Phosphorus-containing hybrid metal salt compound as well as preparation method and application thereof

Abstract

The invention discloses a phosphorus-containing hybrid metal salt compound and a preparation method and application thereof, the phosphorus-containing hybrid metal salt compound and dialkyl phosphinate have good flame-retardant synergy, the flame-retardant efficiency can be improved, and meanwhile, the corrosivity of a dialkyl phosphinate flame retardant can be reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new materials, in particular to a phosphorus-containing hybrid metal salt compound and a preparation method and application thereof. BACKGROUND

[0002] Phosphorus flame retardants are widely used due to their environmental protection and high flame retardant properties. Dialkyl phosphinic acid salt is a typical representative of phosphorus flame retardants. Due to its high phosphorus content and high temperature resistance, it is a widely used halogen-free flame retardant, which can be applied to thermoplastic materials such as nylon, polyester, TPE, and can also be applied to thermosetting materials such as PU, epoxy resin, unsaturated polyester. However, there are still two main problems with dialkyl phosphinic acid salt flame retardant: (1) dialkyl phosphinic acid salt has strong acidity and strong corrosion to processing equipment; (2) for some materials, such as nylon, the use of dialkyl phosphinic acid salt alone, especially some nylon thin products, has insufficient flame retardant properties.

[0003] To solve these two problems, various solutions have been reported. For example, for the flame retardant application of nylon materials, the synergistic effect with phosphite can effectively solve the problem of low flame retardant efficiency, but phosphite still has the problem of corrosion. To solve the corrosion problem, various basic substances or acid absorbents are used, but the use of these basic substances or acid absorbents will reduce the flame retardant properties of dialkyl phosphinic acid salt. There is currently no compound that can both improve flame retardant efficiency and solve corrosion. The existing technology is to find a balance and compromise between improving flame retardation and reducing corrosion. If corrosion is considered, the flame retardant performance will be sacrificed, and if flame retardation is considered, the corrosion will be sacrificed. SUMMARY

[0004] The following is a summary of the subject matter of the detailed description herein. This summary is not intended to limit the scope of protection of the present application.

[0005] The main purpose of the present application is to disclose a phosphate-regulated phosphorus-containing hybrid metal salt compound, and to provide a preparation method and application thereof. Compared with non-hybrid phosphite, when used with dialkyl phosphinic acid salt flame retardant, the compound has good flame retardant synergy, improves the flame retardant efficiency, can meet the UL94 V0 flame retardant requirement of 0.4mm thin, and also reduces the corrosion of dialkyl phosphinic acid salt flame retardant.

[0006] The first aspect of the present application relates to a phosphorus-containing hybrid metal salt compound, which comprises: a metal ion and a phosphorus-containing hybrid anion; The phosphorus-containing hybrid anion comprises: a phosphorus-containing structure anion of formula I, and any one or more of the phosphorus-containing structure anions of structural formula II, the phosphorus-containing structure anions of structural formula III, and the phosphorus-containing structure anions of structural formula IV; The phosphorus-containing structure anions of structural formula I, the phosphorus-containing structure anions of structural formula II, the phosphorus-containing structure anions of structural formula III, and the phosphorus-containing structure anions of structural formula IV are as follows: I, II, III, IV; In structural formula I, m is an integer from 0 to 2.

[0007] In an exemplary embodiment, the metal element in the metal ion is any one of Ca, Mg, Al, Zn, Fe, Sn, Ti, TiO, a rare earth metal element, and the like; optionally, the metal element is Al.

[0008] In an exemplary embodiment, the phosphorus-containing hybrid metal salt compound has a structural formula as follows: V; wherein p is from 0.001 to 0.997, x is from 0.001 to 0.997, y is from 0.001 to 0.997, z is from 0.001 to 0.2, and p+x+y+z = 1; m is an integer from 0 to 2; n is the valence of the metal M, which is an integer from 1 to 4; and M is a metal element.

[0009] The compound of formula V represents a preferred phosphorus-containing hybrid metal salt compound formed from a phosphate and other phosphorus-containing anions, including phosphite, hydrogen phosphite, pyrophosphite.

[0010] In an exemplary embodiment, the phosphorus-containing hybrid metal salt compound has a structural formula as follows: VI, wherein x is from 0.001 to 0.998, y is from 0.001 to 0.998, z is from 0.001 to 0.2, and x+y+z = 1; m is an integer from 0 to 2; n is the valence of the metal M, which is an integer from 1 to 4; and M is a metal element.

[0011] The compound of formula VI represents a preferred phosphorus-containing hybrid metal salt compound formed from a phosphate and other phosphorus-containing anions, including phosphite, hydrogen phosphite.

[0012] In an exemplary embodiment, the phosphorus-containing hybrid metal salt compound has a structural formula as follows: VII, wherein p is 0.001-0.998, x is 0.001-0.998, z is 0.001-0.2, and p+x+z = 1; m is an integer from 0 to 2; n is the valence of the metal M, and is an integer from 1 to 4; and M is a metal element.

[0013] The compound of Formula VII represents a preferred phosphorus-containing heterometallic salt compound formed from a phosphate and other phosphorus-containing anions, including phosphite, pyrophosphite.

[0014] In an exemplary embodiment, the phosphorus-containing heterometallic salt compound has the formula: VIII; wherein p is 0.001-0.998, x is 0.001-0.998, z is 0.001-0.2, and p+x+z = 1; m is an integer from 0 to 2; n is the valence of the metal M, and is an integer from 1 to 4; and M is a metal element.

[0015] The compound of Formula VIII represents a preferred phosphorus-containing heterometallic salt compound formed from a phosphate and other phosphorus-containing anions, including phosphite, pyrophosphite.

[0016] In an exemplary embodiment, the phosphorus-containing heterometallic salt compound has the formula: IX; wherein x is 0.8-0.999, z is 0.001-0.2, and x+z = 1; m is an integer from 0 to 2; n is the valence of the metal M, and is an integer from 1 to 4; and M is a metal element.

[0017] The compound of Formula IX represents a preferred phosphorus-containing heterometallic salt compound formed from a phosphate and other phosphorus-containing anions, including phosphite.

[0018] In an exemplary embodiment, the phosphorus-containing heterometallic salt compound has the formula: X; wherein y is 0.8-0.999, z is 0.001-0.2, and y+z = 1; m is an integer from 0 to 2; n is the valence of the metal M, and is an integer from 1 to 4; and M is a metal element.

[0019] The compound of Formula X represents a preferred phosphorus-containing heterometallic salt compound formed from a phosphate and other phosphorus-containing anions, including phosphite.

[0020] In an exemplary embodiment, the phosphorus-containing heterometallic salt compound has the formula: XI; wherein: p is 0.8-0.999, z is 0.001-0.2, and p+z=1; m is an integer of 0-2; n is the valence of metal M, which is an integer of 1-4; M is a metal element.

[0021] The compound of formula XI represents a preferred phosphorus-containing heterometallic salt compound formed by phosphates and other phosphorus-containing anions, the other phosphorus-containing anion being pyrophosphates.

[0022] The second aspect of the present application provides a method for preparing the above phosphorus-containing heterometallic salt compound, comprising the following steps: 1) reacting the phosphorus-containing hetero-anion donor and the metal ion donor at 80-110°C to obtain a precipitate of the phosphorus-containing heterometallic salt compound; 2) washing and filtering the precipitate and drying the moisture; 3) high-temperature treating the precipitate obtained in step 2) at 120-300°C; and Optionally, 4) crushing the material obtained in step 3).

[0023] In an exemplary embodiment, the phosphorus-containing hetero-anion donor comprises an acid or a soluble salt of the phosphorus-containing structure of formula I, and a mixture of acids or soluble salts of any one or more of the phosphorus-containing structure of formula II, the phosphorus-containing structure of formula III, and the phosphorus-containing structure of formula IV, or The phosphorus-containing hetero-anion donor is an acid or a soluble salt of any one or more of the phosphorus-containing structure of formula II, the phosphorus-containing structure of formula III, and the phosphorus-containing structure of formula IV, or a mixture thereof.

[0024] In an exemplary embodiment, the soluble salt is a sodium salt or a potassium salt.

[0025] In an exemplary embodiment, the metal ion donor is a metal compound, optionally, the metal ion donor is a metal salt compound or a metal oxide or a metal hydroxide.

[0026] In an exemplary embodiment, the metal ion donor is an aluminum-containing compound; optionally, the aluminum-containing compound is at least one of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, and aluminum oxide.

[0027] In an exemplary embodiment, in step 1), the metal ion donor is first dissolved or dispersed in water to form a metal ion donor solution or a suspension-dispersion system, and then reacted with the phosphorus-containing hetero-anion donor.

[0028] In an exemplary embodiment, in step 1), the phosphorus-containing hybrid anion donor and the metal ion donor can be added in a full reaction equivalent molar ratio.

[0029] In an exemplary embodiment, in step 1), the mass concentration of the metal ion donor solution or suspension dispersion system is 15%-50%.

[0030] In an exemplary embodiment, in step 1), the reaction time of the phosphorus-containing hybrid anion donor and the metal ion donor is 1-5 hours.

[0031] In an exemplary embodiment, step 2) includes: filtering and washing the precipitate until the conductivity of the washing water is less than 500 µs / cm.

[0032] In an exemplary embodiment, step 2) includes: drying the moisture of the washed precipitate at 100-120℃.

[0033] In an exemplary embodiment, in step 2), the heating drying can use various ovens, drying rooms, dryers, etc.

[0034] In an exemplary embodiment, step 3) includes: after continuing the slow gradient temperature rising of the material in step 2) for 2-10 hours, the temperature of the material is raised to greater than 120℃ but not more than 300℃, and the temperature is maintained for 1-300 min.

[0035] In an exemplary embodiment, when the phosphorus-containing hybrid anion donor includes: an acid or a soluble salt of a phosphorus-containing structure of structural formula I, and a mixture of an acid or a soluble salt of any one or more of a phosphorus-containing structure of structural formula II, a phosphorus-containing structure of structural formula III, and a phosphorus-containing structure of structural formula IV, the preparation method includes: 1) dissolving the phosphorus-containing hybrid anion donor in water in proportion, adding a metal ion donor to react at 80-110℃ to obtain a precipitate of a phosphorus-containing hybrid metal salt compound; 2) washing and filtering the precipitate, and drying the moisture; 3) treating the precipitate obtained in step 2) at a high temperature of 120-300℃ in an inert atmosphere or vacuum state; 4) according to needs, crushing the material obtained in step 3) to a desired particle size range.

[0036] In an exemplary embodiment, the inert atmosphere in step 3) is a rare gas atmosphere or a nitrogen atmosphere, etc.

[0037] In an exemplary embodiment, in step 1), when the metal ion donor is insoluble in water, the metal ion donor can be first dispersed in water to form a metal ion donor suspension system, and then reacted with the acid in the phosphorus-containing hybrid anion donor without adding high concentration of strong acid.

[0038] In an exemplary embodiment, in step 1), when the metal ion donor is a water-soluble compound, it needs to be reacted under the condition of high concentration of strong acid; at this time, the metal ion donor is reacted with the soluble salt in the phosphorus-containing hybrid anion donor; specifically, the phosphorus-containing hybrid anion donor and the metal ion donor are dissolved in water in the presence of a small amount of strong acid, and reacted at 80-110°C, and finally the pH value of the liquid phase in the reaction system is controlled to be less than 4, to obtain a precipitate of phosphorus-containing hybrid metal salt.

[0039] In an exemplary embodiment, in step 1), the strong acid is selected from any one of concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid and concentrated phosphoric acid.

[0040] In an exemplary embodiment, in step 1), the mass of the strong acid added is 2%-5% of the mass of the phosphorus-containing hybrid anion donor.

[0041] In an exemplary embodiment, in step 1), the pH value of the liquid phase in the reaction system can be adjusted by adding a base or a metal oxide.

[0042] In an exemplary embodiment, when the phosphorus-containing hybrid anion donor is any one or more of the acid or soluble salt of the phosphorus-containing structure of structural formula II, the phosphorus-containing structure of structural formula III and the phosphorus-containing structure of structural formula IV, or a mixture thereof, the preparation method comprises: 1) dissolving the phosphorus-containing hybrid anion donor in water in proportion, adding a metal ion donor, and reacting at 80-110°C, the reaction being carried out in an air atmosphere or an oxygen atmosphere, to obtain a precipitate of phosphorus-containing hybrid metal salt; 2) washing and filtering the precipitate, and drying the water content; 3) high-temperature treating the precipitate obtained in step 2) at 180-300°C in an air atmosphere or an oxygen atmosphere; 4) according to needs, crushing the material obtained in step 3) to a desired particle size range.

[0043] The third aspect of the present application provides a compound, which comprises: a mixture of one or more of the phosphorus-containing hybrid metal salt compounds described above, and other any flame retardant.

[0044] In an exemplary embodiment, the flame retardant is selected from the group consisting of a mixture or combination of one or more of a phosphorus-containing compound, an aluminum-containing compound, a nitrogen-containing compound, a zinc-containing compound, a silicon-containing compound, and the like.

[0045] In an exemplary embodiment, the flame retardant is a phosphorus-containing compound.

[0046] In an exemplary embodiment, the phosphorus-containing compound is selected from the group consisting of a mixture or combination of one or more of a dialkyl phosphinate salt, a monoalkyl phosphinate salt, a hypophosphite salt, a phosphite salt; Preferably, the phosphorus-containing compound is an aluminum salt of diethyl phosphinate.

[0047] In an exemplary embodiment, the phosphorus-containing hybrid metal salt compound has a content of phosphate group of 20% or less, preferably 10% or less, of the total phosphorus-containing anion.

[0048] The fourth aspect of the present application provides a use of a mixture of one or more of the above phosphorus-containing hybrid metal salt compounds as a flame retardant, a flame retardant mixture, and a flame retardant synergist, or for preparing a flame-retardant polymer material, or for imparting flame retardancy to polyester and cellulose pure fabric and mixed fabric by impregnation.

[0049] The fifth aspect of the present application provides a use of the above mixture as a flame retardant, a flame retardant mixture, and a flame retardant synergist, or for preparing a flame-retardant polymer material, or for imparting flame retardancy to polyester and cellulose pure fabric and mixed fabric by impregnation.

[0050] In an exemplary embodiment, the flame retardant includes one or more of a flame retardant for clear varnish and foamed paint, a flame retardant for wood and other cellulose-containing products, and a non-reactive flame retardant for polymers.

[0051] In an exemplary embodiment, the flame-retardant polymer material includes one or more of a flame-retardant polymer molding material, a flame-retardant polymer shaped body, a flame-retardant polymer film, a flame-retardant polymer thread, and a polymer fiber. Preferably, the flame-retardant polymer material includes one or more of a flame-retardant thermoplastic or thermosetting polymer molding material, a flame-retardant polymer shaped body, a flame-retardant polymer film, a flame-retardant polymer thread, and a polymer fiber.

[0052] The sixth aspect of the present application provides a flame-retardant polymer material, the raw material of which includes a polymer matrix, an additive, a filler, or a reinforcing material, and any one of the following: a mixture of one or more of the above phosphorus-containing hybrid metal salt compounds, or a flame retardant mixture containing a mixture of one or more of the above phosphorus-containing hybrid metal salt compounds, or the above described compound mixture, or a flame retardant mixture comprising the above described compound mixture.

[0053] In an exemplary embodiment, the flame retardant polymer material comprises, based on the total mass of the raw materials being 100%: 0.1 wt% to 45 wt% of a compound mixture of one or more of the phosphorus-containing hybrid metal salt compounds, 55 wt% to 99.9 wt% of a polymer matrix, 0 to 44.9 wt% of additives, and 0 to 44.9 wt% of fillers or reinforcing materials.

[0054] In an exemplary embodiment, the flame retardant polymer material comprises, based on the total mass of the raw materials being 100%: 0.1 to 45 wt% of a flame retardant mixture, 55 wt% to 99.9 wt% of a polymer matrix, 0 to 44.9 wt% of additives, and 0 to 44.9 wt% of fillers or reinforcing materials; wherein the flame retardant mixture comprises 0.1 wt% to 50 wt% of a compound mixture of one or more of the phosphorus-containing hybrid metal salt compounds and 50 wt% to 99.9 wt% of a flame retardant.

[0055] In an exemplary embodiment, the flame retardant polymer material comprises, based on the total mass of the raw materials being 100%: 0.1 wt% to 45 wt% of the above described compound mixture, 55 wt% to 99.9 wt% of a polymer matrix, 0 to 55 wt% of additives, and 0 to 55 wt% of fillers or reinforcing materials.

[0056] In an exemplary embodiment, the flame retardant polymer material comprises, based on the total mass of the raw materials being 100%: 0.1 to 45 wt% of a flame retardant mixture, 55 wt% to 99.9 wt% of a polymer matrix, 0 to 55 wt% of additives, and 0 to 55 wt% of fillers or reinforcing materials; wherein the flame retardant mixture comprises 0.1 wt% to 50 wt% of the above described compound mixture and 50 wt% to 99.9 wt% of a flame retardant.

[0057] In an exemplary embodiment, the flame retardant is selected from one or more of dialkylphosphinic acid metal salts, inorganic phosphinic acid salts, phosphite salts, zinc containing compounds, melamine derivatives and the like.

[0058] In an exemplary embodiment, the flame retardant is selected from one or more of: dialkylphosphinic acid and / or salts thereof; condensation products of melamine and / or reaction products of melamine with phosphoric acid and / or reaction products of condensation products of melamine with polyphosphoric acid or mixtures thereof; nitrogen containing phosphates; benzoguanamine, tris(hydroxyethyl)isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, dicyandiamide and / or guanidine; magnesium oxide, calcium oxide, aluminium oxide, zinc oxide, manganese oxide, tin oxide, aluminium hydroxide, boehmite, hydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate and / or zinc stannate; phosphite salts, hydrogen phosphite salts or condensates thereof; phosphate salts and derivatives thereof.

[0059] In an exemplary embodiment, the flame retardant is selected from one or more of: melam, melem, melemine, melamine diphosphate, melamine polyphosphate, melam polyphosphate, melemine polyphosphate and / or melem polyphosphate and / or mixed poly salts thereof and / or ammonium dihydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate.

[0060] In an exemplary embodiment, the flame retardant is selected from one or more of: aluminium phosphinate, zinc phosphinate, calcium phosphinate, sodium phosphite, monophenyl phosphinic acid and salts thereof, mixtures of dialkyl phosphinic acid and salts thereof with monoalkyl phosphinic acid and salts thereof, 2-carboxyethyl alkyl phosphinic acid and salts thereof, 2-carboxyethyl methyl phosphinic acid and salts thereof, 2-carboxyethyl aryl phosphinic acid and salts thereof, 2-carboxyethyl phenyl phosphinic acid and salts thereof, DOPO and salts thereof and adducts on p-benzoquinone.

[0061] In an exemplary embodiment, the polymer matrix is selected from any one or more of: polyurethanes (PU), thermoplastic elastomers (TPE), epoxy resins, unsaturated polyesters, nylons, polyesters and polyketone resins (POK) and the like.

[0062] Compared with the prior art, the present application has the following technical effects: In the present application, the phosphorus-containing hybrid metal salt compound is different from a single phosphorus-containing metal compound or a mixture of several phosphorus-containing metal compounds involved in hybridization, and exhibits different properties, and is a compound with a new hybrid structure. The phosphorus-containing hybrid metal salt compound can be synergistically compounded with a dialkyl phosphinate salt flame retardant, which can greatly improve the flame retardant performance, and also improve the corrosion performance, thereby achieving the purpose of the present application. The single-component phosphorus-containing metal compound or the mixture of several components without hybridization cannot achieve high flame retardancy while improving corrosion resistance.

[0063] From the hybridization results, the content of phosphate in the hybrid does not affect the formation of the hybrid, and similar XRD results of the hybrid can be obtained with different phosphate contents. However, from the application, the higher the content of phosphate, the more obvious the improvement of the corrosion resistance of the dialkyl phosphinate salt, but it is not conducive to flame retardancy. Therefore, in order to maintain the balance between flame retardancy and corrosion resistance, the content of phosphate in the hybrid is preferably controlled to be less than 20%, and more preferably controlled to be less than 10%.

[0064] The phosphate-regulated phosphorus-containing hybrid metal salt compound described in the present application can also be used as a flame retardant.

[0065] Other features and advantages of the present application will be described in the following description, and some of them will become apparent from the description, or will be understood by those skilled in the art through implementation of the present application. Other advantages of the present application can be achieved and obtained through the schemes described in the specification and the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0066] The accompanying drawings are used to provide an understanding of the technical solutions of the present application, and constitute a part of the specification, and are used together with the embodiments of the present application to explain the technical solutions of the present application, and do not constitute a limitation on the technical solutions of the present application.

[0067] Figure 1 Structure formula of the phosphoric acid-phosphorous acid hybrid aluminum salt (0.003:0.997) of the present application (the numbers represent the molar ratio of anions involved in hybridization); Figure 2 Phosphorus nuclear magnetic resonance results of the phosphoric acid-phosphorous acid hybrid aluminum salt (0.003:0.997) of the present application and the same proportion mixture; Figure 3 XRD pattern of the phosphoric acid-phosphorous acid hybrid aluminum salt (0.003:0.997) of the present application; Figure 4 XRD pattern of the mixture of aluminum phosphite and aluminum phosphate. DETAILED DESCRIPTION

[0068] In order to make the purpose, technical scheme and advantages of the present application more clear, the embodiments of the present application will be described in detail below. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other as long as there is no conflict.

[0069] The present application will be further described in detail below with reference to the embodiments, but the present application is not limited to the embodiments. Any equivalent replacement made according to the disclosure of the present application in the technical field belongs to the protection scope of the present application.

[0070] Preparation of phosphorus-containing hybrid metal salt compound Example 1 Synthesis of phosphorus acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt The molecular structure of the phosphorus acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt of the present application is shown in Figure 1 .

[0071] Preparation process: In a 2L reaction kettle, 126g (1mol) of sodium phosphite and 0.66g (0.004mol) of sodium phosphate were dissolved in 189.1g of water, and the mixture was fully stirred and dissolved to obtain a sodium phosphite and sodium phosphate mixed solution. In a 500mL beaker, 114.1g of aluminum sulfate was dissolved in 266.2g of water and transferred to a dropping funnel. The reaction kettle was heated to 90℃, and the aluminum sulfate solution was started to be added dropwise. The addition was completed in 2 hours, and the reaction was continued for 1 hour.

[0072] The hot filtrate was filtered, and the precipitate was washed multiple times until the conductivity of the washing water was less than 200µs / cm, and the washing was stopped. The material was transferred to an oven, and heated to 120℃ under a nitrogen atmosphere, and dried for 60min. The moisture content of the solid was 0.1wt%.

[0073] The temperature was increased to 180℃ at a rate of 2℃ / min under a nitrogen atmosphere, and maintained for 60min. The temperature was increased to 260℃ at a rate of 1℃ / min, and maintained for 30min. The temperature was decreased to room temperature, and the product was discharged to obtain the phosphorus acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt.

[0074] The material was crushed, and the average particle size D50 was 40μm. The yield was 96.7%.

[0075] The product was tested for phosphorus spectrum P-NMR and XRD. The results are shown in Table 1 and Figures 2-3 .

[0076] Example 2 Synthesis of phosphorus acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt The same as Example 1, except that the final temperature of the high temperature treatment was set to 280℃, and the P-NMR and XRD of the test sample were tested. The results are shown in Table 1 andFigures 2-3 as shown.

[0077] Example 3 Synthesis of phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt Preparation process: In a 2L reactor, 123g (1.5mol) of phosphorous acid and 0.69g of concentrated phosphoric acid (0.006mol) with a concentration of 85% were dissolved in 288.6g of water, and the solution was fully stirred and dissolved to obtain a mixed solution of phosphorous acid and phosphoric acid. In a 500mL beaker, 78.5g of aluminum hydroxide was dispersed in 200g of water and transferred to a dropping funnel. The reactor was heated and the temperature was raised to 90°C, and the aluminum hydroxide suspension was started to be added dropwise. The addition was completed in 2 hours, the pH value was adjusted to 2.6 by the aluminum hydroxide solid, and the reaction was continued for 1 hour at the same temperature.

[0078] The hot filtration was stopped, and the precipitate was washed multiple times until the conductivity of the washing water was less than 200µs / cm. The material was transferred to an oven, and the temperature was raised to 120°C under a nitrogen atmosphere, and dried for 60min. The moisture content of the solid was 0.1wt%.

[0079] The temperature was raised to 180°C at a rate of 2°C / min under a nitrogen atmosphere, and maintained for 60min. The temperature was raised to 260°C at a rate of 1°C / min, and maintained for 60min. The temperature was lowered to room temperature, and the product was discharged to obtain the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt.

[0080] The material was crushed, and the average particle size D50 was 38μm. The yield was 98.5%, and P-NMR and XRD tests were performed. The results are shown in Table 1 and Figures 2-3 as shown.

[0081] Example 4 Synthesis of phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt Preparation process: In a 2L reactor, 126g (1mol) of sodium phosphite was dissolved in 189.1g of water, and the solution was fully stirred and dissolved to obtain an aqueous solution of sodium phosphite. In a 500mL beaker, 114g of aluminum sulfate was dissolved in 266.2g of water and transferred to a dropping funnel. The reactor was heated, and the temperature was raised to 90°C under an air atmosphere, and the aluminum sulfate solution was started to be added dropwise. The addition was completed in 2 hours, and the reaction was continued for 1 hour at the same temperature.

[0082] The hot filtration was stopped, and the precipitate was washed multiple times until the conductivity of the washing water was less than 200µs / cm. The material was transferred to an oven, and the temperature was raised to 120°C under an air atmosphere, and dried for 60min. The moisture content of the solid was 0.1wt%.

[0083] The temperature was raised to 180°C at a rate of 2°C / min under air atmosphere, and maintained for 60 min. The temperature was then raised to 260°C at a rate of 1°C / min, and maintained for 30 min. The temperature was then lowered to room temperature, and the product was discharged. Phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt was obtained. The product was crushed, and the average particle size D50 was 40 μm. The yield was 96.7%.

[0084] The sample was tested for phosphorus spectrum NMR and XRD. The results are shown in Table 1 and Figures 2-3 .

[0085] Example 5 Synthesis of phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt Preparation process: In a 2L reaction kettle, 123 g (1.5 mol) of phosphorous acid was dissolved in 288.6 g of water under stirring to obtain an aqueous phosphorous acid solution. In a 500 mL beaker, 78.5 g of aluminum hydroxide was dispersed in 200 g of water, and transferred to a dropping funnel. The reaction kettle was heated, and the temperature was raised to 90°C under air atmosphere. The aluminum hydroxide suspension was started to be added dropwise, and the addition was completed in 2 hours. The pH value was adjusted to 2.6 by the aluminum hydroxide solid, and the reaction was continued for 1 hour.

[0086] The hot filtration was performed, and the precipitate was washed for multiple times until the conductivity of the washing water was less than 200 µs / cm. The washing was stopped. The product was transferred to an oven, and the temperature was raised to 120°C under air atmosphere. The product was dried for 60 min, and the moisture content of the solid was 0.1 wt%.

[0087] The temperature was raised to 180°C at a rate of 2°C / min under air atmosphere, and maintained for 60 min. The temperature was then raised to 260°C at a rate of 1°C / min, and maintained for 60 min. The temperature was then lowered to room temperature, and the product was discharged. Phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt was obtained.

[0088] The product was crushed, and the average particle size D50 was 38 μm. The yield was 98.5%. The product was tested for P-NMR and XRD. The results are shown in Table 1 and Figures 2-3 .

[0089] Example 6 Synthesis of phosphoric acid (0.01)-phosphorous acid (0.99) hybrid aluminum salt The same as in Example 3, except that the ratio of phosphoric acid and phosphorous acid involved in the hybridization was adjusted to be 0.01:0.99 in terms of molar ratio. Phosphoric acid (0.01)-phosphorous acid (0.99) hybrid aluminum salt was prepared. The product was tested for P-NMR and XRD. The results are shown in Table 1.

[0090] Example 7 Synthesis of phosphoric acid (0.003)-phosphorous acid (0.990)-phosphinic acid (0.007) hybrid aluminum salt The same as example 1, except that the reactants are increased in phosphorous acid, and the ratio of the three reactants is: phosphate: phosphite: hydrogen phosphite molar ratio of 0.003: 0.990: 0.007, phosphorous acid (0.003)-phosphite (0.990)-hydrogen phosphite (0.007) hybrid aluminum salt is prepared. And P-NMR and XRD test results, as shown in Table 1.

[0091] Example 8 Synthesis of phosphorous acid (0.003)-phosphite (0.990)-pyrophosphite (0.007) hybrid aluminum salt The same as example 1, except that the reactants are increased in phosphorous acid, and the ratio of the three reactants is: phosphate: phosphite: hydrogen phosphite molar ratio of 0.003: 0.990: 0.007, phosphorous acid (0.003)-phosphite (0.990)-hydrogen phosphite (0.007) hybrid aluminum salt is prepared. And P-NMR and XRD test results, as shown in Table 1.

[0092] Example 9 Synthesis of phosphorous acid (0.003)-phosphite (0.990)-hydrogen phosphite (0.007) hybrid aluminum salt The same as example 7, except that the reactants are changed from phosphite to pyrophosphite, and the ratio of the three reactants is: phosphate: pyrophosphite: hydrogen phosphite molar ratio of 0.003: 0.990: 0.007, phosphorous acid (0.003)-phosphite (0.990)-hydrogen phosphite (0.007) hybrid aluminum salt is prepared. P-NMR and XRD test results, as shown in Table 1.

[0093] Example 10 Synthesis of phosphorous acid (0.003)-phosphite (0.990)-hydrogen phosphite (0.004)-pyrophosphite (0.003) hybrid aluminum salt The same as example 7, except that the reactants are increased in phosphorous acid, and the ratio of the four reactants is: phosphate: phosphite: hydrogen phosphite: pyrophosphite molar ratio of 0.003: 0.990: 0.004: 0.003, phosphorous acid (0.003)-phosphite (0.990)-hydrogen phosphite (0.004)-pyrophosphite (0.003) hybrid aluminum salt is prepared. P-NMR and XRD test results, as shown in Table 1.

[0094] Example 11 Synthesis of phosphorous acid (0.003)-phosphite (0.997) hybrid zinc salt The same as example 3, except that the reactants are changed from aluminum hydroxide to equal molar zinc oxide, and phosphorous acid (0.003)-phosphite (0.997) hybrid zinc salt is prepared. P-NMR and XRD test results, as shown in Table 1.

[0095] Example 12 Synthesis of Phosphato (0.003) -phosphite (0.997) hybrid lanthanum salt The same as example 3, except that aluminum hydroxide was replaced by equimolar lanthanum oxide in the reactants, to produce phosphato (0.003) -phosphite (0.997) hybrid lanthanum salt. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0096] Example 13 Synthesis of Phosphato (0.003) -phosphite (0.997) hybrid yttrium salt The same as example 3, except that aluminum hydroxide was replaced by equimolar yttrium oxide in the reactants, to produce phosphato (0.003) -phosphite (0.997) hybrid yttrium salt. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0097] Example 14 Synthesis of Phosphato (0.003) -phosphite (0.997) hybrid samarium salt The same as example 3, except that aluminum hydroxide was replaced by equimolar samarium oxide in the reactants, to produce phosphato (0.003) -phosphite (0.997) hybrid samarium salt. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0098] Example 15 Synthesis of Phosphato (0.003) -phosphite (0.997) hybrid ytterbium salt The same as example 3, except that aluminum hydroxide was replaced by equimolar ytterbium oxide in the reactants, to produce phosphato (0.003) -phosphite (0.997) hybrid ytterbium salt. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0099] Example 16 Synthesis of Monohydrogenphosphato (0.003) -phosphite (0.997) hybrid calcium salt The same as example 1, except that phosphate was replaced by equimolar monohydrogenphosphate in the reactants, and aluminum sulfate was replaced by equimolar calcium chloride, to produce monohydrogenphosphato (0.003) -phosphite (0.997) hybrid calcium salt. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0100] Comparative Example 1 Aluminum phosphate and aluminum phosphite were mixed uniformly in the proportions of the phosphorus-containing anions participating in hybridization according to example 1, and P-NMR and XRD tests were performed, and the results are shown in Table 1 and Figure 4 .

[0101] Comparative Example 2 Aluminum phosphate, aluminum phosphite, and aluminum hydrophosphite were mixed uniformly in the proportions of the phosphorus-containing anions participating in hybridization according to example 7, and P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0102] Comparative Example 3 Aluminum phosphate, aluminum phosphite and aluminum pyrophosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 8, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0103] Comparative Example 4 Aluminum phosphate, aluminum pyrophosphite and aluminum hydrogen phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 9, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0104] Comparative Example 5 Aluminum phosphate, aluminum phosphite, aluminum hydrogen phosphite and aluminum pyrophosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 10, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0105] Comparative Example 6 Zinc phosphate and zinc phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 11, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0106] Comparative Example 7 Lanthanum phosphate and lanthanum phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 12, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0107] Comparative Example 8 Yttrium phosphate and yttrium phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 13, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0108] Comparative Example 9 Samarium phosphate and samarium phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example X1, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0109] Comparative Example 10 Ytterbium phosphate and ytterbium phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example X2, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0110] Comparative Example 11 Calcium monohydrogen phosphate and calcium phosphite were mixed uniformly in the proportions of the participating hybridized phosphorus-containing anions according to Example 14, and P-NMR and XRD tests were performed, the results of which are shown in Table 1.

[0111] Comparative Example 12 The same as Example 1, except that no high-temperature heat treatment was performed, and the sample prepared was tested for P-NMR and XRD, the results of which are shown in Table 1.

[0112] Comparative Example 13 The aluminum phosphate and the aluminum phosphite were mixed uniformly according to the participating hybrid phosphorus anion ratio of Example 1, and the same high-temperature heat treatment as Example 1 was performed, and the P-NMR and XRD of the obtained sample were tested, and the results are shown in Table 1.

[0113] Comparative Example 14 The same as Example 1, except that the phosphate was replaced by an equal molar of hydrogen phosphite, that is, the molar ratio of the reactants hydrogen phosphite: phosphite was 0.003:0.997. The P-NMR and XRD of the prepared sample were tested, and the results are shown in Table 1.

[0114] Comparative Example 15 The same as Example 1, except that the molar ratio of the reactants hydrogen phosphite and phosphite was adjusted to 0.997:003. The P-NMR and XRD of the prepared sample were tested, and the results are shown in Table 1.

[0115] Comparative Example 16 The same as Example 1, except that the phosphate was replaced by an equal molar of pyrophosphite, that is, the molar ratio of the reactants pyrophosphite: phosphite was 0.003:0.997. The P-NMR and XRD of the prepared sample were tested, and the results are shown in Table 1.

[0116] Comparative Example 17 The same as Example 1, except that the reactants were replaced by hydrogen phosphite and pyrophosphite, and the molar ratio of the reactants hydrogen phosphite: pyrophosphite was 0.003:0.997. The P-NMR and XRD of the prepared sample were tested, and the results are shown in Table 1.

[0117] Comparative Example 18 The same as Example 1, except that the reactants were replaced by hydrogen phosphite, phosphite and pyrophosphite, and the molar ratio of the reactants hydrogen phosphite: phosphite: pyrophosphite was 0.003:0.994:0.003. The P-NMR and XRD of the prepared sample were tested, and the results are shown in Table 1.

[0118] Comparative Example 19 The same as Example 3, except that the molar ratio of the participating hybrid phosphoric acid and phosphite was adjusted to 0.3:0.7, and the phosphoric acid (0.3)-phosphite (0.7) hybrid aluminum salt was prepared. And P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0119] The products in Examples 1-16 and Comparative Examples 1-19 were tested by nuclear magnetic phosphorus spectrum P-NMR and XRD.

[0120] The phosphorus spectrum P-NMR is tested by dissolving the product with sodium hydroxide solution, and then the NMR test is performed. The NMR result can qualitatively and quantitatively test the hybrid ratio of phosphate and phosphite. The results of Examples 1-5 are shown in Table 1. Figure 2 Figure 2 In the NMR spectrum, the peaks at displacement amounts 1.517 and 5.013 are characteristic peaks of phosphite, and the peak at displacement amount 5.546 is a peak of phosphate. Since the sample of hybrid is dissolved with alkali solution when the NMR test is performed, the hybrid structure is destroyed, and the phosphate and phosphite exist in an independent form, the characteristic peaks of the anions participating in the hybrid are displayed, and the proportion of the anions participating in the hybrid is determined by calculating the peak area. The phosphorus-containing hybrid anions existing in the compound are determined by NMR, but it cannot be determined whether the anions participating in the hybrid are a hybrid structure or a mixture structure, so the XRD of the hybrid and the single component can be compared to determine it.

[0121] Figure 3 The XRD results of the phosphoric acid-phosphite hybrid aluminum salt of Examples 1-5 of the present application are shown in Table 1, Figure 4 The XRD results of the aluminum phosphite and aluminum phosphate mixture are shown in Table 1. From the results, even at a low content of 0.3% of phosphate, the hybrid aluminum salt and the mixture of the two aluminum salts show completely different XRD results, indicating that the phosphorus-containing hybrid of the present application is a new structure compound, which is different from the mixture. It is found by research that different hybrid ratios of phosphate and phosphite can obtain similar phosphoric acid-phosphite hybrid aluminum salt according to the preparation process of the present application.

[0122] Therefore, whether the hybrid is formed can be determined according to the XRD results. If the XRD result shows an XRD different from the mixture, it indicates that the hybrid is formed, and if the XRD result shows an XRD of a mixture of two or more substances, it indicates that it is not a hybrid. All the phosphate-containing hybrid aluminum salts of the present application have similar XRD results. Figure 3 The test results are shown in Table 1.

[0123] Table 1 Conclusion: The results of Examples 1-5 show that different preparation methods can obtain the same hybrid aluminum salt; The results of Comparative Examples 1-11 show that the hybrid is not a mixture of several components mixed together; The results of Comparative Example 12 show that without high temperature treatment, the hybrid cannot be obtained; The results of Comparative Example 13 show that just mixing several mixtures and heat treating at high temperature cannot obtain the hybrid;​ The results of Comparative Examples 14-18 show that without the presence of phosphate, other phosphorus-containing compounds in any proportion do not produce a hybrid according to the method of the present application; The results of Comparative Example 19 show that the preparation thereof produces a hybrid with a higher phosphate content than claimed in the present application, and although a hybrid is produced, its flame retardancy can be affected in the following applications.

[0124] Use of phosphorus-containing hybrid metal salts Example 17 A phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 1 was compounded with aluminum diethylphosphinate, wherein the hybrid aluminum salt was present in a proportion of 20 wt%, and was designated as flame retardant-1. This flame retardant system was applied to a 30 wt% glass fiber reinforced high temperature nylon PPA according to the following formulation: PPA (polyphthalamide) 57% Glass fiber 30% Flame retardant-1 12% Other additives 1% Preparation process: a twin-screw extruder was used to prepare the flame-retardant glass fiber reinforced high temperature nylon PPA according to the conventional process. The PPA type was N-600, and the manufacturer was Zhejiang Xinhengcheng Co., Ltd.

[0125] Performance test: the flame retardant performance of the material (flame-retardant test piece thickness 0.4 mm) and the corrosion performance of the flame retardant system were tested according to the following methods.

[0126] (1) Flame retardant performance Flame retardant test method: tested according to UL94 V0 standard, i.e. 5 samples were tested, each sample was ignited twice; each sample was ignited for 10 s, then removed from the flame, and required to be extinguished within 10 s after leaving the flame (i.e. the afterflame time was not more than 10 s); at the same time, the total afterflame time of 10 ignitions of 5 samples was required to be not more than 50 s; it was required that no burning drips appeared during the ignition process; if the sample was not completely burned out, after the ignition ended, no flame smoldering for more than 30 s could appear. If the flame retardant test passed, it was recorded as PASS, and if the flame retardant test failed, it was recorded as FAIL. In the case of PASS, the relative difference in flame retardant performance could be distinguished by the total afterflame time, the shorter the time, the better the flame retardant performance. If the flame-retardant sample burned out and did not extinguish, it was recorded as not extinguished, and if the flame-retardant sample was not burned out and extinguished, but the total afterflame time was more than 50 s, it was recorded as > 50 s. Generally, the thinner the test piece, the more difficult it is to be flame-retardant, and the longer the afterflame time will be.

[0127] (2) Corrosion performance The flame-retardant glass fiber reinforced high-temperature nylon PPA was granulated using a twin-screw extruder, and then the particles were dried to less than 0.2% moisture, and a standard flame-retardant sample was injected using an injection molding machine, and a total of 2100 molds were injected (about 12 hours of continuous injection was required). The check ring of the injection molding machine was replaced with a special easily corroded metal material CPM9V. Before each experiment, the mass m1 of the check ring was tested, after the injection was completed, the check ring was cleaned, and the mass m2 of the check ring was tested again, and the weight loss rate LOSS% was calculated according to the following formula: LOSS% = (m1-m2) / m1x100% The greater the weight loss rate, the worse the corrosion resistance. The corrosion results are the average of 2 tests.

[0128] The test results are shown in Table 2.

[0129] Example 18 The same as Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 2 was compounded with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20wt%, and was recorded as flame retardant-2. It was applied to the same material system, and the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 2.

[0130] Example 19 The same as Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 3 was compounded with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20wt%, and was recorded as flame retardant-3. It was applied to the same material system, and the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 2.

[0131] Example 20 The same as Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 4 was compounded with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20wt%, and was recorded as flame retardant-4. It was applied to the same material system, and the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 2.

[0132] Example 21 The same as Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 5 was compounded with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20wt%, and was recorded as flame retardant-5. It was applied to the same material system, and the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 2.

[0133] Example 22 The same as example 17, except that phosphoric acid (0.01)-phosphorous acid (0.99) hybrid aluminum salt prepared according to example 6 was used to compound with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20wt%, recorded as flame retardant-6. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results were shown in Table 2.

[0134] Comparative example 20 The same as example 17, except that no flame retardant was used, and the glass fiber content was still 30%. The flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results were shown in Table 2.

[0135] Comparative example 21 The same as example 17, except that an equal amount of aluminum phosphite was used to replace phosphoric acid (0.01)-phosphorous acid (0.99) hybrid aluminum salt to compound with aluminum diethylphosphinate, wherein the aluminum phosphite accounted for 20wt%, recorded as flame retardant-7. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results were shown in Table 2.

[0136] Comparative example 22 The same as comparative example 20, except that the amount of flame retardant-7 was adjusted to 15%. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results were shown in Table 2.

[0137] Comparative example 23 The same as example 17, except that phosphoric acid (0.3)-phosphorous acid (0.7) hybrid aluminum salt prepared according to comparative example 18 was used to compound with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20wt%, recorded as flame retardant-8. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results were shown in Table 2.

[0138] Table 2: Application results of hybrids Conclusion: The results of examples 17-22 and comparative examples 20-22 showed that the application effects of phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salts prepared by several preparation methods were close, compared with non-hybrid systems, less flame retardant could achieve the same flame retardant effect, which could improve the flame retardant efficiency and had lower corrosion. Moreover, from the data comparison of examples 17-21 and example 22, it could be seen that with the increase of the proportion of phosphate in the hybrid, the flame retardant time became longer, the flame retardant became worse, and the corrosion increased. Comparative example 23 showed that when the content of phosphate in the hybrid reached 30%, although the corrosion resistance was better, the flame retardant could not meet the requirements, and the purpose of the application could not be achieved.

[0139] Example 23 The same as example 17, except using phosphoric acid (0.003)-phosphorous acid (0.990)-phosphorous acid (0.007) hybridized aluminum salt prepared according to example 7, compounded with aluminum diethylphosphinate, wherein the hybridized aluminum salt accounts for 20wt%, noted as flame retardant-9. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0140] Example 24 The same as example 17, except using phosphoric acid (0.003)-phosphorous acid (0.990)-phosphorous acid (0.007) hybridized aluminum salt prepared according to example 7, compounded with aluminum diethylphosphinate, wherein the hybridized aluminum salt accounts for 20wt%, noted as flame retardant-9. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0141] Example 25 The same as example 17, except using phosphoric acid (0.003)-phosphorous acid (0.990)-phosphorous acid (0.007) hybridized aluminum salt prepared according to example 7, compounded with aluminum diethylphosphinate, wherein the hybridized aluminum salt accounts for 20wt%, noted as flame retardant-9. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0142] Example 26 The same as example 17, except using phosphoric acid (0.003)-phosphorous acid (0.990)-phosphorous acid (0.004)-phosphorous acid (0.003) hybridized aluminum salt prepared according to example 10, compounded with aluminum diethylphosphinate, wherein the hybridized aluminum salt accounts for 20wt%, noted as flame retardant-12. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0143] Comparative example 24 The same as example 17, except using the phosphoric acid aluminum and phosphorous acid aluminum mixture sample prepared according to comparative example 1, compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounts for 20wt%, noted as flame retardant-13. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0144] Comparative example 25 The same as example 17, except using the phosphoric acid aluminum, phosphorous acid aluminum and phosphorous acid aluminum mixture sample prepared according to comparative example 2, compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounts for 20wt%, noted as flame retardant-14. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0145] Comparative Example 26 The same as Example 17, except that the aluminum phosphate, aluminum phosphite and aluminum pyrophosphite mixture sample prepared in Comparative Example 3 was compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounted for 20wt%, recorded as flame retardant-15. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0146] Comparative Example 27 The same as Example 17, except that the aluminum phosphate, aluminum pyrophosphite and aluminum hydrogen phosphite mixture sample prepared in Comparative Example 4 was compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounted for 20wt%, recorded as flame retardant-16. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0147] Comparative Example 28 The same as Example 17, except that the aluminum phosphate, aluminum phosphite, aluminum hydrogen phosphite and aluminum pyrophosphite mixture sample prepared in Comparative Example 5 was compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounted for 20wt%, recorded as flame retardant-17. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 3.

[0148] Table 3: Application results of hybrid Conclusion: The results of Examples 23-26 and Comparative Examples 24-28 show that whether it is binary hybrid or multiple hybrid, its flame retardancy and corrosion resistance are better than that of the corresponding mixture, and the purpose of the application can be achieved.

[0149] Example 27 The same as Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid zinc salt prepared according to Example 11 was compounded with aluminum diethylphosphinate, wherein the hybrid zinc salt accounted for 20wt%, recorded as flame retardant-18. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 4.

[0150] Example 28 The same as Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid lanthanum salt prepared according to Example 12 was compounded with aluminum diethylphosphinate, wherein the hybrid lanthanum salt accounted for 20wt%, recorded as flame retardant-19. It was applied to the same material system, and the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 4.

[0151] Example 29 The same as example 17, except using the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid yttrium salt prepared according to example 13, compounded with aluminum diethylphosphinate, where the hybrid yttrium salt accounts for 20wt%, noted as flame retardant-20. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, the results are shown in Table 4.

[0152] Example 30 The same as example 17, except using the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid samarium salt prepared according to example 14, compounded with aluminum diethylphosphinate, where the hybrid samarium salt accounts for 20wt%, noted as flame retardant-Y1. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, the results are shown in Table 4.

[0153] Example 31 The same as example 17, except using the phosphoric acid (0.003)-phosphorous acid (0.997) hybrid ytterbium salt prepared according to example 15, compounded with aluminum diethylphosphinate, where the hybrid ytterbium salt accounts for 20wt%, noted as flame retardant-Y2. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, the results are shown in Table 4.

[0154] Example 32 The same as example 17, except using the monohydrogen phosphate (0.003)-phosphorous acid (0.997) hybrid calcium salt prepared according to example 16, compounded with aluminum diethylphosphinate, where the hybrid calcium salt accounts for 20wt%, noted as flame retardant-21. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, the results are shown in Table 4.

[0155] Comparative example 29 The same as example 17, except using the phosphoric acid-zinc phosphite mixture sample prepared according to comparative example 6, compounded with aluminum diethylphosphinate, where the mixed zinc salt accounts for 20wt%, noted as flame retardant-22. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, the results are shown in Table 4.

[0156] Comparative example 30 The same as example 17, except using the phosphoric acid-lanthanum phosphite mixture sample prepared according to comparative example 7, compounded with aluminum diethylphosphinate, where the mixed lanthanum salt accounts for 20wt%, noted as flame retardant-23. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, the results are shown in Table 4.

[0157] Comparative example 31 The same as example 17, except using the sample of mixture of yttrium phosphate and yttrium phosphite prepared in comparative example 8, compounded with aluminum diethylphosphinate, wherein the mixed yttrium salt accounts for 20wt%, recorded as flame retardant-24. Applied to the same material system, the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 4.

[0158] Comparative example 32 The same as example 17, except using the sample of mixture of samarium phosphate and samarium phosphite prepared in comparative example 9, compounded with aluminum diethylphosphinate, wherein the mixed samarium salt accounts for 20wt%, recorded as flame retardant-Y3. Applied to the same material system, the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 4.

[0159] Comparative example 33 The same as example 17, except using the sample of mixture of ytterbium phosphate and ytterbium phosphite prepared in comparative example 10, compounded with aluminum diethylphosphinate, wherein the mixed ytterbium salt accounts for 20wt%, recorded as flame retardant-Y4. Applied to the same material system, the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 4.

[0160] Comparative example 34 The same as example 17, except using the sample of mixture of calcium monohydrogen phosphate and calcium phosphite prepared in comparative example 11, compounded with aluminum diethylphosphinate, wherein the mixed calcium salt accounts for 20wt%, recorded as flame retardant-25. Applied to the same material system, the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 4.

[0161] Table 4: Application results of hybrids Conclusion: The results of examples 27-32 and comparative examples 29-34 show that the phosphorus-containing hybrids of other metal salts still have good flame retardancy and corrosion resistance, and the flame retardancy and corrosion resistance are better than those of the corresponding mixtures, which can achieve the purpose of the application. In terms of flame retardancy, the flame retardant time is slightly longer than that of the aluminum salt, indicating that the flame retardancy is slightly lower than that of the aluminum salt hybrid, but the corrosion resistance is better.

[0162] Comparative example 35 The same as example 17, except using the sample prepared in comparative example 12, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 12 accounts for 20wt%, recorded as flame retardant-26. Applied to the same material system, the flame retardant properties of the material were tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0163] Comparative example 36 The same as example 17, except using the sample prepared in comparative example 13, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 13 accounts for 20wt%, noted as flame retardant-27. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0164] Comparative example 37 The same as example 17, except using the sample prepared in comparative example 14, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 14 accounts for 20wt%, noted as flame retardant-28. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0165] Comparative example 38 The same as example 17, except using the sample prepared in comparative example 15, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 15 accounts for 20wt%, noted as flame retardant-29. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0166] Comparative example 39 The same as example 17, except using the sample prepared in comparative example 16, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 16 accounts for 20wt%, noted as flame retardant-30. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0167] Comparative example 40 The same as example 17, except using the sample prepared in comparative example 17, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 17 accounts for 20wt%, noted as flame retardant-31. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0168] Comparative example 41 The same as example 17, except using the sample prepared in comparative example 18, compounded with aluminum diethylphosphinate, wherein the sample of comparative example 18 accounts for 20wt%, noted as flame retardant-32. Applied to the same material system, the flame retardant performance of the material was tested and the corrosion performance of the flame retardant system was investigated, and the results are shown in Table 5.

[0169] Table 5: application results of comparative examples Conclusion: Comparative examples 35-41 show that the compound obtained without containing phosphate is not only not a hybrid, but also cannot achieve the purpose of flame retardance and corrosion in application.

[0170] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and that changes, modifications, substitutions and variations can be made by those skilled in the art without departing from the scope of the present application.

Claims

1. A phosphorus-containing hybrid metal salt compound, said phosphorus-containing hybrid metal salt compound comprising: Metal ions and phosphorus-containing hybrid anions; in, The phosphorus-containing hybrid anions include: The phosphorus-containing anion of structural formula I, and Any one or more of the phosphorus-containing anions of structural formula II, structural formula III, and structural formula IV. The phosphorus-containing anions of structural formula I, structural formula II, structural formula III, and structural formula IV are as follows: I, II, III, IV: In structural formula I, m is an integer between 0 and 2; The metal element in the metal ion is any one of Ca, Mg, Al, Zn, Fe, Sn, Ti, TiO, or rare earth metals.

2. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: V； Where p is 0.001-0.997, x is 0.001-0.997, y is 0.001-0.997, z is 0.001-0.2, and p + x + y + z = 1; m is an integer from 0 to 2; n is the valence of metal M, which is an integer from 1 to 4; M is a metallic element.

3. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: WE, Where x is 0.001-0.998, y is 0.001-0.998, z is 0.001-0.2, and x+y+z=1; m is an integer from 0 to 2; n is the valence of metal M, which is an integer from 1 to 4; M is a metallic element.

4. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: VII, Where p is 0.001-0.998, x is 0.001-0.998, z is 0.001-0.2, and p+x+z=1; m is an integer from 0 to 2; n is the valence of metal M, which is an integer from 1 to 4; M is a metallic element.

5. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: VIII; Where: p is 0.001-0.998, y is 0.001-0.998, z is 0.001-0.2, and p+y+z=1; m is an integer from 0 to 2; n is the valence of metal M, which is an integer from 1 to 4; M is a metallic element.

6. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: IX; Where: x is 0.8-0.999, z is 0.001-0.2, and x+z=1; m is an integer from 0 to 2; n is the valence of metal M, an integer from 1 to 4; M is a metallic element.

7. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: X； Where: y is 0.8-0.999, z is 0.001-0.2, and y+z=1; m is an integer from 0 to 2; n is the valence of metal M, which is an integer from 1 to 4; M is a metallic element.

8. The phosphorus-containing hybrid metal salt compound according to claim 1, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is: XI; Where: p is 0.8-0.999, z is 0.001-0.2, and p+z=1; m is an integer from 0 to 2; n is the valence of metal M, an integer from 1 to 4; M is a metallic element.

9. A method for preparing a phosphorus-containing hybrid metal salt compound according to any one of claims 1 to 8, comprising the following steps: 1) React phosphorus-containing hybrid anion donor and metal ion donor at 80-110℃ to obtain a precipitate of phosphorus-containing hybrid metal salt compound; 2) Wash, filter, and dry the precipitate; 3) Treat the precipitate obtained in step 2) at a high temperature of 120-300℃; as well as Optionally, 4) crush the material obtained in step 3); The metal ion donor is a metal salt compound, a metal oxide, or a metal hydroxide; The phosphorus-containing hybrid anion donor includes an acid or soluble salt of phosphorus-containing structure I, and a mixture of any one or more of the following: phosphorus-containing structures: Formula II, Formula III, and Formula IV. The phosphorus-containing hybrid anion donor is any one or more acids or soluble salts or mixtures thereof from the phosphorus-containing structures of Formula II, Formula III, and Formula IV.

10. The preparation method according to claim 9, wherein, When the phosphorus-containing hybrid anion donor comprises an acid or soluble salt of phosphorus-containing structure I, and a mixture of any one or more of the following: phosphorus-containing structures: Formula II, Formula III, and Formula IV, the preparation method includes: 1) Dissolve the phosphorus-containing hybrid anion donor in water in a certain proportion, add the metal ion donor and react at 80-110℃ to obtain a precipitate of phosphorus-containing hybrid metal salt compound; 2) Wash, filter, and dry the precipitate; 3) The precipitate obtained in step 2) is treated at a high temperature of 120-300℃ under an inert atmosphere or vacuum. 4) As needed, crush the material obtained in step 3) to the required particle size range; Optionally, the inert atmosphere in step 3) is a rare gas atmosphere or a nitrogen atmosphere.

11. The preparation method according to claim 9, wherein, When the phosphorus-containing hybrid anion donor is any one or more acids or soluble salts or mixtures thereof of phosphorus-containing structures of Formula II, Formula III, and Formula IV, the preparation method includes: 1) Dissolve the phosphorus-containing hybrid anion donor in water in a certain proportion, add the metal ion donor, and react at 80-110°C. The reaction is carried out in an air atmosphere or an oxygen atmosphere to obtain a precipitate of phosphorus-containing hybrid metal salt. 2) Wash the precipitate, filter it, and dry it in an air or oxygen atmosphere; 3) Treat the precipitate obtained in step 2) at a high temperature of 180-300℃ in an air or oxygen atmosphere; 4) Crush the material obtained in step 3) to the required particle size range as needed.

12. A compound, said compound comprising: The phosphorus-containing hybrid metal salt compound according to any one of claims 1 to 8 or a mixture of one or more phosphorus-containing hybrid metal salt compounds prepared by the preparation method according to any one of claims 9 to 11, and other arbitrary flame retardants; Optionally, the flame retardant is selected from one or more of phosphorus-containing compounds, aluminum-containing compounds, nitrogen-containing compounds, zinc-containing compounds, and silicon-containing compounds, or a mixture or composition thereof. Optionally, the flame retardant is a phosphorus-containing compound, which is selected from any one or more mixtures or combinations of dialkyl phosphinates, monoalkyl phosphinates, hypophosphites, and phosphites. Optionally, the phosphorus-containing compound is aluminum diethylphosphonate.

13. The phosphorus-containing hybrid metal salt compound according to any one of claims 1 to 8 or a mixture of one or more phosphorus-containing hybrid metal salt compounds prepared by the preparation method according to any one of claims 9 to 11, or the compound according to claim 12, for use as a flame retardant, flame retardant mixture and flame retardant synergist, or for use in the preparation of flame retardant polymer materials, or for use in equipping polyester and cellulose pure fabrics and blended fabrics with flame retardancy by impregnation; Optionally, the flame retardant includes one or more of the following: flame retardants for varnishes and foamed coatings, flame retardants for wood and other cellulosic products, and non-reactive flame retardants for polymers. Optionally, the flame-retardant polymer material includes one or more of flame-retardant thermoplastic or thermosetting polymer molding materials, flame-retardant polymer molded articles, flame-retardant polymer films, flame-retardant polymer filaments, and polymer fibers.

14. A flame-retardant polymer material, wherein the raw materials include a polymer matrix, additives, fillers or reinforcing materials, and any one of the following: The phosphorus-containing hybrid metal salt compound according to any one of claims 1 to 8, or a mixture of one or more phosphorus-containing hybrid metal salt compounds prepared by the preparation method according to any one of claims 9 to 11, or A flame retardant mixture containing one or more of the phosphorus-containing hybrid metal salt compounds according to any one of claims 1 to 8 or prepared by the preparation method according to any one of claims 9 to 11, or The compound according to claim 12, or A flame retardant mixture containing the compound of claim 12.

15. The flame retardant polymer material according to claim 14, wherein, Based on the total mass of raw materials as 100%, the following raw materials are included: 0.1 wt% to 45 wt% of one or more of the phosphorus-containing hybrid metal salt compounds, 55 to 99.9 wt% of the polymer matrix, 0 to 44.9 wt% of the additives, and 0 to 44.9 wt% of the fillers or reinforcing materials; or 0.1 to 45 wt% of a flame retardant mixture, 55 wt% to 99.9 wt% of a polymer matrix, 0 to 44.9 wt% of additives, and 0 to 44.9 wt% of fillers or reinforcing materials; wherein, The flame retardant mixture comprises 0.1 wt% to 50 wt% of one or more of the phosphorus-containing hybrid metal salt compounds and 50 wt% to 99.9 wt% of the flame retardant; or 0.1 wt% to 45 wt% of the compound, 55 wt% to 99.9 wt% of the polymer matrix, 0 to 55 wt% of the additives, and 0 to 55 wt% of the fillers or reinforcing materials; or 0.1 to 45 wt% of a flame retardant mixture, 55 wt% to 99.9 wt% of a polymer matrix, 0 to 55 wt% of additives, and 0 to 55 wt% of fillers or reinforcing materials; wherein, The flame retardant mixture comprises 0.1 wt% to 50 wt% of the compound and 50 wt% to 99.9 wt% of the flame retardant.

16. The flame retardant polymer material according to claim 14 or 15, wherein, The flame retardant is selected from one or more of dialkyl hypophosphite metal salts, inorganic hypophosphite, phosphites, zinc-containing compounds, and melamine derivatives; and / or The polymer matrix is ​​selected from any one or more of the following: polyurethane, thermoplastic elastomer, epoxy resin, unsaturated polyester, nylon, polyester and polyketone resin.

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