A phosphorus-containing hybrid metal salt compound, a preparation method and application thereof

Abstract

A phosphorus-containing hybrid metal salt compound, its preparation method, and its application are disclosed. The phosphorus-containing hybrid metal salt compound exhibits good flame retardant synergy with dialkylphosphinates, which can improve flame retardant efficiency and reduce the corrosiveness of dialkylphosphinate flame retardants.

Description

Technical Field

[0001] This article relates to the field of new materials, specifically to a phosphorus-containing hybrid metal salt compound, its preparation method, and its applications. Background Technology

[0002] Phosphorus-based flame retardants are widely used due to their environmentally friendly and highly flame-retardant properties. Dialkyl phosphinates are a typical example of phosphorus-based flame retardants. Due to their high phosphorus content and high temperature resistance, they are widely used halogen-free flame retardants that can be applied to thermoplastic materials such as nylon, polyester, and TPE, as well as thermosetting materials such as PU, epoxy resin, and unsaturated polyester. However, dialkyl phosphinate flame retardants still have two main problems: (1) Dialkyl phosphinates are highly acidic and corrosive to processing equipment; (2) For some materials, such as nylon, the flame retardant performance of using only dialkyl phosphinates is insufficient, especially for some thin nylon products.

[0003] Several solutions have been reported to address these two issues. For example, in the flame-retardant application of nylon materials, the low flame-retardant efficiency can be effectively solved through synergy with phosphites, but phosphites still present corrosion problems. To address the corrosion issue, various alkaline substances or acid scavengers have been proposed, but their use reduces the flame-retardant properties of dialkylphosphinates. Currently, there is no compound that can both improve flame-retardant efficiency and solve corrosion problems. Existing technologies seek a balance and compromise between improving flame retardancy and reducing corrosion; prioritizing corrosion sacrifices flame-retardant performance, while focusing on flame retardancy sacrifices corrosion. Summary of the Invention

[0004] The following is an overview of the subject matter described in detail herein. This overview is not intended to limit the scope of protection of this application.

[0005] The main objective of this application is to disclose a phosphate-regulated phosphorus-containing hybrid metal salt compound, and to provide its preparation method and applications. Compared to non-hybridized phosphites, this compound exhibits good flame-retardant synergy when used with dialkylphosphinate flame retardants, improving flame-retardant efficiency and meeting the UL94 V0 flame-retardant requirement for thicknesses as thin as 0.4 mm, while also reducing the corrosiveness of dialkylphosphinate flame retardants.

[0006] The first aspect of this application relates to a phosphorus-containing hybrid metal salt compound, said phosphorus-containing hybrid metal salt compound comprising: Metal ions and phosphorus-containing hybrid anions; 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 structure I, m is an integer between 0 and 2.

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

[0008] In one exemplary embodiment, 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.

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

[0010] In one exemplary embodiment, the structural formula of the phosphorus-containing hybrid metal salt compound is: VI, 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.

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

[0012] In one exemplary embodiment, 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.

[0013] Compound VII represents a preferred phosphorus-containing hybrid metal salt compound formed by phosphate and other phosphorus-containing anions, including phosphite and pyrophosphite.

[0014] In one exemplary embodiment, 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.

[0015] Compound VIII represents a preferred phosphorus-containing hybrid metal salt compound formed by phosphate and other phosphorus-containing anions, including hydrogen phosphite and pyrophosphite.

[0016] In one exemplary embodiment, 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.

[0017] Formula IX represents a preferred phosphorus-containing hybrid metal salt compound formed by phosphate and other phosphorus-containing anions, wherein the other phosphorus-containing anions are phosphites.

[0018] In one exemplary embodiment, 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.

[0019] Compound X represents a preferred phosphorus-containing hybrid metal salt compound formed by phosphate and other phosphorus-containing anions, wherein the other phosphorus-containing anion is hydrogen phosphite.

[0020] In one exemplary embodiment, 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.

[0021] The compound of formula XI represents a preferred phosphorus-containing hybrid metal salt compound formed by phosphate and other phosphorus-containing anions, wherein the other phosphorus-containing anions are pyrophosphate.

[0022] The second aspect of this application provides a method for preparing the above-mentioned phosphorus-containing hybrid metal salt compound, 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) The precipitate obtained in step 2) is subjected to high-temperature treatment at 120-300℃; and Optionally, 4) crush the material obtained in step 3).

[0023] In one exemplary embodiment, the phosphorus-containing hybrid anion donor comprises an acid or soluble salt of the phosphorus-containing structure of Formula I, and a mixture of any one or more of the phosphorus-containing structures of Formula II, Formula III, and Formula IV, or 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.

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

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

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

[0027] In one 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 hybrid anion donor.

[0028] In one exemplary embodiment, in step 1), the phosphorus-containing hybrid anion donor and the metal ion donor may be added in an equimolar ratio for complete reaction.

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

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

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

[0032] In one exemplary embodiment, step 2) includes drying the washed precipitate at 100-120°C to remove moisture.

[0033] In one exemplary embodiment, in step 2), heating and drying can be performed using various ovens, drying rooms, dryers, etc.

[0034] In one exemplary embodiment, step 3) includes: continuing to slowly and gradually increase the temperature of the material in step 2) for 2-10 hours, raising the temperature of the material to a level greater than 120°C but not exceeding 300°C, and maintaining that temperature for 1-300 minutes.

[0035] In an exemplary embodiment, when the phosphorus-containing hybrid anion donor comprises: an acid or soluble salt of a phosphorus-containing structure of Formula I, and a mixture of any one or more acids or soluble salts of a phosphorus-containing structure of Formula II, a phosphorus-containing structure of Formula III, and a phosphorus-containing structure of Formula IV, the preparation method comprises: 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) Crush the material obtained in step 3) to the required particle size range as needed.

[0036] In one 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 dispersion system, and then react with the acid in the phosphorus-containing hybrid anion donor, without the need to add a 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 react under high-concentration strong acid conditions; at this time, the metal ion donor reacts 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 one 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 one 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 one exemplary embodiment, in step 1), the pH value of the liquid phase in the reaction system can be adjusted by adding an alkali or a metal oxide.

[0042] In an exemplary embodiment, when the phosphorus-containing hybrid anion donor is any one or more acids or soluble salts or mixtures thereof of the phosphorus-containing structure 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, filter, and dry the precipitate; 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.

[0043] A third aspect of this application provides a compound comprising: one or more of the above-mentioned phosphorus-containing hybrid metal salt compounds, and other arbitrary flame retardants.

[0044] In one exemplary embodiment, the flame retardant is selected from one or more mixtures or compositions of phosphorus-containing compounds, aluminum-containing compounds, nitrogen-containing compounds, zinc-containing compounds, silicon-containing compounds, etc.

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

[0046] In one exemplary embodiment, the phosphorus-containing compound is selected from any one or more mixtures or compositions of dialkylphosphinates, monoalkylphosphinates, hypophosphites, and phosphites. Preferably, the phosphorus-containing compound is aluminum diethylphosphonate.

[0047] In one exemplary embodiment, the phosphate content in the phosphorus-containing hybrid metal salt compound is less than 20% of the total phosphorus-containing anions, preferably less than 10%.

[0048] The fourth aspect of this application provides the use of one or more of the above-mentioned phosphorus-containing hybrid metal salt compounds as flame retardants, flame retardant mixtures and flame retardant synergists, or for the preparation of flame retardant polymer materials, or for the application of flame retardancy to pure polyester and cellulose fabrics and blended fabrics by impregnation.

[0049] The fifth aspect of this application provides the use of the above-mentioned compound as a flame retardant, a flame retardant mixture and a flame retardant synergist, or for the preparation of flame retardant polymer materials, or for the application of flame retardancy to pure polyester and cellulose fabrics and blended fabrics by impregnation.

[0050] In one exemplary embodiment, 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.

[0051] In one exemplary embodiment, the flame-retardant polymer material includes one or more of the following: flame-retardant polymer molding material, flame-retardant polymer molded body, flame-retardant polymer film, flame-retardant polymer filament, and polymer fiber; Preferably, the flame-retardant polymer material includes one or more of the following: flame-retardant thermoplastic or thermosetting polymer molding materials, flame-retardant polymer molded articles, flame-retardant polymer films, flame-retardant polymer filaments, and polymer fibers.

[0052] The sixth aspect of this application provides a flame-retardant polymer material, the raw materials of which include a polymer matrix, additives, fillers or reinforcing materials, and any one of the following: One or more of the above-mentioned phosphorus-containing hybrid metal salt compounds, or Flame retardant mixtures containing one or more of the above-mentioned phosphorus-containing hybrid metal salt compounds, or The above-mentioned compound, or Flame retardant mixtures containing the above-mentioned compound.

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

[0054] In one exemplary embodiment, the flame-retardant polymer material, based on 100% of the total mass of the raw materials, comprises the following raw materials: A mixture of flame retardants ranging from 0.1 to 45 wt%, 55 wt% to 99.9 wt% polymer matrix, Additives ranging from 0 to 44.9 wt%, and 0 to 44.9 wt% filler or reinforcing material; 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.

[0055] In one exemplary embodiment, the flame-retardant polymer material, based on 100% of the total mass of the raw materials, comprises the following raw materials: The compound is present in amounts ranging from 0.1 wt% to 45 wt%. 55 wt% to 99.9 wt% polymer matrix, 0 to 55 wt% additives, and 0 to 55 wt% of fillers or reinforcing materials.

[0056] In one exemplary embodiment, the flame-retardant polymer material, based on 100% of the total mass of the raw materials, comprises the following raw materials: A mixture of flame retardants ranging from 0.1 to 45 wt%, 55 wt% to 99.9 wt% polymer matrix, 0 to 55 wt% additives, and 0 to 55 wt% filler or reinforcing material; 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.

[0057] In one exemplary embodiment, the flame retardant is selected from one or more of dialkyl hypophosphite metal salts, inorganic hypophosphite, phosphite, zinc-containing compounds, melamine derivatives, etc.

[0058] In one exemplary embodiment, the flame retardant is selected from one or more of the following: Dialkylphosphonic acids and / or their salts; The condensation products of melamine, and / or the reaction products of melamine with phosphoric acid, and / or the reaction products of melamine condensation products with polyphosphoric acid or mixtures thereof; Nitrogenous phosphates; Benzoguanidine, tris(hydroxyethyl) isocyanurate, allantoin, glycyrrhizin, melamine, melamine cyanurate, dicyandiamide and / or guanidine; Magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrate talc, hydrated calcium aluminate, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate and / or zinc stannate; Phosphites, hydrogen phosphites, or their condensates; Phosphates and their derivatives.

[0059] In one exemplary embodiment, the flame retardant is selected from one or more of the following: Melamine, melamine, melon, dimelamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melon polyphosphate and / or melamine polyphosphate and / or their mixed polysalts and / or ammonium hydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate.

[0060] In one exemplary embodiment, the flame retardant is selected from one or more of the following: Aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, monophenylphosphite and its salts, dialkylphosphine and its salts and mixtures of monoalkylphosphine and its salts, 2-carboxyethylalkylphosphine and its salts, 2-carboxyethylmethylphosphine and its salts, 2-carboxyethylarylphosphine and its salts, 2-carboxyethylphenylphosphine and its salts, DOPO and its salts, and adducts on p-benzoquinone.

[0061] In one exemplary embodiment, the polymer matrix is ​​selected from any one or more of the following: Polyurethane (PU), thermoplastic elastomer (TPE), epoxy resin, unsaturated polyester, nylon, polyester and polyketone resin (POK), etc.

[0062] Compared with the prior art, this application has the following technical effects: In this application, the phosphorus-containing hybrid metal salt compound differs from a single phosphorus-containing metal compound or a mixture of several phosphorus-containing metal compounds involved in the hybridization, exhibiting different properties and representing a compound with a novel hybrid structure. This phosphorus-containing hybrid metal salt compound can be synergistically compounded with dialkylphosphinate flame retardants, significantly improving flame retardant performance while also improving corrosion resistance, thus achieving the objective of this application. In contrast, non-hybridized single-component phosphorus-containing metal compounds or mixtures of several compounds cannot achieve both high flame retardancy and improved corrosion resistance.

[0063] Based on the hybridization results, the amount of phosphate in the hybrid does not affect the formation of the hybrid; similar XRD results can be obtained for hybrids with different phosphate contents. However, from an application perspective, a higher phosphate content significantly improves the corrosion resistance of dialkylphosphinates but is detrimental to flame retardancy. Therefore, to maintain a balance between flame retardancy and corrosion resistance, the phosphate content in the hybrid is preferably controlled below 20%, and more preferably below 10%.

[0064] The phosphate-regulated phosphorus-containing hybrid metal salt compounds described in this application can also function as flame retardants.

[0065] Other features and advantages of this application will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the application. Other advantages of this application can be realized and obtained by means of the embodiments described in the description and the accompanying drawings. Attached Figure Description

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

[0067] Figure 1 The structural formula of the phosphate-phosphorous acid hybrid aluminum salt (0.003 : 0.997, where the numbers represent the molar ratio of the anions involved in the hybridization) of this application is shown below. Figure 2 The phosphorus NMR spectra of the phosphoric acid-phosphorous aluminum hybrid salt (0.003:0.997) and a mixture of the same proportions are shown in this application. Figure 3 The image shows the XRD pattern of the aluminum phosphate-phosphorous acid hybrid salt (0.003:0.997) of this application. Figure 4 The image shows the XRD pattern of a mixture of aluminum phosphite and aluminum phosphate. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of this application clearer, the embodiments of this application will be described in detail below. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be arbitrarily combined with each other.

[0069] The following detailed description of the present application is provided in conjunction with embodiments, but is not intended to limit the present application. Any equivalent substitutions made in accordance with the disclosure of the present application shall fall within the protection scope of the present application.

[0070] Preparation of phosphorus-containing hybrid metal salt compounds Example 1 Synthesis of Phosphoric Acid (0.003)-Phosphorous Acid (0.997) Hybrid Aluminum Salt The molecular structure of the phosphate (0.003)-phosphorous acid (0.997) hybrid aluminum salt of this application is shown in [reference needed]. Figure 1 .

[0071] Preparation process: In a 2L reactor, 126g (1mol) of sodium phosphite and 0.66g (0.004mol) of sodium phosphate were dissolved in 189.1g of water and stirred thoroughly to obtain a mixed solution of sodium phosphite and sodium phosphate. In a 500mL beaker, 114.1g of aluminum sulfate was dissolved in 266.2g of water and transferred to a dropping funnel. The reactor was heated to 90℃, and the aluminum sulfate solution was added dropwise over 2 hours. The mixture was then kept at this temperature and the reaction continued for another hour.

[0072] Filter while hot and wash the precipitate multiple times until the conductivity of the wash water is less than 200 µS / cm, then stop washing. Transfer the material to an oven and dry at 120°C for 60 minutes under a nitrogen atmosphere until the moisture content of the solids is 0.1 wt%.

[0073] Under a nitrogen atmosphere, the temperature is increased to 180°C at a rate of 2°C / min and held for 60 min. Then, the temperature is increased to 260°C at a rate of 1°C / min and held for 30 min. The temperature is then reduced to room temperature and the product is discharged to obtain a phosphoric acid (0.003)-phosphorous acid (0.997) hybrid aluminum salt.

[0074] The material was crushed, with an average particle size D50 of 40 μm and a yield of 96.7%.

[0075] The product was tested using phosphorus spectroscopy (P-NMR) and XRD. The results are shown in Table 1. Figure 2-3 As shown.

[0076] Example 2 Synthesis of Phosphoric Acid (0.003)-Phosphorous Acid (0.997) Hybrid Aluminum Salt Similar to Example 1, except that the final high-temperature treatment temperature was set to 280°C, the P-NMR and XRD of the samples were tested, and the results are shown in Table 1 and... Figure 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 (0.006mol) of 85% concentrated phosphoric acid were dissolved in 288.6g of water and stirred thoroughly 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 to 90℃, and the aluminum hydroxide suspension was added dropwise over 2 hours. The pH was adjusted to 2.6 using aluminum hydroxide solids, and the reaction was continued at this temperature for another hour.

[0078] Filter while hot and wash the precipitate multiple times until the conductivity of the wash water is less than 200 µS / cm, then stop washing. Transfer the material to an oven and dry at 120°C for 60 minutes under a nitrogen atmosphere until the moisture content of the solids is 0.1 wt%.

[0079] Under a nitrogen atmosphere, the temperature is increased to 180°C at a rate of 2°C / min and held for 60 min. Then, the temperature is increased to 260°C at a rate of 1°C / min and held for 60 min. The temperature is then reduced to room temperature and the product is discharged to obtain a phosphate (0.003)-phosphorous acid (0.997) hybrid aluminum salt.

[0080] The material was pulverized, with an average particle size D50 of 38 μm and a yield of 98.5%. P-NMR and XRD analyses were performed, and the results are shown in Table 1. Figure 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 stirred thoroughly 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 to 90°C under an air atmosphere, and the aluminum sulfate solution was added dropwise over 2 hours. The reaction was then maintained at this temperature for another hour.

[0082] Filter while hot and wash the precipitate multiple times until the conductivity of the wash water is less than 200 µS / cm, then stop washing. Transfer the material to an oven and dry at 120°C for 60 minutes in air, until the moisture content of the solids is 0.1 wt%.

[0083] In an air atmosphere, the temperature was increased to 180℃ at a rate of 2℃ / min and held for 60 min, then increased to 260℃ at a rate of 1℃ / min and held for 30 min. The mixture was then cooled to room temperature and discharged to obtain a (0.003)-(0.997)-phosphorous acid hybrid aluminum salt. The material was then pulverized, with an average particle size D50 of 40 μm and a yield of 96.7%.

[0084] Phosphorus NMR and XRD were performed on the samples. The results are shown in Table 1 and... Figure 2-3 As shown.

[0085] Example 5 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 was dissolved in 288.6g of water and stirred thoroughly to obtain an aqueous solution of phosphorous 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 to 90°C under air atmosphere, and the aluminum hydroxide suspension was added dropwise over 2 hours. The pH was adjusted to 2.6 using aluminum hydroxide solids, and the reaction was continued at this temperature for another hour.

[0086] Filter while hot and wash the precipitate multiple times until the conductivity of the wash water is less than 200 µS / cm, then stop washing. Transfer the material to an oven and dry at 120°C for 60 minutes in air, until the moisture content of the solids is 0.1 wt%.

[0087] In an air atmosphere, the temperature is increased to 180℃ at a rate of 2℃ / min and held for 60min. Then, the temperature is increased to 260℃ at a rate of 1℃ / min and held for 60min. The temperature is then reduced to room temperature and the product is discharged to obtain a phosphate (0.003)-phosphorous acid (0.997) hybrid aluminum salt.

[0088] The material was pulverized, with an average particle size D50 of 38 μm and a yield of 98.5%. P-NMR and XRD analyses were performed, and the results are shown in Table 1. Figure 2-3 As shown.

[0089] Example 6 Synthesis of Phosphoric Acid (0.01)-Phosphorous Acid (0.99) Hybrid Aluminum Salt Similar to Example 3, except that the ratio of phosphoric acid and phosphorous acid involved in the hybridization was adjusted to a molar ratio of 0.01:0.99, a phosphoric acid (0.01)-phosphorous acid (0.99) hybrid aluminum salt was prepared. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0090] Example 7 Synthesis of a hybrid aluminum salt of phosphoric acid (0.003)-phosphorous acid (0.990)-hydrophosphorous acid (0.007) Similar to Example 1, except that hydrogen phosphite was added to the reactants, and the molar ratio of the three reactants was phosphate:phosphite:hydrophosphite 0.003:0.990:0.007, a phosphoric acid (0.003)-phosphite (0.990)-hydrophosphite (0.007) hybrid aluminum salt was prepared. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0091] Example 8 Synthesis of a hybrid aluminum salt of phosphoric acid (0.003)-phosphorous acid (0.990)-pyrophosphorous acid (0.007) Similar to Example 1, except that pyrophosphite was added to the reactants, and the molar ratio of the three reactants was phosphate:phosphite:pyrophosphite 0.003: 0.990: 0.007, a phosphoric acid (0.003)-phosphite (0.990)-pyrophosphite (0.007) hybrid aluminum salt was prepared. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0092] Example 9 Synthesis of a phosphoric acid (0.003)-pyrophosphorous acid (0.990)-hydrophosphorous acid (0.007) hybrid aluminum salt Similar to Example 7, except that phosphite was replaced with pyrophosphite in the reactants, and the molar ratio of the three reactants was phosphate:pyrophosphite:hydrophosphite of 0.003:0.990:0.007, to prepare a phosphoric acid (0.003)-pyrophosphite (0.990)-hydrophosphite (0.007) hybrid aluminum salt. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0093] Example 10 Synthesis of a hybrid aluminum salt of phosphoric acid (0.003)-phosphorous acid (0.990)-hydrophosphorous acid (0.004)-pyrophosphorous acid (0.003) Similar to Example 7, except that pyrophosphite was added to the reactants, and the molar ratio of the four reactants was phosphate:phosphite:hydrophosphite:pyrophosphite of 0.003:0.990:0.004:0.003, a phosphoric acid (0.003)-phosphite (0.990)-hydrophosphite (0.004)-pyrophosphite (0.003) hybrid aluminum salt was prepared. P-NMR and XRD tests were performed, and the results are shown in Table 1.

[0094] Example 11 Synthesis of phosphoric acid (0.003)-phosphorous acid (0.997) hybrid zinc salt Similar to Example 3, except that aluminum hydroxide was replaced with an equimolar amount of zinc oxide in the reactants, a (0.003)-phosphorous acid (0.997) hybrid zinc salt was prepared. P-NMR and XRD analyses were performed, and the results are shown in Table 1.

[0095] Example 12 Synthesis of lanthanum salts hybridized with phosphoric acid (0.003)-phosphorous acid (0.997) Similar to Example 3, except that aluminum hydroxide was replaced with an equimolar amount of lanthanum oxide in the reactants, a lanthanum salt of phosphoric acid (0.003)-phosphorous acid (0.997) hybrid was prepared. P-NMR and XRD analyses were performed, and the results are shown in Table 1.

[0096] Example 13 Synthesis of yttrium salts with phosphoric acid (0.003)-phosphorous acid (0.997) hybridization Similar to Example 3, except that aluminum hydroxide was replaced with an equimolar amount of yttrium oxide in the reactants, a 0.003-0.997 phosphate-phosphorous acid hybrid yttrium salt was prepared. P-NMR and XRD analyses were performed, and the results are shown in Table 1.

[0097] Example 14 Synthesis of samarium salts hybridized with phosphoric acid (0.003)-phosphorous acid (0.997) Similar to Example 3, except that aluminum hydroxide was replaced with an equimolar amount of samarium oxide in the reactants, a (0.003)-phosphorous acid (0.997) hybrid samarium salt was prepared. P-NMR and XRD analyses were performed, and the results are shown in Table 1.

[0098] Example 15 Synthesis of ytterbium salt with phosphoric acid (0.003)-phosphorous acid (0.997) hybridization Similar to Example 3, except that aluminum hydroxide was replaced with an equimolar amount of ytterbium oxide in the reactants, a 0.003-0.997 phosphoric acid hybrid ytterbium salt was prepared. P-NMR and XRD analyses were performed, and the results are shown in Table 1.

[0099] Example 16 Synthesis of a phosphate monohydrogen ion (0.003)-phosphorous acid (0.997) hybrid calcium salt Similar to Example 1, except that phosphate was replaced with an equimolar amount of monohydrogen phosphate and aluminum sulfate was replaced with an equimolar amount of calcium chloride, a monohydrogen phosphate (0.003)-phosphorous acid (0.997) hybrid calcium salt was prepared. 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 according to the proportion of phosphorus-containing anions involved in the hybridization as in Example 1, and P-NMR and XRD tests were performed. The results are shown in Table 1 and [Table data missing]. Figure 4 As shown.

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

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

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

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

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

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

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

[0108] Comparative Example 9 Samarium phosphate and samarium phosphite were mixed uniformly according to the proportion of phosphorus-containing anions involved in the hybridization as in Example 14, and P-NMR and XRD tests were performed. The results are shown in Table 1.

[0109] Comparative Example 10 Ytterbium phosphate and ytterbium phosphite were mixed uniformly according to the proportion of phosphorus-containing anions involved in the hybridization as in Example 15, and P-NMR and XRD tests were performed. The results are shown in Table 1.

[0110] Comparative Example 11 Calcium monohydrogen phosphate and calcium phosphite were mixed uniformly according to the proportion of phosphorus-containing anions involved in the hybridization as in Example 16, and P-NMR and XRD tests were performed. The results are shown in Table 1.

[0111] Comparative Example 12 Similar to Example 1, except that no high-temperature heat treatment was performed, the prepared samples were tested for P-NMR and XRD, and the results are shown in Table 1.

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

[0113] Comparative Example 14 Similar to Example 1, except that phosphate ions were replaced with an equimolar amount of hydrogen phosphite ions, i.e., the molar ratio of hydrogen phosphite ions to phosphite ions was 0.003:0.997. The prepared samples were tested using P-NMR and XRD, and the results are shown in Table 1.

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

[0115] Comparative Example 16 Similar to Example 1, except that phosphate was replaced with an equimolar amount of pyrophosphite, i.e., the molar ratio of pyrophosphite to phosphite was 0.003:0.997. The prepared samples were tested using P-NMR and XRD, and the results are shown in Table 1.

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

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

[0118] Comparative Example 19 Similar to Example 3, except that the ratio of phosphoric acid and phosphorous acid involved in the hybridization was adjusted to a molar ratio of 0.3:0.7, a phosphoric acid (0.3)-phosphorous acid (0.7) hybrid aluminum salt was prepared. 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 subjected to phosphorus nuclear magnetic resonance (P-NMR) and XRD tests.

[0120] Phosphorus NMR spectroscopy involves dissolving the product in sodium hydroxide solution before performing phosphorus NMR analysis. The NMR results allow for qualitative and quantitative determination of the hybridization ratio of phosphate and phosphite ions. The results obtained in Examples 1-5 are as follows: Figure 2 As shown. Figure 2 In the NMR analysis, the characteristic peaks at shifts of 1.517 and 5.013 are for phosphate, while the peak at shift 5.546 is for phosphate. Because the hybrid sample is dissolved in an alkaline solution during NMR testing, the hybrid structure is disrupted, and phosphate and phosphate exist independently. This reveals the individual characteristic peaks of the hybrid anions, and the proportion of hybrid anions is determined by calculating the peak areas. While NMR confirmed the presence of phosphorus-containing hybrid anions in the compound, it did not determine whether the hybrid anions constituted a hybrid structure or a mixture structure. Therefore, comparison with the XRD patterns of the hybrid and the single components is necessary to determine the specific composition.

[0121] Figure 3 The XRD results of the phosphate-phosphorous acid hybrid aluminum salts of Examples 1-5 of this application are shown. Figure 4 XRD results for a mixture of aluminum phosphite and aluminum phosphate are shown. The results indicate that even at a low phosphate content of 0.3%, the hybrid aluminum salt and the mixture of the two aluminum salts exhibit completely different XRD results, demonstrating that the phosphorus-containing hybrid of this application is a novel compound, distinct from the mixture of the two. Further research revealed that different phosphate and phosphite hybridization ratios, based on the preparation process described in this application, yield similar phosphate-phosphite hybrid aluminum salts.

[0122] Therefore, the XRD results can be used to determine whether a characteristic spectrum different from that of the mixture has been formed. If the XRD results show an XRD pattern different from that of the mixture, it indicates the formation of a hybrid. If the XRD results show an XRD pattern of a mixture of two or more substances, it indicates that it is not a hybrid. All phosphate-containing hybrid aluminum salts in this application have characteristics similar to... Figure 3 Similar XRD results were obtained. The test results are shown in Table 1.

[0123] Table 1 in conclusion: The results of Examples 1-5 demonstrate that different preparation methods can yield the same hybrid aluminum salt; The results of Comparative Examples 1-11 demonstrate that the hybrid is not a mixture of several components; The results of Comparative Example 12 show that hybrids cannot be obtained without high-temperature treatment; The results of Comparative Example 13 show that simply subjecting several mixtures to high-temperature heat treatment does not yield hybrids. The results of Comparative Examples 14-18 demonstrate that without the presence of phosphate, no other phosphorus-containing compounds can be obtained using the method of this application in any proportion, resulting in hybrids similar to those of this application. The results of Comparative Example 19 show that a hybrid with a higher phosphate content was prepared. Although the hybrid can be obtained, its flame retardancy will be affected in the following applications.

[0124] Applications of phosphorus-containing hybrid metal salts Example 17 The phosphate (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 1 was compounded with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-1. This flame retardant system was applied to 30 wt% glass fiber reinforced high-temperature nylon PPA according to the following formulation: PPA (polyphthalamide) 57% 30% Fiberglass Flame retardant-1 12% Other adjuvants 1% Preparation process: Flame-retardant glass fiber reinforced high-temperature nylon PPA was prepared using a twin-screw extruder according to conventional processes. The PPA model was N-600, and the manufacturer was Zhejiang Xinhecheng Co., Ltd.

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

[0126] (1) Flame retardant properties Flame retardancy test method: Test according to UL94 V0 standard, i.e., test 5 specimens, each specimen is ignited twice; each time the specimen is ignited for 10 seconds, then removed from the flame, the specimen must extinguish within 10 seconds of being removed from the flame (i.e., afterflame time not exceeding 10 seconds); at the same time, the total afterflame time of the 5 specimens for a total of 10 ignitions must not exceed 50 seconds; the specimen must not drip during the ignition process; if the specimen does not burn completely, there must not be a smoldering flame for more than 30 seconds after ignition. A pass in the flame retardancy test is marked as PASS, and a failure is marked as FAIL. In the case of a PASS, the relative difference in flame retardancy performance can be distinguished by the total flame extension time; the shorter the time, the better the flame retardancy performance. If the flame retardant specimen burns completely without extinguishing, it is marked as non-extinguishing; if the flame retardant specimen does not burn completely but the total flame extension time is greater than 50 seconds, it is marked as >50s. Generally, the thinner the specimen, the more difficult it is to retard flame, and the longer the flame extension time will be.

[0127] (2) Corrosion performance Flame-retardant glass fiber reinforced high-temperature nylon PPA was granulated using a twin-screw extruder. The granules were then dried to a moisture content below 0.2%, and standard flame-retardant specimens were injection molded using an injection molding machine. A total of 2100 injection molding cycles were performed (approximately 12 hours of continuous injection molding). 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 measured. After injection molding, the check ring was cleaned, and its mass m2 was measured again. The weight loss rate (LOSS%) was calculated using the following formula: LOSS% = (m1 - m2) / m1 × 100% A higher weight loss rate indicates poorer corrosion resistance. The corrosion result is the average of two tests.

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

[0129] Example 18 Similar to Example 17, except that the (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 2 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-2. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 2.

[0130] Example 19 Similar to Example 17, except that the (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 3 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-3. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 2.

[0131] Example 20 Similar to Example 17, except that the (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 4 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-4. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 2.

[0132] Example 21 Similar to Example 17, except that the (0.003)-phosphorous acid (0.997) hybrid aluminum salt prepared according to Example 5 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-5. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 2.

[0133] Example 22 Similar to Example 17, except that the (0.01)-phosphorous acid (0.99) hybrid aluminum salt prepared according to Example 6 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-6. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 2.

[0134] Comparative Example 20 Similar to Example 17, except that no flame retardant was used and the glass fiber content was still 30%, the flame retardant properties of the material were tested and the corrosion properties of the flame retardant system were examined. The results are shown in Table 2.

[0135] Comparative Example 21 Similar to Example 17, except that an equal amount of aluminum phosphite was used to replace the phosphate (0.01)-phosphite (0.99) hybrid aluminum salt, and it was compounded with aluminum diethylphosphinate, wherein the aluminum phosphite accounted for 20 wt%, and was designated as flame retardant-7. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system. The results are shown in Table 2.

[0136] Comparative Example 22 Similar to Comparative Example 20, except that the amount of flame retardant-7 was adjusted to 15%. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 2.

[0137] Comparative Example 23 Similar to Example 17, except that the (0.3)-(0.7) phosphoric acid hybrid aluminum salt prepared according to Comparative Example 18 was compounded with aluminum diethylphosphinate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-8. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 2.

[0138] Table 2: Results of Hybrid Application in conclusion: The results of Examples 17-22 and Comparative Examples 20-22 demonstrate that the phosphate (0.003)-phosphorous acid (0.997) hybrid aluminum salts prepared by various methods exhibit similar application effects. Compared to non-hybrid systems, they achieve the same flame-retardant effect with less flame retardant, improving flame-retardant efficiency while exhibiting lower corrosivity. Furthermore, a comparison of the data from Examples 17-21 and Example 22 shows that as the proportion of phosphate in the hybrid increases, the flame-retardant time lengthens, flame retardancy deteriorates, and corrosivity increases. Comparative Example 23 shows that while a phosphate content of 30% in the hybrid provides better corrosion resistance, the flame retardancy is insufficient to meet the requirements and fails to achieve the objectives of this application.

[0139] Example 23 Similar to Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.990)-hydrophosphorous acid (0.007) hybrid aluminum salt prepared according to Example 7 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-9. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system. The results are shown in Table 3.

[0140] Example 24 Similar to Example 17, except that the phosphoric acid (0.003)-phosphorous acid (0.990)-pyrophosphorous acid (0.007) hybrid aluminum salt prepared according to Example 8 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, denoted as flame retardant-10. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 3.

[0141] Example 25 Similar to Example 17, except that the phosphoric acid (0.003)-pyrophosphorous acid (0.990)-hydrophosphorous acid (0.007) hybrid aluminum salt prepared according to Example 9 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-11. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 3.

[0142] Example 26 Similar to Example 17, except that a hybrid aluminum salt of phosphoric acid (0.003)-phosphorous acid (0.990)-hydrophosphorous acid (0.004)-pyrophosphorous acid (0.003) prepared according to Example 10 was used in combination with aluminum diethylphosphonate, wherein the hybrid aluminum salt accounted for 20 wt%, and was designated as flame retardant-12. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system. The results are shown in Table 3.

[0143] Comparative Example 24 Similar to Example 17, except that the aluminum phosphate and aluminum phosphite mixture sample prepared in Comparative Example 1 was used, and compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounted for 20 wt%, denoted as flame retardant-13. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 3.

[0144] Comparative Example 25 Similar to Example 17, except that the mixture of aluminum phosphate, aluminum phosphite, and aluminum hydrogen phosphite prepared in Comparative Example 2 was used, and compounded with aluminum diethylphosphonate, wherein the mixed aluminum salt accounted for 20 wt%, denoted as flame retardant-14. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 3.

[0145] Comparative Example 26 Similar to Example 17, except that the mixture of aluminum phosphate, aluminum phosphite, and aluminum pyrophosphite prepared in Comparative Example 3 was used, and compounded with aluminum diethylphosphonate, wherein the mixed aluminum salt accounted for 20 wt%, denoted as Flame Retardant-15. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 3.

[0146] Comparative Example 27 Similar to Example 17, except that the mixture of aluminum phosphate, aluminum pyrophosphite, and aluminum hydrogen phosphite prepared in Comparative Example 4 was used, and compounded with aluminum diethylphosphonate, wherein the mixed aluminum salt accounted for 20 wt%, denoted as Flame Retardant-16. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 3.

[0147] Comparative Example 28 Similar to Example 17, except that the mixture of aluminum phosphate, aluminum phosphite, aluminum hydrogen phosphite, and aluminum pyrophosphite prepared in Comparative Example 5 was used, and compounded with aluminum diethylphosphinate, wherein the mixed aluminum salt accounted for 20 wt%, denoted as Flame Retardant-17. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 3.

[0148] Table 3: Results of Hybrid Application Conclusion: The results of Examples 23-26 and Comparative Examples 24-28 show that both binary and multi-component hybrids exhibit superior flame retardancy and corrosivity compared to their corresponding mixtures, thus achieving the objectives of this application.

[0149] Example 27 Similar to Example 17, except that the (0.003)-phosphorous acid (0.997) hybrid zinc salt prepared according to Example 11 was compounded with aluminum diethylphosphonate, wherein the hybrid zinc salt accounted for 20 wt%, and was designated as flame retardant-18. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 4.

[0150] Example 28 Similar to Example 17, except that the lanthanum phosphate (0.003)-phosphorous acid (0.997) hybrid salt prepared according to Example 12 was compounded with aluminum diethylphosphonate, wherein the lanthanum phosphate hybrid salt accounted for 20 wt%, and was designated as flame retardant-19. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 4.

[0151] Example 29 Similar to Example 17, except that the (0.003)-(0.997) yttrium phosphoric acid hybrid salt prepared according to Example 13 was used in combination with aluminum diethylphosphinate, wherein the hybrid yttrium salt accounted for 20 wt%, denoted as Flame Retardant-20. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 4.

[0152] Example 30 Similar to Example 17, except that a (0.003)-(0.997)-phosphorous acid hybrid samarium salt prepared according to Example 14 was used in combination with aluminum diethylphosphonate, wherein the hybrid samarium salt accounted for 20 wt%, denoted as flame retardant-Y1. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 4.

[0153] Example 31 Similar to Example 17, except that the 0.003-0.997 phosphoric acid-phosphorous acid hybrid ytterbium salt prepared according to Example 15 was compounded with aluminum diethylphosphonate, wherein the hybrid ytterbium salt accounted for 20 wt%, denoted as flame retardant-Y2. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 4.

[0154] Example 32 Similar to Example 17, except that a 0.003 wt% (20 wt%) (-0.997 wt%) (monohydrogen phosphate-phosphorous acid-21) hybrid calcium salt prepared according to Example 16 was used in combination with aluminum diethylphosphonate. The flame retardant properties of the material and the corrosion properties of the flame retardant system were tested using the same material system. The results are shown in Table 4.

[0155] Comparative Example 29 Similar to Example 17, except that the zinc phosphate and zinc phosphite mixture sample prepared in Comparative Example 6 was used, and compounded with aluminum diethylphosphinate, wherein the mixed zinc salt accounted for 20 wt%, denoted as flame retardant-22. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 4.

[0156] Comparative Example 30 Similar to Example 17, except that the lanthanum phosphate and lanthanum phosphite mixture sample prepared in Comparative Example 7 was used, and compounded with aluminum diethylphosphinate, wherein the mixed lanthanum salt accounted for 20 wt%, denoted as flame retardant-23. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 4.

[0157] Comparative Example 31 Similar to Example 17, except that the yttrium phosphate and yttrium phosphite mixture sample prepared in Comparative Example 8 was used, and compounded with aluminum diethylphosphinate, wherein the mixed yttrium salt accounted for 20 wt%, denoted as flame retardant-24. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 4.

[0158] Comparative Example 32 Similar to Example 17, except that the samarium phosphate and samarium phosphite mixture sample prepared in Comparative Example 9 was used, and compounded with aluminum diethylphosphinate, wherein the mixed samarium salt accounted for 20 wt%, denoted as flame retardant-Y3. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 4.

[0159] Comparative Example 33 Similar to Example 17, except that the ytterbium phosphate and ytterbium phosphite mixture sample prepared in Comparative Example 10 was used, and compounded with aluminum diethylphosphinate, wherein the mixed ytterbium salt accounted for 20 wt%, denoted as flame retardant-Y4. Applied to the same material system, the flame retardant properties of the material and the corrosion properties of the flame retardant system were tested, and the results are shown in Table 4.

[0160] Comparative Example 34 Similar to Example 17, except that the mixture of dicalcium phosphate and calcium phosphite prepared in Comparative Example 11 was used, and compounded with aluminum diethylphosphonate, wherein the mixed calcium salt accounted for 20 wt%, denoted as flame retardant-25. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 4.

[0161] Table 4: Results of Hybrid Application in conclusion: The results of Examples 27-32 and Comparative Examples 29-34 show that phosphorus-containing hybrids of other metal salts still exhibit good flame retardancy and corrosivity, and their flame retardancy and corrosivity are superior to their corresponding mixtures, thus achieving the objectives of this application. In terms of flame retardancy, compared to aluminum salts, their flame retardancy time is slightly longer, indicating that their flame retardancy is slightly lower than that of aluminum salt hybrids, but their corrosivity is better.

[0162] Comparative Example 35 Similar to Example 17, except that the sample prepared in Comparative Example 12 was used and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 12 accounted for 20 wt%, denoted as flame retardant-26. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 5.

[0163] Comparative Example 36 Similar to Example 17, except that the sample prepared in Comparative Example 13 was used and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 13 accounted for 20 wt%, denoted as flame retardant-27. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system. The results are shown in Table 5.

[0164] Comparative Example 37 Similar to Example 17, except that the sample prepared in Comparative Example 14 was used, and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 14 accounted for 20 wt%, denoted as Flame Retardant-28. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 5.

[0165] Comparative Example 38 Similar to Example 17, except that the sample prepared in Comparative Example 15 was used and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 15 accounted for 20 wt%, denoted as flame retardant-29. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 5.

[0166] Comparative Example 39 Similar to Example 17, except that the sample prepared in Comparative Example 16 was used and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 16 accounted for 20 wt%, denoted as Flame Retardant-30. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system. The results are shown in Table 5.

[0167] Comparative Example 40 Similar to Example 17, except that the sample prepared in Comparative Example 17 was used and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 17 accounted for 20 wt%, designated as flame retardant-31. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system. The results are shown in Table 5.

[0168] Comparative Example 41 Similar to Example 17, except that the sample prepared in Comparative Example 18 was used and compounded with aluminum diethylphosphinate, wherein the sample from Comparative Example 18 accounted for 20 wt%, designated as flame retardant-32. The same material system was applied to test the flame retardant properties of the material and examine the corrosion properties of the flame retardant system; the results are shown in Table 5.

[0169] Table 5: Results of Comparative Application in conclusion: Comparative Examples 35-41 demonstrate that the compounds obtained without phosphate groups are not only not hybrids, but their flame retardancy and corrosivity also fail to achieve the objectives of this application.

[0170] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A compound comprising one or more phosphorus-containing hybrid metal salt compounds and other flame retardants, wherein, The structural formula of the phosphorus-containing hybrid metal salt compound is one of the following: 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; 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; 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; 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; IX, Where x is 0.8-0.999, z is 0.001-0.2, and x+z=1; X， Where y is 0.8-0.999, z is 0.001-0.2, and y+z=1; or XI, Where p is 0.8-0.999, z is 0.001-0.2, and p+z=1; In the structural formulas V, VI, VII, VIII, IX, X, and XI, 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, which is any one of Ca, Mg, Al, Zn, Fe, Sn, Ti, and rare earth metals.

2. The compound according to claim 1, wherein, The phosphorus-containing hybrid metal salt compound is prepared by the following steps: 1a) A phosphorus-containing hybrid anion donor and a metal ion donor are reacted at 80-110 °C to obtain a precipitate of a phosphorus-containing hybrid metal salt compound; 2a) Wash, filter, and dry the precipitate; as well as 3a) The precipitate obtained in step 2a) is subjected to high-temperature treatment at 120-300℃; 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 structure II, phosphorus-containing structure III, and phosphorus-containing structure IV. or 1b) Dissolve any one or more of the phosphorus-containing structures of Formula II, Formula III and Formula IV in water in proportion, add a 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 a phosphorus-containing hybrid metal salt compound. 2b) Wash the precipitate, filter it, and dry it in an air or oxygen atmosphere; 3b) Treat the precipitate obtained in step 2b) at a high temperature of 180-300°C in an air or oxygen atmosphere; The metal ion donor is a metal salt compound, a metal oxide, or a metal hydroxide; The phosphorus-containing structures of structural formula I, structural formula II, structural formula III, and structural formula IV are as follows: I, II, III, IV。 3. The compound according to claim 2, wherein, The preparation process of the phosphorus-containing hybrid metal salt compound further includes pulverizing the material obtained in step 3a), or pulverizing the material obtained in step 3b) to the required particle size range.

4. The compound according to claim 2, wherein, The phosphorus-containing hybrid metal salt compound is also prepared by the following steps: 1a) Dissolve the phosphorus-containing hybrid anion donor in water in a certain proportion, add the metal ion donor and react at 80-110°C to obtain a precipitate of phosphorus-containing hybrid metal salt compound; 2a) Wash, filter, and dry the precipitate; 3a) The precipitate obtained in step 2a) is treated at high temperature of 120-300℃ under an inert atmosphere or vacuum.

5. The compound according to claim 4, wherein, The preparation process of the phosphorus-containing hybrid metal salt compound also includes pulverizing the material obtained in step 3a) to the required particle size range.

6. The compound according to claim 4 or 5, wherein, The inert atmosphere in step 3a) is a rare gas atmosphere or a nitrogen atmosphere.

7. The compound according to claim 1, wherein 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.

8. The compound according to claim 7, wherein the flame retardant is a phosphorus-containing compound selected from any one or more mixtures or compositions of dialkylphosphinates, monoalkylphosphinates, hypophosphites, and phosphites.

9. The compound according to claim 8, wherein the phosphorus-containing compound is aluminum diethylphosphonate.

10. The compound according to claim 1 is used as a flame retardant, a flame retardant mixture and a flame retardant synergist, or for the preparation of flame retardant polymer materials, or for the application of flame retardancy to pure polyester and cellulose fabrics and blended fabrics by impregnation.

11. The use according to claim 10, wherein the flame retardant comprises one or more of flame retardants for varnishes and foamed coatings, flame retardants for wood and other cellulosic products, and non-reactive flame retardants for polymers.

12. The use according to claim 10, wherein the flame-retardant polymer material comprises 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.

13. 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 compound according to claim 1, or A flame retardant mixture containing the compound of claim 1.

14. The flame-retardant polymer material according to claim 13, wherein, based on 100% of the total mass of raw materials, it comprises the following raw materials: 0.1 wt% to 45 wt% of the compound, 55 wt% to 99.9 wt% of the polymer matrix, 0 wt% to 55 wt% of the additives, and 0 wt% to 55 wt% of the filler or reinforcing material; or The mixture comprises 0.1 wt% to 45 wt% of a flame retardant blend, 55 wt% to 99.9 wt% of a polymer matrix, 0 wt% to 55 wt% of an additive, and 0 wt% to 55 wt% of a filler or reinforcing material; wherein the flame retardant blend comprises 0.1 wt% to 50 wt% of the blend and 50 wt% to 99.9 wt% of the flame retardant.

15. The flame-retardant polymer material according to claim 14, wherein, The flame retardant is selected from one or more of dialkylphosphine metal salts, inorganic phosphinates, 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, nylon, polyester, and polyketone resin.

16. The flame-retardant polymer material according to claim 15, wherein, The polyester includes unsaturated polyester.

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