flame retardant effect, so that it can improve the flame retardant effect through synergistic effect when preparing composite materials, thereby achieving the effect of improving the flame retardant effect of epoxy resin and reducing the amount of smoke.

[0017] Preferably, the flavonol compound includes one of quercetin, naringenin, luteolin and hesperetin.

[0018] Preferably, the dichloride-containing organophosphorus organosilicon compound includes one of methyl phosphoryl dichloride, phenyl phosphoryl dichloride, phenyl dichlorophosphate and diphenyldichlorosilane.

[0019] The solvent includes one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide and chloroform.

[0020] The molar ratio of the flavonol compound to the dichloroorganophosphorus organosilicon compound is 1:2.5.

[0021] In another aspect, the present application provides the use of the above-mentioned flavonol hyperbranched flame retardant or the above-mentioned method in preparing a flame-retardant composite material;

[0022] The flame retardant composite material includes epoxy resin flame retardant composite material and thermoplastic resin flame retardant composite material.

[0023] Furthermore, the method for preparing the epoxy resin flame retardant composite material comprises the following steps:

[0024] The epoxy resin and the curing agent are added to the first flame retardant, stirred under vacuum conditions, and immediately poured into a mold after obtaining an intermediate product, to perform a curing reaction, and then cooled to room temperature to obtain the epoxy resin composite material.

[0025] Furthermore, the method for preparing the thermoplastic resin flame retardant composite material comprises the following steps:

[0026] The thermoplastic resin is added to the second flame retardant, and the mixture is dried, mixed, extruded, granulated and thermoplasticized to obtain the thermoplastic resin flame retardant composite material.

[0027] Preferably, the first flame retardant and the second flame retardant include flavonol hyperbranched flame retardants.

[0028] Preferably, the epoxy resin comprises E51 epoxy resin.

[0029] Preferably, the curing agent comprises 4,4-diaminodiphenylmethane (DDM).

[0030] Preferably, the thermoplastic resin includes polycarbonate resin and polypropylene resin.

[0031] Preferably, the weight ratio of the first flame retardant, the epoxy resin and the curing agent is (0.5-5):(75-80):(19-20).

[0032] Preferably, the weight ratio of the second flame retardant to the thermoplastic resin is (0.5-5):(95-100).

[0033] Preferably, the stirring method comprises magnetic stirring; wherein the temperature of the magnetic stirring is 60° C. to 80° C., and the time of the magnetic stirring is 0.5 to 0.8 h.

[0034] Preferably, the temperature of the curing reaction is calculated according to a programmed temperature rise mode, and the programmed temperature rise mode is: curing temperature = 100°C / 3h+140°C / 3h.

[0035] Preferably, the drying method includes vacuum drying; wherein the vacuum drying temperature is 80° C. and the vacuum drying time is 24 hours.

[0036] Preferably, the thermoplastic temperature is 260°C to 275°C.

[0037] More specifically, the mixing, the extruding and the granulation are performed by a screw extruder.

[0038] The beneficial effects of this application are:

[0039] 1. The flavonol hyperbranched flame retardant of the present application can improve the flame retardant effect through synergistic effect when preparing epoxy resin by providing phosphate groups with efficient gas phase flame retardant effect and flavonol structures with condensed flame retardant effect, thereby achieving the effect of improving the flame retardant effect of the prepared resin composite material, reducing the amount of smoke and increasing its mechanical properties.

[0040] 2. The flavonol hyperbranched flame retardant of the present application achieves the effect of ensuring the increase of the mechanical properties of the composite material by introducing rigid benzene rings and forming a cross-linked structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is the hydrogen-NMR spectrum of the flavonol hyperbranched flame retardant in Example 1 of the present invention (wherein Chemical shift is chemical shift and intensity is signal intensity);

[0042] Figure 2 The thermogravimetric curve of the flavonol hyperbranched flame retardant in Example 1 of the present invention (wherein Temperature is temperature, Weight is weight fraction, and Deriv.Weight is derivative weight);

[0043] Figure 3 This is a thermogravimetric curve of the epoxy resin composite material in Example 1 of the present invention (wherein Temperature is temperature, Weight is weight fraction, and Deriv.Weight is derivative weight). DETAILED DESCRIPTION

[0044] The technical solution of the present application is further described in detail below in conjunction with the accompanying drawings, but the protection scope of the present application is not limited to the following.

[0045] Example 1

[0046] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0047] S1, quercetin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of tetrahydrofuran and dissolved under magnetic stirring at room temperature to obtain solution I;

[0048] S2, adding phenylphosphoryl dichloride (48.5 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0049] S3, after filtering solution II, air-dry it for 12 hours to obtain a solid, put the solid into a beaker with 500 mL of deionized water, stir and filter it, and then vacuum dry the solid at 80°C for 12 hours, grind and sieve 100 mesh, and collect the product. (H-NMR spectrum as shown Figure 1 As shown, the thermogravimetric curve of the flame retardant is Figure 2 As shown, the thermogravimetric curve of epoxy resin composite material is as follows Figure 3 shown).

[0050] Example 2

[0051] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0052] S1, quercetin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of chloroform and dissolved under magnetic stirring at room temperature to obtain solution I;

[0053] S2, adding methylphosphoryl dichloride (33.3 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0054] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0055] Example 3

[0056] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0057] S1, quercetin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of N,N-dimethylformamide and dissolved under magnetic stirring at room temperature to obtain solution I;

[0058] S2, adding phenyl dichlorophosphate (52.8 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0059] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0060] Example 4

[0061] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0062] S1, quercetin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of dichloromethane and dissolved under magnetic stirring at room temperature to obtain solution I;

[0063] S2, diphenyldichlorosilane (63.3 g, 0.25 mol) was added dropwise to solution I, and the mixture was reacted for 2 h at 0-5 °C in a nitrogen atmosphere, and then the mixture was heated to room temperature and reacted for 6 h to obtain solution II;

[0064] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0065] Example 5

[0066] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0067] S1, naringenin (27.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of tetrahydrofuran and dissolved under magnetic stirring at room temperature to obtain solution I;

[0068] S2, adding phenylphosphoryl dichloride (48.5 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0069] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0070] Example 6

[0071] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0072] S1, naringenin (27.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of chloroform and dissolved under magnetic stirring at room temperature to obtain solution I;

[0073] S2, adding methylphosphoryl dichloride (33.3 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0074] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0075] Example 7

[0076] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0077] S1, naringenin (27.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of N,N-dimethylformamide and dissolved under magnetic stirring at room temperature to obtain solution I;

[0078] S2, adding phenyl dichlorophosphate (52.8 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0079] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0080] Example 8

[0081] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0082] S1, naringenin (27.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of dichloromethane and dissolved under magnetic stirring at room temperature to obtain solution I;

[0083] S2, diphenyldichlorosilane (63.3 g, 0.25 mol) was added dropwise to solution I, and the mixture was reacted for 2 h at 0-5 °C in a nitrogen atmosphere, and then the mixture was heated to room temperature and reacted for 6 h to obtain solution II;

[0084] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0085] Example 9

[0086] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0087] S1, luteolin (28.7 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of tetrahydrofuran and dissolved under magnetic stirring at room temperature to obtain solution I;

[0088] S2, adding phenylphosphoryl dichloride (48.5 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0089] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0090] Example 10

[0091] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0092] S1, luteolin (28.7 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of chloroform and dissolved under magnetic stirring at room temperature to obtain solution I;

[0093] S2, adding methylphosphoryl dichloride (33.3 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0094] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0095] Embodiment 11

[0096] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0097] S1, luteolin (28.7 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of N,N-dimethylformamide and dissolved under magnetic stirring at room temperature to obtain solution I;

[0098] S2, adding phenyl dichlorophosphate (52.8 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0099] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 ml of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0100] Example 12

[0101] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0102] S1, luteolin (28.7 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of chloroform and dissolved under magnetic stirring at room temperature to obtain solution I;

[0103] S2, diphenyldichlorosilane (63.3 g, 0.25 mol) was added dropwise to solution I, and the mixture was reacted for 2 h at 0-5 °C in a nitrogen atmosphere, and then the mixture was heated to room temperature and reacted for 6 h to obtain solution II;

[0104] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0105] Embodiment 13

[0106] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0107] S1, hesperidin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of tetrahydrofuran and dissolved under magnetic stirring at room temperature to obtain solution I;

[0108] S2, adding phenylphosphoryl dichloride (48.5 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0109] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0110] Embodiment 14

[0111] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0112] S1, hesperidin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of chloroform and dissolved under magnetic stirring at room temperature to obtain solution I;

[0113] S2, adding methylphosphoryl dichloride (33.3 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0114] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0115] Embodiment 15

[0116] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0117] S1, hesperidin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of N,N-dimethylformamide and dissolved under magnetic stirring at room temperature to obtain solution I;

[0118] S2, adding phenyl dichlorophosphate (52.8 g, 0.25 mol) dropwise into solution I, reacting for 2 h at 0-5 °C nitrogen atmosphere, then heating to room temperature and reacting for 6 h to obtain solution II;

[0119] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0120] Example 16

[0121] The preparation method of a flavonol hyperbranched flame retardant comprises the following steps:

[0122] S1, hesperidin (30.3 g, 0.1 mol) and triethylamine (25.3 g, 0.25 mol) were dissolved in 500 mL of dichloromethane and dissolved under magnetic stirring at room temperature to obtain solution I;

[0123] S2, diphenyldichlorosilane (63.3 g, 0.25 mol) was added dropwise to solution I, and the mixture was reacted for 2 h at 0-5 °C in a nitrogen atmosphere, and then the mixture was heated to room temperature and reacted for 6 h to obtain solution II;

[0124] S3. Filter solution II and air-dry for 12 hours to obtain a solid. Put the solid into a beaker with 500 mL of deionized water, stir and filter. Dry the solid in a vacuum oven at 80° C. for 12 hours, grind and sieve 100 mesh, and collect the product.

[0125] Application Example 1

[0126] Weigh 79.6 parts of epoxy resin, 19.9 parts of curing agent and 0.5 parts of flavonol hyperbranched flame retardant in Example 1, stir them under vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and perform a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0127] Application Example 2

[0128] Weigh 78.8 parts of epoxy resin, 19.7 parts of curing agent and 1.5 parts of flavonol hyperbranched flame retardant in Example 2, stir them under vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0129] Application Example 3

[0130] Weigh 77.6 parts of epoxy resin, 19.4 parts of curing agent and 3 parts of flavonol hyperbranched flame retardant in Example 3, stir them under vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0131] Application Example 4

[0132] Weigh 76 parts of epoxy resin, 19 parts of curing agent and 5 parts of flavonol hyperbranched flame retardant of Example 4, stir them under vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0133] Application Example 5

[0134] Weigh 79.6 parts of epoxy resin, 19.9 parts of curing agent and 0.5 parts of flavonol hyperbranched flame retardant in Example 5, stir them under vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0135] Application Example 6

[0136] Weigh 79.2 parts of epoxy resin, 19.8 parts of curing agent and 1 part of flavonol hyperbranched flame retardant in Example 6, stir them under vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0137] Application Example 7

[0138] Weigh 78.4 parts of epoxy resin, 19.6 parts of curing agent and 2 parts of flavonol hyperbranched flame retardant in Example 7, stir them magnetically under vacuum at 80°C for 30 minutes, then pour them into a mold, and carry out a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0139] Application Example 8

[0140] Weigh 77.6 parts of epoxy resin, 19.4 parts of curing agent and 3 parts of flavonol hyperbranched flame retardant of Example 8, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0141] Application Example 9

[0142] Weigh 76.8 parts of epoxy resin, 19.2 parts of curing agent and 4 parts of flavonol hyperbranched flame retardant in Example 9, stir them magnetically under vacuum at 80°C for 30 minutes, then pour them into a mold, and carry out a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0143] Application Example 10

[0144] Weigh 76 parts of epoxy resin, 19 parts of curing agent and 5 parts of flavonol hyperbranched flame retardant in Example 10, stir them magnetically under vacuum at 80°C for 30 minutes, then pour them into a mold, and perform a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0145] Application Example 11

[0146] Weigh 78.8 parts of epoxy resin, 19.7 parts of curing agent and 1.5 parts of flavonol hyperbranched flame retardant in Example 11, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0147] Application Example 12

[0148] Weigh 78 parts of epoxy resin, 19.5 parts of curing agent and 2.5 parts of flavonol hyperbranched flame retardant in Example 12, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0149] Application Example 13

[0150] Weigh 77.2 parts of epoxy resin, 19.3 parts of curing agent and 3.5 parts of flavonol hyperbranched flame retardant in Example 13, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0151] Application Example 14

[0152] Weigh 76.4 parts of epoxy resin, 19.1 parts of curing agent and 4.5 parts of flavonol hyperbranched flame retardant of Example 14, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0153] Application Example 15

[0154] Weigh 78.4 parts of epoxy resin, 19.6 parts of curing agent and 2 parts of flavonol hyperbranched flame retardant in Example 15, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0155] Application Example 16

[0156] Weigh 76.8 parts of epoxy resin, 19.2 parts of curing agent and 4 parts of flavonol hyperbranched flame retardant of Example 16, stir them with vacuum magnetic stirring at 80°C for 30 minutes, then pour them into a mold, and carry out curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid flame-retardant epoxy resin composite material.

[0157] Application Example 17

[0158] 99.5 parts of the dried polycarbonate and 0.5 parts of the flavonol hyperbranched flame retardant of Example 1 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0159] Application Example 18

[0160] 98 parts of the dried polycarbonate and 2 parts of the flavonol hyperbranched flame retardant of Example 2 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded at 260° C. to 275° C. into various standard specimens.

[0161] Application Example 19

[0162] 98.5 parts of the dried polycarbonate and 1.5 parts of the flavonol hyperbranched flame retardant of Example 3 were added to a twin-screw extruder for mixing, extrusion, and granulation, and then injection-molded at 260° C. to 275° C. into various standard specimens.

[0163] Application Example 20

[0164] 96 parts of the dried polycarbonate and 4 parts of the flavonol hyperbranched flame retardant of Example 4 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded at 260° C. to 275° C. into various standard specimens.

[0165] Application Example 21

[0166] 95 parts of the dried polycarbonate and 5 parts of the flavonol hyperbranched flame retardant of Example 5 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded at 260° C. to 275° C. into various standard specimens.

[0167] Application Example 22

[0168] 98.5 parts of the dried polycarbonate and 1.5 parts of the flavonol hyperbranched flame retardant of Example 6 were added to a twin-screw extruder for mixing, extrusion, and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0169] Application Example 23

[0170] 97.5 parts of the dried polycarbonate and 2.5 parts of the flavonol hyperbranched flame retardant of Example 7 were added to a twin-screw extruder for mixing, extrusion, and granulation, and then injection-molded at 260° C. to 275° C. into various standard specimens.

[0171] Application Example 24

[0172] 96 parts of the dried polycarbonate and 4 parts of the flavonol hyperbranched flame retardant of Example 8 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0173] Application Example 25

[0174] 95 parts of the dried polycarbonate and 5 parts of the flavonol hyperbranched flame retardant of Example 9 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0175] Application Example 26

[0176] 99.5 parts of the dried polycarbonate and 0.5 parts of the flavonol hyperbranched flame retardant of Example 10 were added to a twin-screw extruder for mixing, extrusion, and granulation, and then injection-molded at 260° C. to 275° C. into various standard specimens.

[0177] Application Example 27

[0178] 99 parts of the dried polycarbonate and 1 part of the flavonol hyperbranched flame retardant of Example 11 were added to a twin-screw extruder for mixing, extrusion, and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0179] Application Example 28

[0180] 95 parts of the dried polycarbonate and 5 parts of the flavonol hyperbranched flame retardant of Example 12 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0181] Application Example 29

[0182] 98.5 parts of the dried polycarbonate and 1.5 parts of the flavonol hyperbranched flame retardant of Example 13 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0183] Application Example 30

[0184] 97.5 parts of the dried polycarbonate and 2.5 parts of the flavonol hyperbranched flame retardant of Example 14 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0185] Application Example 31

[0186] 98.5 parts of the dried polycarbonate and 1.5 parts of the flavonol hyperbranched flame retardant of Example 15 were added to a twin-screw extruder for mixing, extrusion, and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0187] Application Example 32

[0188] 98 parts of the dried polycarbonate and 2 parts of the flavonol hyperbranched flame retardant of Example 16 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0189] Application Example 33

[0190] 99.5 parts of dried polypropylene and 0.5 parts of the flavonol hyperbranched flame retardant of Example 1 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0191] Application Example 34

[0192] 97 parts of dried polypropylene and 3 parts of the flavonol hyperbranched flame retardant of Example 2 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0193] Application Example 35

[0194] 95 parts of dried polypropylene and 5 parts of the flavonol hyperbranched flame retardant of Example 3 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0195] Application Example 36

[0196] 99.5 parts of dried polypropylene and 0.5 parts of the flavonol hyperbranched flame retardant of Example 4 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0197] Application Example 37

[0198] 99 parts of dried polypropylene and 1 part of the flavonol hyperbranched flame retardant of Example 5 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0199] Application Example 38

[0200] 96.5 parts of dried polypropylene and 3.5 parts of the flavonol hyperbranched flame retardant of Example 6 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0201] Application Example 39

[0202] 95.5 parts of dried polypropylene and 4.5 parts of the flavonol hyperbranched flame retardant of Example 7 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0203] Application Example 40

[0204] 98 parts of dried polypropylene and 2 parts of the flavonol hyperbranched flame retardant of Example 8 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0205] Application Example 41

[0206] 99.5 parts of dried polypropylene and 0.5 parts of the flavonol hyperbranched flame retardant of Example 9 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0207] Application Example 42

[0208] 99 parts of dried polypropylene and 1 part of the flavonol hyperbranched flame retardant of Example 10 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0209] Application Example 43

[0210] 96.5 parts of dried polypropylene and 3.5 parts of the flavonol hyperbranched flame retardant of Example 11 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0211] Application Example 44

[0212] 98 parts of dried polypropylene and 2 parts of the flavonol hyperbranched flame retardant of Example 12 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0213] Application Example 45

[0214] 96 parts of dried polypropylene and 4 parts of the flavonol hyperbranched flame retardant of Example 13 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0215] Application Example 46

[0216] 99.5 parts of dried polypropylene and 0.5 parts of the flavonol hyperbranched flame retardant of Example 14 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0217] Application Example 47

[0218] 96.5 parts of dried polypropylene and 3.5 parts of the flavonol hyperbranched flame retardant of Example 15 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0219] Application Example 48

[0220] 98 parts of dried polypropylene and 2 parts of the flavonol hyperbranched flame retardant of Example 16 were added to a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0221] Comparative Example 1

[0222] Weigh 80 parts of epoxy resin and 20 parts of 4,4'-diaminodiphenylmethane (DDM curing agent), stir them magnetically under vacuum at 80°C for 30 minutes, then pour them into a mold and perform a curing reaction through a programmed temperature rise process of 100°C / 3h+140°C / 3h to obtain a solid, which is a pure epoxy resin thermosetting material (EP).

[0223] Comparative Example 2

[0224] The dried polycarbonate is added into a twin-screw extruder for mixing, extrusion and granulation, and then injection-molded into various standard specimens at 260° C. to 275° C.

[0225] Comparative Example 3

[0226] The dried polypropylene is added into a twin-screw extruder for mixing, extrusion and granulation, and then injection molded into various standard specimens at 260°C to 275°C.

[0227] Experimental examples verify the experimental results

[0228] In order to verify the fireproof effect of the composite material prepared by the flavonol hyperbranched flame retardant of the present application, an experiment was conducted. The limiting oxygen index (LOI) and vertical burning rating (UL-94) of comparative examples 1 to 2 and application examples 1 to 48 as well as the improvement of mechanical properties were tested. The data are shown in the following table:

[0229]

[0230]

[0231] As can be seen from the table above, the introduction of phosphophenyl and silylphenyl groups significantly improves the flame retardancy and mechanical properties of the composite material. And from the TGA data, it can be seen that after adding the flame retardant, its thermal stability is significantly improved. The main reason is that after adding the flame retardant, the stability of the resin is significantly improved due to the introduction of rigid benzene rings and phosphorus and silicon groups.

[0232] Depend on Figure 3 It can be obtained that the glass transition temperature of the pure epoxy resin in Comparative Example 1 is 133.3° C., which is significantly lower than that of the epoxy resin composite material after adding the flame retardant described in Examples 1 and 16, and this is consistent with the results shown by TGA.

[0233] Therefore, when preparing a composite material, the flavonol hyperbranched flame retardant of the present application can not only improve the flame retardant effect and reduce the amount of smoke, but also ensure the thermal stability of the composite material and enhance the impact performance of the composite material.

[0234] The above is only a preferred embodiment of the present application. It should be understood that the present application is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the concept described herein through the above teachings or the technology or knowledge in the relevant field. The changes and modifications made by those skilled in the art shall not deviate from the spirit and scope of the present application, and shall be within the scope of protection of the claims attached to the present application.

Claims

1. A flavonol hyperbranched flame retardant, characterized in that: The structural formula is as shown in Formula I: Formula I: Among them, the wavy lines in the structural formula are repeating units in the structure; In the formula I, R n (n=1 to 7) is a hydroxyl group.

2. The flavonol hyperbranched flame retardant according to claim 1, characterized in that The R' includes a phosphine ring group and a silylphenyl group.

3. A method for preparing the flavonol hyperbranched flame retardant according to claim 1 or 2, characterized in that: The following steps are involved: Mixing a flavonol compound, a solvent and triethylamine to obtain a solution I; Add the dichlorinated organophosphorus organosilicon compound dropwise into the solution I, react for 2 h in a nitrogen atmosphere at 0-5° C., then heat to room temperature and continue to react for 6 h to obtain solution II; The solution II is filtered, air-dried, washed, dried and ground, and then the solid is collected to obtain the flavonol hyperbranched flame retardant.

4. The method according to claim 3, characterized in that The flavonol compound includes one of quercetin, naringenin, luteolin and hesperetin; And / or, the dichloride-containing organophosphorus organosilicon compound includes one of methyl phosphoryl dichloride, phenyl phosphoryl dichloride, phenyl dichlorophosphate and diphenyldichlorosilane; And / or, the solvent includes one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide and chloroform.

5. The method according to claim 3, characterized in that: The molar ratio of the flavonol compound to the dichloroorganophosphorus organosilicon compound is 1:2.

5.

6. Use of the flavonol hyperbranched flame retardant according to claims 1 to 2 or the method according to any one of claims 3 to 5 in preparing a flame retardant composite material; in, The flame retardant composite material includes epoxy resin flame retardant composite material and thermoplastic resin flame retardant composite material.

7. The use according to claim 6, characterized in that: The method for preparing the epoxy resin flame retardant composite material comprises the following steps: Adding epoxy resin and curing agent to the first flame retardant, stirring under vacuum conditions, and immediately pouring the intermediate product into a mold after obtaining it, performing a curing reaction, and then cooling it to room temperature to obtain the epoxy resin composite material; And / or, the method for preparing the thermoplastic resin flame retardant composite material comprises the following steps: Adding a second flame retardant to a thermoplastic resin, drying, mixing, extruding, granulating and thermoplasticizing the resin, to obtain the thermoplastic resin flame retardant composite material; Wherein, the first flame retardant and the second flame retardant include flavonol hyperbranched flame retardants.

8. The use according to claim 7, characterized in that: The first flame retardant and the second flame retardant include flavonol hyperbranched flame retardants; And / or, the epoxy resin comprises E51 type epoxy resin; and / or, the curing agent comprises 4,4-diaminodiphenylmethane (DDM); And / or, the thermoplastic resin includes polycarbonate resin and polypropylene resin.

9. The use according to claim 7, characterized in that: The weight ratio of the first flame retardant, the epoxy resin and the curing agent is (0.5-5): (75-80): (19-20); And / or, the weight ratio of the second flame retardant to the thermoplastic resin is (0.5-5):(95-100).

10. The use according to claim 7, characterized in that: The stirring method includes magnetic stirring; wherein the temperature of the magnetic stirring is 60° C. to 80° C., and the time of the magnetic stirring is 0.5 to 0.8 h; The temperature of the curing reaction is calculated according to a programmed temperature rise mode, and the programmed temperature rise mode is: curing temperature = 100°C / 3h+140°C / 3h; And / or, the drying method includes vacuum drying; wherein the vacuum drying temperature is 80° C. and the vacuum drying time is 24 hours; And / or, the thermoplastic temperature is 260°C to 275°C.

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