Dialkylphosphate compositions, methods for their preparation and use

Abstract

Dialkyl phosphate composition, its preparation method and use. The dialkyl phosphate composition includes diethyl phosphate having a chemical formula represented by formula (I) and long-chain dialkyl phosphate having a chemical formula represented by formula (II). The dialkyl phosphate composition is easy to prepare, has a small addition amount, high flame retardancy efficiency for polymer materials, and excellent thermal stability. It overcomes the disadvantage of low flame retardancy efficiency of diethyl phosphate for polymer materials, and also overcomes the disadvantages of low thermal stability and a large amount of smoke during combustion of long-chain dialkyl phosphate, and can be widely used for flame retardancy of polymer materials that require high-temperature processing.

Description

Technical Field

[0001] The present invention relates to a method for preparing and using a dialkylphosphate composition, and belongs to the field of preparing flame-retardant polymer materials.

Background Art

[0002] Dialkylphosphates, especially aluminum diethylphosphate, are widely used as halogen-free flame retardants for polymer materials. However, among conventional dialkylphosphates, dialkylphosphates other than diisobutylphosphate and dipropylphosphate with high volatility have limited flame-retardant efficiency for polymer materials, and it is necessary to use a synergist in combination to reach the UL-94 V0 grade for polymer materials.

[0003] US Patents US6207736, US6255371, US6547992, etc. disclose that diethylphosphate and inorganic compounds such as ammonium polyphosphate, melamine polyphosphate, and / or zinc stannate synergistically provide flame-retardant glass fiber-reinforced polyamides and polyesters. However, the dosage of the flame retardant is large, the thermal stability of ammonium polyphosphate is not high, and melamine polyphosphate is likely to migrate in polymer materials.

[0004] US Patent US7420007 discloses aluminum diethylphosphate containing 6% or less of telomeric dialkylphosphonate. Here, the short-chain polymerized phosphate is a dialkylphosphate containing a C4-C 10 Dialkylphosphate containing a long-chain alkyl group. Chinese Patent CN104072537B discloses a method for removing long-chain dialkylphosphate in the preparation process of diethylphosphate. All of these patents emphasize avoiding the generation and use of long-chain dialkylphosphates with high content.

[0005] The dialkylphosphinic acid hybrid salts prepared by reacting two or more alkenes in the same reaction system, which are disclosed in another application of the present applicant, have high flame retardancy efficiency and high thermal stability, but are not convenient in terms of preparation and accurate control of the content of each component, and there is room for improvement.

[0006] Surprisingly, the dialkylphosphinate composition composed of a relatively high content of long-chain dialkylphosphinate and diethylphosphinate is easy to prepare, the control of the content of each component is simple, the reproducibility is high, it has a very high flame retardancy efficiency, does not require the use of a synergist, and can achieve flame retardancy of polymer materials only with the composition itself. It is unexpected that a composition composed of two or more dialkylphosphinates with low flame retardancy efficiency and unable to achieve a good flame retardancy grade for polymer materials can achieve a high flame retardancy grade for polymer materials.

Summary of the Invention

[0007] In order to solve the above technical problems, the present invention provides a method for preparing and using a dialkylphosphinate composition. The composition of the dialkylphosphinate includes component A and component B. This composition is easy to prepare, the control of the component content is simple, the addition amount of the flame retardant is small, the flame retardancy efficiency for polymer materials is high, and the economy is high.

[0008] According to a first aspect of the present invention, a dialkylphosphinate composition is provided. The dialkylphosphinate composition includes component A and component B. The component A is at least one selected from compounds having a chemical formula represented by formula (I). The component B is at least one selected from compounds having a chemical formula represented by formula (II). JPEG2025524479000002.jpg41170Here, M and N are central atoms, and R1 and R2 are each independently selected from C4-C 12 alkyl groups, R1 and R2 may be the same or different, and when R1 and R2 are simultaneously isobutyl groups, this is not the case.

[0009] M and N are each independently selected from metal elements, and the metal element is at least one selected from Group IIA, IIIA, IVA, VA metal elements, transition metal elements, and lanthanoid metal elements.

[0010] Optionally, R1 and R2 are each independently selected from C4-C6 alkyl groups.

[0011] m and n are the valences of metals M and N respectively, and m and n are each independently selected from 2, 3 or 4.

[0012] Optionally, the dialkylphosphate composition is composed of component A and component B.

[0013] Optionally, the molar ratio of component A to component B is 1-4.5:4.5-1.

[0014] In the present invention, R1 and R2 are each independently selected from C4-C 12 alkyl groups, which may be the same or different, provided that they are not both isobutyl groups at the same time. The C4-C 12 alkyl group may be a linear or branched alkyl, and includes, but is not limited to, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group.

[0015] Optionally, each of R1 and R2 is independently at least one selected from an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, and a tert-octyl group, provided that they are not both isobutyl groups at the same time.

[0016] Optionally, each of R1 and R2 is independently at least one selected from an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, and a tert-hexyl group, provided that they are not both isobutyl groups at the same time.

[0017] Optionally, each of R1 and R2 is independently at least one selected from an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, provided that they are not both isobutyl groups at the same time.

[0018] Optionally, the Group IIA metal element is at least one selected from Be, Mg, Ca, Sr, and Ba.

[0019] The Group IIIA metal element is Al.

[0020] The Group IVA metal element is Sn.

[0021] The Group VA metal element is Sb.

[0022] The transition metal element is at least one selected from Fe, Zn, Cu, Ti, Zr, and Mn.

[0023] The lanthanoid metal element is Ce.

[0024] Optionally, the metal element is at least one selected from Al, Zn, Ca, and Fe.

[0025] Optionally, the metal element is at least one selected from Al, Zn, and Ca.

[0026] Optionally, the metal element is Al, and m = n = 3.

[0027] In the present invention, component A is at least one of diethylphosphinate having a chemical formula represented by formula (I). Here, component A may be pure diethylphosphinate, for example, aluminum diethylphosphinate, or a mixture of diethylphosphinates composed of different metal ions, for example, a mixture composed of aluminum diethylphosphinate and zinc diethylphosphinate or iron diethylphosphinate. Optionally, component A is a single diethylphosphinate. Optionally, component A is aluminum diethylphosphinate.

[0028] In the actual preparation process, the diethylphosphinate contains a small amount of oligomers, for example, ethylbutylphosphinate and ethylhexylphosphinate. However, if the molar number of these oligomers is less than 10 mol% with respect to the total molar number of the diethylphosphinate, there is no visible effect on the flame retardant function of the diethylphosphinate. Therefore, in the present invention, the diethylphosphinate containing 10 mol% or less of oligomers is regarded as pure diethylphosphinate. When calculating the molar number of the diethylphosphinate, the molecular weight of the diethylphosphinate is used.

[0029] In the present invention, component B is at least one long-chain dialkylphosphate having a chemical formula represented by formula (II). Here, component B may be a single long-chain dialkylphosphate, for example, di-n-butylphosphate, or a mixture of dialkylphosphates having different long-chain alkyl groups, for example, a mixture consisting of di-n-butylphosphate and di-n-hexylphosphate. Further, it may be a mixture of long-chain dialkylphosphates consisting of different metal ions, for example, a mixture consisting of aluminum di-n-butylphosphate and iron di-n-butylphosphate, or a mixture of dialkylphosphates having the same chemical formula but different isomeric structures, for example, a mixture consisting of aluminum di-n-butylphosphate and aluminum n-butyl sec-butylphosphate.

[0030] In the composition of the present invention, the molar ratio of component A to component B is 1 - 4.5:4.5 - 1. If it exceeds 4.5:1 or is less than 1:4.5, the flame retardancy efficiency of the resulting composition is not high in either case. If the proportion of diethylphosphate is too low, the thermal stability of the composition decreases.

[0031] Optionally, the molar ratio of component A to component B is 1 - 4.5:4 - 1.

[0032] Optionally, the molar ratio of component A to component B is 1 - 4.5:3 - 1.

[0033] Optionally, the molar ratio of component A to component B is 1 - 4.5:2 - 1.

[0034] Optionally, the molar ratio of component A to component B is 1 - 4.5:1.

[0035] Optionally, the molar ratio of component A to component B is 1 - 4.3:1.

[0036] Optionally, the molar ratio of component A to component B is 1 - 4:1.

[0037] In the embodiments of the present invention, when long-chain dialkylphosphate and diethylphosphate are used alone respectively, at the same dosage, neither of them can achieve a flame-retardant grade effective as a polymer material, for example, the UL-94 V0 grade. However, the compositions composed of them can achieve an excellent flame-retardant effect on polymer materials, for example, UL-94 V0. This is very surprising.

[0038] The composition described in the present invention can be obtained by physically mixing component A and component B respectively, that is, after obtaining diethylphosphate and long-chain dialkylphosphate, according to a specific molar ratio. This physical mixing process may be carried out before the processing of the flame-retardant polymer material or during the preparation process of the flame-retardant polymer material. For convenience, the composition of component A and component B obtained by this method is abbreviated as a physical composition.

[0039] According to a second aspect of the present invention, a method for preparing the dialkylphosphate composition is provided. The method comprises reacting a raw material having diethylphosphoric acid and / or its alkali metal salt having an anion in the chemical formula of formula (I), dialkylphosphoric acid and / or its alkali metal salt having an anion in the chemical formula of formula (II), a metal element M source and a metal element N source in an aqueous phase to carry out reaction I to obtain the dialkylphosphate composition, or mixing component A and component B to obtain the dialkylphosphate composition. Said component A is selected from said component A, and said component B is selected from said component B.

[0040] In the present invention, the particle size of the composition obtained by coprecipitation (that is, the reaction I carried out in the aqueous phase) is much larger than that of pure aluminum dibutylphosphate. Thereby, the disadvantage of large dust in the physical mixing process is overcome.

[0041] In the present invention, in the coprecipitation reaction, the amount of water is not limited, and any amount that can precipitate the product is acceptable.

[0042] Optionally, the preparation method comprises reacting a raw material containing diethylphosphinic acid having an anion in the chemical formula of formula (I) and / or its alkali metal salt, at least one R1R2 group phosphinic acid having an anion in the chemical formula of formula (II) and / or its alkali metal salt, a metal element M and an N source in an aqueous phase to carry out Reaction I, obtaining a dialkylphosphinate precipitate, separating and drying the precipitate to obtain a dialkylphosphinate composition composed of the chemical formulas represented by formula (I) and formula (II). For convenience, the composition prepared by this method is abbreviated as a coprecipitation composition.

[0043] In the present invention, the molar ratio of diethylphosphinic acid having an anion in the chemical formula of formula (I) and / or its alkali metal salt, dialkylphosphinic acid having an anion in the chemical formula of formula (II) and / or its alkali metal salt, a metal element M source and a metal element N source is the molar ratio of the corresponding components in the dialkylphosphinate composition or close thereto.

[0044] Optionally, the conditions of Reaction I are a temperature of 0 - 250 °C, a pressure of 0.1 MPa - 10 MPa, and a time of 0.01 - 20 h.

[0045] Optionally, Reaction I is carried out under conditions where the pH is 0 - 4.

[0046] Optionally, the metal element is Al, that is, M = N = Al. The pH of Reaction I is 0 - 4, preferably 1 - 3.5, more preferably 2.3 - 3.3.

[0047] Specifically, if the pH of Reaction I is too low, no precipitation will occur. If the pH is too high, metal ion hydroxides will be generated and impurities will enter.

[0048] Optionally, the metal element M source is at least one selected from salts of the metal element M.

[0049] The metal element N source is at least one selected from salts of the metal element N.

[0050] Optionally, the salt of the metal element M is at least one selected from nitrates, sulfates, hydrochlorides, acetates, and oxides of the metal element M.

[0051] Optionally, the salt of the metal element N is at least one selected from nitrates, sulfates, hydrochlorides, acetates, and oxides of the metal element N.

[0052] Optionally, the molar ratio of the diethylphosphinic acid and / or its alkali metal salt, the R1R2 group phosphinic acid and / or its alkali metal salt to the sources of the metal elements M and N is the theoretical equivalent calculated based on formulas (I) and (II) or close thereto.

[0053] The separation of the dialkylphosphinate precipitate uses ordinary methods, such as filtration, centrifugation, and methods of removing the liquid phase to leave the solid phase. Drying uses common methods such as baking.

[0054] Optionally, the addition order of the reactants when performing Reaction I can be adjusted arbitrarily. For example, the diethylphosphinic acid and / or its alkali metal salt and the R1R2 group phosphinic acid and / or its alkali metal salt are uniformly mixed, and then reacted with the raw materials of the metal elements M and N in the aqueous phase.

[0055] Optionally, when performing Reaction I, the diethylphosphinic acid and / or its alkali metal salt and the R1R2 group phosphinic acid and / or its alkali metal salt are respectively added to the aqueous phase containing the metal elements M and N raw materials for reaction.

[0056] In the dialkylphosphate composition obtained by Reaction I, the contents of Component A and Component B are obtained by ordinary means such as the original input amount, the molar ratio of dialkylphosphate ions, and elemental analysis. In simple cases, for example, when Component A is aluminum diethylphosphate and Component B is aluminum dibutylphosphate, the obtained composition is dissolved in alkaline water or acidic water. Then, the molar ratio of diethylphosphate ions to dibutylphosphate ions is determined by the peak area of the phosphorus NMR spectrum, and the molar ratio of these two becomes the molar ratio of Component A to Component B. In more complex cases, for example, in the case of different metal ions, the molar ratio of Component A to Component B can be calculated by methods such as elemental analysis.

[0057] Diethylphosphonic acid and / or its alkali metal salt and R1R2 group phosphonic acid and / or its alkali metal salt can be prepared by known methods. For example, diethylphosphonic acid and / or its alkali metal salt can be obtained by an addition reaction of ethylene with phosphonic acid and / or its alkali metal salt in an aqueous solution in the presence of a free radical initiator.

[0058] In the preparation of diethylphosphonic acid and / or its alkali metal salt and R1R2 group phosphonic acid and / or its alkali metal salt, at least one of phosphate ion, phosphite ion, alkylphosphonate ion, and alkylphosphinate ion may be generated during the reaction process. These acid ions may form corresponding metal salt precipitates and be incorporated into the composition under specific conditions. Therefore, optionally, the dialkylphosphate composition composed of the compounds having the structures represented by Formula (I) and Formula (II) also includes metal salts formed by at least one of M or N metal ions and phosphate ion, phosphite ion, alkylphosphonate ion, and alkylphosphinate ion. The molar content of these phosphorus-containing metal salts in the dialkylphosphate composition is 10% or less. The number of moles is calculated based on the number of moles of phosphorus element contained. Optionally, the molar content of these phosphorus-containing metal salts in the dialkylphosphate composition is 5% or less.

[0059] Preferably, the dialkylphosphate composition consisting of component A and component B is a coprecipitation composition. Since this coprecipitation composition has the advantages of large particle size and less dust during use, it overcomes the disadvantages of small particle size and large dust of component A and / or component B in the physical composition.

[0060] According to the third aspect of the present invention, a flame retardant is provided. The flame retardant is at least one selected from the dialkylphosphate composition and the dialkylphosphate composition prepared by the method.

[0061] According to the fourth aspect of the present invention, a flame-retardant material is provided. The flame-retardant material includes a flame retardant P and a thermoplastic polymer material. The flame retardant P is at least one selected from the flame retardants.

[0062] Optionally, the mass content of the flame retardant P in the flame-retardant material is 1-35%.

[0063] Optionally, the upper limit of the mass content of the flame retardant P in the flame-retardant material is independently selected from 35%, 30%, 25%, 20%, 15%, 10%, 5%, and the lower limit is independently selected from 1%, 30%, 25%, 20%, 15%, 10%, 5%.

[0064] Optionally, the flame-retardant material includes 1-35 wt% of the flame retardant P and 65-99 wt% of the thermoplastic polymer material.

[0065] In the present invention, the thermoplastic polymer material refers to a plastic having the property of softening when heated and hardening when cooled.

[0066] Specifically, the amount of the flame retardant P used depends on the thermoplastic polymer material.

[0067] Optionally, the mass content of the flame retardant P in the flame-retardant material is 3-20%.

[0068] Optionally, the flame retardant material further contains a functional additive.

[0069] The functional additive includes at least one selected from the group consisting of a reinforcing agent, a dripping inhibitor, a stabilizer, a pigment, a dye, a carbon generation catalyst, a dispersant, a nucleating agent, an inorganic filler, and an antioxidant.

[0070] Preferably, the mass content of the functional additive in the flame retardant material is 5 - 40%.

[0071] Optionally, the upper limit of the mass content of the functional additive in the flame retardant material is independently selected from 40%, 35%, 30%, 25%, 20%, 15%, 10%, and the lower limit is independently selected from 5%, 35%, 30%, 25%, 20%, 15%, 10%.

[0072] Optionally, the reinforcing agent is selected from glass fibers.

[0073] Optionally, the dripping inhibitor is selected from Teflon.

[0074] Optionally, the inorganic filler is at least one selected from mica, calcium carbonate, calcium oxide, and silica.

[0075] Optionally, the flame retardant material further contains a flame retardant Q.

[0076] The flame retardant Q is at least one selected from nitrogen - based flame retardants and boron - based flame retardants.

[0077] Optionally, the nitrogen - based flame retardant is at least one selected from melamine cyanurate, melamine polyphosphate, and ammonium polyphosphate.

[0078] The boron - based flame retardant is selected from zinc borate.

[0079] Optionally, the mass content of the flame retardant Q in the flame retardant material is 0.5 - 20%.

[0080] Optionally, the upper limit of the mass content of the flame retardant Q in the flame retardant material is independently selected from 20%, 15%, 10%, 5%, 1%, and the lower limit is independently selected from 0.5%, 15%, 10%, 5%, 1%.

[0081] Optionally, the thermoplastic polymer material is at least one selected from polyamide and polyester.

[0082] Optionally, the polyamide is at least one selected from aliphatic polyamide, aromatic polyamide, semi-aromatic polyamide, and copolymer of semi-aromatic polyamide and aliphatic polyamide.

[0083] According to the common knowledge in the technical field, polyamide is also called nylon, which is a general term for polymers containing -NH-C(O)- amide groups in the structural unit, and is synthesized by the condensation or ring-opening reaction of one or more dicarboxylic acids and one or more diamines, and / or one or more amino acids, and / or one or more lactams. According to the composition of its main chain, polyamide is usually divided into aliphatic polyamide, aromatic polyamide and semi-aromatic polyamide. Semi-aromatic polyamide refers to that at least one monomer structure of the synthetic monomers contains an aromatic group.

[0084] Optionally, the aliphatic polyamide is one or more mixtures arbitrarily selected from the copolymer of polyamide 6 and polyamide 66, polyamide 6, and polyamide 66.

[0085] Optionally, the semi-aromatic polyamide can be prepared using any one or more aromatic dicarboxylic acids and any one or more aliphatic diamines, or can also be prepared using any one or more aromatic diamines and any one or more aliphatic dicarboxylic acids. One or more selected from dicarboxylic acids, diamines, lactams and amino acids can be further added to the reaction system to prepare a polyamide copolymer having corresponding performance. The dicarboxylic acid to be added is an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid. The diamine to be added is an aromatic diamine and / or an aliphatic diamine. The lactam to be added may be an aliphatic or aromatic lactam. The amino acid to be added may be an aromatic or aliphatic amino acid.

[0086] Optionally, the semi-aromatic polyamide is prepared using one or more aromatic dicarboxylic acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and one or more aliphatic diamines selected from butanediamine, hexamethylenediamine, octanediamine, decanediamine, 2-methylpentanediamine.

[0087] Optionally, the semi-aromatic polyamide is prepared using an aliphatic diamine, an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid.

[0088] Optionally, the semi-aromatic polyamide is prepared using an aliphatic diamine and an aromatic dicarboxylic acid. Optionally, an aliphatic dicarboxylic acid may be further added. The molar fraction of the aliphatic dicarboxylic acid is 0-45% of the total amount of dicarboxylic acids. That is, the number of moles of aliphatic dicarboxylic acid / (the number of moles of aliphatic dicarboxylic acid + the number of moles of aromatic dicarboxylic acid) = 0-45%.

[0089] Optionally, the aromatic dicarboxylic acid is one or more selected from terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. The aliphatic diamine is one or more selected from butanediamine, hexamethylenediamine, octanediamine, decanediamine, and 2-methylpentanediamine. The aliphatic dicarboxylic acid is one or more selected from adipic acid, succinic acid, sebacic acid, and suberic acid.

[0090] Optionally, the polyamide is one or more selected from polyhexamethylene terephthalamide (abbreviation: PA6T), polyhexamethylene isophthalamide (abbreviation: PA6I), terephthalic acid / hexamethylenediamine / caprolactam copolymer (abbreviation: PA6T / 6), terephthalic acid / hexamethylenediamine / adipic acid copolymer (abbreviation: PA6T / 66), terephthalic acid / hexamethylenediamine / adipic acid / isophthalic acid copolymer (abbreviation: PA6T / 6I / 66), polynonamethylene terephthalamide (abbreviation: PA9T), polydecandiamine terephthalamide (abbreviation: PA10T), polydodecyl terephthalamide (abbreviation: PA12T), terephthalic acid / hexamethylenediamine / dodecyl lactam copolymer (abbreviation: PA6T / 12), poly(m-xylylene adipamide) (abbreviation: MXD6), terephthalic acid / hexamethylenediamine / 2-methylpentanediamine copolymer (abbreviation: PA6T / 2-MPMDT), and terephthalic acid / 2,2,4-trimethylhexamethylenediamine / 2,4,4-trimethylhexamethylenediamine copolymer.

[0091] Optionally, the aliphatic polyamide is at least one selected from polyamide 6, polyamide 66, and a copolymer of polyamide 6 and polyamide 66.

[0092] Optionally, the semi-aromatic polyamide is selected from polyphthalamide (PPA).

[0093] Optionally, the polyester is selected from polybutylene terephthalate (PBT).

[0094] The present invention has the following beneficial effects. (1) The dialkylphosphate composition containing component A and component B provided by the present invention has a small addition amount, a high flame retardancy efficiency for polymer materials, and high economic efficiency. It overcomes the drawback that the flame retardancy efficiency of diethylphosphate and long-chain dialkylphosphate for polymer materials is low, and solves the drawback that the thermal stability of long-chain dialkylphosphate used alone is low, and can be widely used for the flame retardancy of polymer materials that require high-temperature processing. (2) The dialkylphosphate composition containing component A and component B provided by the present invention is easy to prepare, the ratio of different components can be accurately controlled, and the physical properties and stability of the flame retardant material can be guaranteed.

Brief Description of the Drawings

[0095]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0096] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

[0097] Unless otherwise specified, all raw materials used in the examples of the present invention were purchased through commercial channels.

[0098] The raw materials used in the examples are as follows. PA66 (also called polyamide 66 or nylon 66): Zytel 70G35 HSL NC010 of DuPont, USA, glass fiber content 35% by weight.

[0099] PA6 (also known as polyamide 6 or nylon 6): Zytel 73G30L NC010 from DuPont in the United States, with a glass fiber content of 30% by weight.

[0100] Aluminum diethylphosphinate: Exolit OP1230 from Clariant in Germany, D 50 = 30.80 μm.

[0101] Zinc diethylphosphinate: Clariant in Germany.

[0102] Antioxidant 1010: Pentaerythritol ester of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid], Shanghai Macklin Biochemical Co., Ltd.

[0103] Antioxidant 168: Tris[2,4-di-tert-butylphenyl]phosphite, from Strem in the United States.

[0104] Compound antioxidant: A mixture of antioxidant 1010 (pentaerythritol ester of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]) and antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite) in a weight ratio of 1:1.

[0105] Combustion test standard: GB / T 2408-2008 standard.

[0106] Nuclear magnetic resonance (NMR) test: Instrument model AVANCE III 400 MHz, Bruker in Germany.

[0107] Nuclear magnetic resonance - phosphorus ( 31 P-NMR) test method: Preliminary delay D1 = 10 seconds, Bruker in Germany, with the ratio of peak areas being the ratio of the number of moles of each phosphonate ion.

[0108] Instrument model used for X-ray diffraction (XRD) test: D8 ADVANCE DAVINCI, Bruker in Germany.

[0109] Particle size D50: Dry test using the Sympatec laser particle size analyzer Heloise - oasis HELOS (H3938) in Germany.

[0110] Example 1 Preparation of aluminum dialkylphosphonate composition The molar ratio of aluminum diethylphosphonate having the chemical formula represented by formula (I) to aluminum dibutylphosphonate having the chemical formula represented by formula (II) is 1.2:1. Preparation of sodium diethylphosphonate: Dissolve 100 g of sodium phosphonate monohydrate in 500 g of water, put it into a 1 L stainless steel autoclave, replace the autoclave with nitrogen gas twice, evacuate it, and then introduce ethylene up to 0.8 MPa. After heating the reaction solution to about 90 °C, a 4% aqueous sodium persulfate solution with a mass concentration of 10 ml / h was introduced at a constant rate, ethylene was continuously introduced into the autoclave, and the introduction amount of ethylene was measured by a gas flow meter. After 8 hours, since the pressure of the system no longer decreased, the reaction was stopped, cooled, the pressure was released, purged with N2, and the material was discharged to obtain a transparent reaction solution.

[0111] Preparation of sodium dibutylphosphonate: Dissolve 100 g of sodium phosphonate monohydrate in 500 g of water, put it into a 1 L stainless steel autoclave, replace the autoclave with nitrogen gas twice, evacuate it, and then introduce butene until the pressure no longer rises. After heating the reaction solution to about 90 °C, a 4% aqueous sodium persulfate solution with a mass concentration of 10 ml / h was added at a constant rate, butene was continuously introduced into the autoclave, and the introduction amount of butene was measured by a gas flow meter. After 25.5 hours, since the pressure of the system no longer decreased, the reaction was stopped, cooled, the pressure was released, purged with N2, and the material was discharged to obtain a transparent reaction solution.

[0112] Preparation of Aluminum Dialkylphosphonate Composition: Take 135.37 g (containing 0.18 mol of phosphorus) of the sodium diethylphosphonate solution and 164.52 g (containing 0.18 mol of phosphorus) of the sodium dibutylphosphonate solution, mix them uniformly, and then slowly mix them with an aqueous solution containing 39.99 g of aluminum sulfate octadecahydrate with a mass concentration of 10% at normal pressure. Control the reaction temperature at 70 °C, adjust the pH value to below 3.0 to obtain a large amount of precipitate. After adding and mixing the raw materials, keep them warm for 0.5 hour. Perform hot filtration, wash the filter cake with clear water, and then dry it at 120 °C to obtain 50.06 g of a white solid aluminum dialkylphosphonate composition.

[0113] The aluminum dialkylphosphonate composition obtained in this test was dissolved in an aqueous solution of sodium hydroxide and subjected to phosphorus nuclear magnetic resonance. As a result, the content of diethylphosphonate ion mol was 54.55%, and the total content of dibutylphosphonate ion mol was 45.45%. That is, in the aluminum dialkylphosphonate composition, the molar ratio of aluminum diethylphosphonate having the chemical formula represented by formula (I) to aluminum dibutylphosphonate having the chemical formula represented by formula (II) was 1.2:1.

[0114] The prepared aluminum dialkylphosphonate composition was measured by XRD. The interlayer distances corresponding to the two characteristic peaks with the highest relative intensity obtained by XRD measurement were 11.835 Å (100%) and 9.680 Å (45.1%), respectively.

[0115] The particle size of the prepared aluminum dialkylphosphonate composition was measured. As a result, D 50 = 17.78 μm.

[0116] Note: The diethylphosphinic acid ion contains 98 mol% of diethylphosphinic acid ions and 2 mol% of short-chain polymerized diethylphosphinic acid ions. The dibutylphosphinic acid ion contains n-butyl sec-butylphosphinic acid ions (R1≠R2, being an n-butyl group and a sec-butyl group respectively), di-n-butylphosphinic acid ions (R1 = R2 = n-butyl group), di-sec-butylphosphinic acid ions (R1 = R2 = sec-butyl group), and short-chain polymerized dibutylphosphinic acid ions. The same applies hereinafter.

[0117] Example 2 Preparation of Aluminum Dialkylphosphinate Composition The molar ratio of aluminum diethylphosphinate having the chemical formula represented by formula (I) to aluminum dibutylphosphinate having the chemical formula represented by formula (II) is 2.4:1. Preparation of Aluminum Dialkylphosphinate Composition: 180.49 g of a sodium diethylphosphinate solution (containing 0.24 mol of phosphorus) prepared by the method of Example 1 and 109.68 g of a sodium dibutylphosphinate solution (containing 0.12 mol of phosphorus) were uniformly mixed, and then slowly mixed with an aqueous solution containing 39.99 g of aluminum sulfate octadecahydrate with a mass concentration of 10% at normal pressure. The reaction temperature was controlled at 70 °C, and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After adding and mixing the raw materials, it was kept warm for 0.5 hour. It was hot-filtered, the filter cake was washed with clear water, and then dried at 120 °C to obtain 48.56 g of a white solid, the aluminum dialkylphosphinate composition.

[0118] The aluminum dialkylphosphonate composition obtained in this test was dissolved in an aqueous solution of sodium hydroxide, and phosphorus nuclear magnetic resonance was performed. As a result, the content of diethylphosphonate ion mole was 69.98%, the total content of dibutylphosphonate ion mole was 29.17%, and the content of other phosphorus-containing impurities, for example, the content of ethylphosphonate ion mole was 0.10%, the content of ethylphosphonate ion mole was 0.13%, the content of butylphosphonate ion mole was 0.43%, and the content of butylphosphonate ion mole was 0.19%. That is, in the aluminum dialkylphosphonate composition, the molar ratio of aluminum diethylphosphonate having the chemical formula represented by formula (I) to aluminum dibutylphosphonate having the chemical formula represented by formula (II) was 2.4:1. The phosphorus nuclear magnetic resonance spectrum ( 31 P-NMR) is shown in Figure 1.

[0119] The prepared aluminum dialkylphosphonate composition was measured by XRD. The interlayer distances corresponding to the two characteristic peaks with the highest relative intensities obtained by XRD measurement were 11.867 Å (78.7%) and 9.681 Å (100%), respectively.

[0120] As a result of measuring the particle size of the prepared aluminum dialkylphosphonate composition, D 50 = 23.27 μm.

[0121] Example 3 Preparation of Aluminum Dialkylphosphonate Composition The molar ratio of aluminum diethylphosphonate having the chemical formula represented by formula (I) to aluminum dibutylphosphonate having the chemical formula represented by formula (II) is 3.6:1. Preparation of Aluminum Dialkylphosphonate Composition: 203.05 g of a sodium diethylphosphonate solution (containing 0.27 mol of phosphorus) prepared by the method of Example 1 and 82.26 g of a sodium dibutylphosphonate solution (containing 0.09 mol of phosphorus) were uniformly mixed. Then, they were slowly mixed with an aqueous solution containing 39.99 g of aluminum sulfate octadecahydrate with a mass concentration of 10% at normal pressure, the reaction temperature was controlled at 70 °C, the pH value was adjusted to 3.0 or less, and a large amount of precipitate was obtained. After adding and mixing the raw materials, it was kept warm for 0.5 h. It was hot-filtered, the filter cake was washed with clear water, and then dried at 120 °C to obtain 47.72 g of a white solid aluminum dialkylphosphonate composition.

[0122] The aluminum dialkylphosphonate composition obtained in this test was dissolved in an aqueous solution of sodium hydroxide, and phosphorus nuclear magnetic resonance was performed. As a result, the content of diethylphosphonate ion mol was 78.36%, and the total content of dibutylphosphonate ion mol was 21.64%. That is, in the aluminum dialkylphosphonate composition, the molar ratio of aluminum diethylphosphonate having the chemical formula represented by formula (I) to aluminum dibutylphosphonate having the chemical formula represented by formula (II) was 3.6:1.

[0123] The prepared aluminum dialkylphosphonate composition was measured by XRD. The interlayer distances corresponding to the two characteristic peaks with the highest relative intensities obtained by XRD measurement were 11.701 Å (27.2%) and 9.659 Å (100%), respectively.

[0124] The particle size of the prepared aluminum dialkylphosphonate composition was measured. As a result, D 50 = 49.20 μm.

[0125] Figure 2 shows the XRD spectra of the aluminum dialkylphosphonate compositions prepared in Examples 1-3. As can be seen from Figure 2, in the region of the strongest absorption peak, there are two independent peaks with basically constant peak values (d values), which belong to aluminum diethylphosphonate and aluminum dibutylphosphonate respectively, indicating that the composition obtained in the present invention is a physical mixture of diethylphosphate and long-chain dialkylphosphate.

[0126] Comparative Example 1: Preparation of Aluminum Dibutylphosphonate 100 g of sodium phosphonate monohydrate was dissolved in 500 g of water, put into a 1 L stainless steel autoclave, the reaction kettle was replaced with nitrogen gas twice, evacuated, and then butene was introduced until the pressure no longer rose. After heating the reaction solution to about 90 °C, an aqueous sodium persulfate solution with a mass concentration of 4% was added at a constant rate of 10 ml / h, butene was continuously introduced into the reaction kettle, and the introduction amount of butene was measured with a gas flow meter. After 25.5 hours, since the pressure of the system no longer decreased, the reaction was stopped, cooled, the pressure was released, N2 purged, and the material was discharged to obtain a transparent reaction solution. 394 g of a part of the above solution (containing 0.3996 mol of phosphorus) was slowly mixed with an aqueous solution containing 44.38 g of aluminum sulfate octadecahydrate with a mass concentration of 10%, the reaction temperature was controlled at 70 °C, the pH value was adjusted to 3.0 or less, and a large amount of precipitate was obtained. After adding and mixing the raw materials, the mixture was kept warm for 0.5 hour. It was hot-filtered, the filter cake was washed with clear water, and then dried at 120 °C to obtain 67.28 g of white solid aluminum dibutylphosphonate.

[0127] As a result of measuring the particle size of the prepared aluminum dibutylphosphonate, D 50 = 2.27 μm.

[0128] Comparative Example 2: Preparation of Aluminum Dihexylphosphonate Referring to Comparative Example 1, aluminum dihexylphosphonate was prepared using 1-hexene instead of 1-butene. Since the product was sticky, D 50 could not be accurately measured.

[0129] Comparative Example 3 Preparation of Iron Dihexylphosphate Referring to Comparative Example 1, iron dihexylphosphate was prepared using 1-hexene instead of 1-butene and using iron(III) chloride hexahydrate instead of aluminum sulfate 18-hydrate. Since the product was sticky, D 50 could not be accurately measured.

[0130] Example 4 Polyamide PA66, the aluminum dialkylphosphate composition prepared in Example 1, and the composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4, the temperature was set to 280 °C, taken out and cooled after 5 minutes, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0131] Example 5 Polyamide PA6, the aluminum dialkylphosphate composition prepared in Example 1, and the composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4, the temperature was set to 260 °C, taken out and cooled after 5 minutes, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 260 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0132] Example 6 Polyamide PA66, the aluminum dialkylphosphonate composition prepared in Example 2, and the composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set at 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0133] Example 7 Polyamide PA6, the aluminum dialkylphosphonate composition prepared in Example 2, and the composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set at 260 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 260 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0134] Example 8 Polyamide PA66, the aluminum dialkylphosphonate composition prepared in Example 3, and the composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set at 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0135] Example 9 Polyamide PA6, the aluminum dialkylphosphinate composition prepared in Example 3, and the composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set at 260 °C, taken out and cooled after 5 minutes, and then dried. Thereafter, it was filled into a mold, preheated in a flat vulcanizer at 260 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0136] Example 10 Polyamide PA66, aluminum diethylphosphinate, aluminum dibutylphosphinate prepared in Comparative Example 1, and the composite antioxidant were added to a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:10:10:0.4 (where the molar ratio of aluminum diethylphosphinate to aluminum dibutylphosphinate is 1.43:1), mixed, the temperature was set at 280 °C, taken out and cooled after 5 minutes, and then dried. Thereafter, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0137] Example 11 Polyamide PA66, aluminum diethylphosphinate, aluminum dibutylphosphinate prepared in Comparative Example 1, and the composite antioxidant were added to a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:15:5:0.4 (where the molar ratio of aluminum diethylphosphinate to aluminum dibutylphosphinate is 4.3:1), mixed, the temperature was set at 280 °C, taken out and cooled after 5 minutes, and then dried. Thereafter, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-0.

[0138] Example 12 Polyamide PA66, aluminum diethylphosphinate, aluminum dibutylphosphinate prepared in Comparative Example 1, and a composite antioxidant were mixed in a weight ratio of 79.6:3:17:0.4 (where the molar ratio of aluminum diethylphosphinate to aluminum dibutylphosphinate is 1:4) by adding them to a mixer with a rotational speed of 50 rpm per minute, respectively. The temperature was set at 280°C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was UL94 V-1.

[0139] Example 13 Polyamide PA66, zinc diethylphosphinate, aluminum dibutylphosphinate prepared in Comparative Example 1, and a composite antioxidant were mixed in a weight ratio of 79.6:4.3:15.7:0.4 (where the molar ratio of zinc diethylphosphinate to aluminum dibutylphosphinate is 1:2) by adding them to a mixer with a rotational speed of 50 rpm per minute, respectively. The temperature was set at 280°C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 3.2 mm sample was UL94 V-1.

[0140] Example 14 Polyamide PA66, aluminum diethylphosphinate, aluminum dihexylphosphinate prepared in Comparative Example 2, and a composite antioxidant were mixed in a weight ratio of 79.6:13.65:6.35:0.4 (where the molar ratio of aluminum diethylphosphinate to aluminum dihexylphosphinate is 4:1) by adding them to a mixer with a rotation speed of 50 rpm / min, respectively. The temperature was set to 280 °C, taken out and cooled after 5 minutes, and then dried. Thereafter, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardancy grade of the 1.6 mm sample was UL94 V-0.

[0141] Example 15 Polyamide PA6, aluminum diethylphosphinate, iron dihexylphosphinate prepared in Comparative Example 3, and a composite antioxidant were mixed in a weight ratio of 79.6:13.5:6.5:0.4 (where the molar ratio of aluminum diethylphosphinate to iron dihexylphosphinate is 4:1) by adding them to a mixer with a rotation speed of 50 rpm / min, respectively. The temperature was set to 260 °C, taken out and cooled after 5 minutes, and then dried. Thereafter, it was filled into a mold, preheated in a flat vulcanizer at 260 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardancy grade of the 1.6 mm sample was UL94 V-0.

[0142] Comparative Example 4 Polyamide PA66, aluminum diethylphosphinate, and a composite antioxidant were mixed in a weight ratio of 79.6:20:0.4 in a mixer with a rotation speed of 50 rpm / min. The temperature was set to 280 °C, taken out and cooled after 5 minutes, and then dried. Thereafter, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardancy grades of the 1.6 mm and 3.2 mm samples were without UL94 grade.

[0143] Comparative Example 5 Polyamide PA66, zinc diethylphosphinate, and a composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set to 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame-retardant grades of the 1.6 mm and 3.2 mm samples were without UL94 grade.

[0144] Comparative Example 6 Polyamide PA66, aluminum dibutylphosphinate prepared in Comparative Example 1, and a composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set to 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame-retardant grades of the 1.6 mm and 3.2 mm samples were without UL94 grade.

[0145] Comparative Example 7 Polyamide PA66, aluminum dihexylphosphinate prepared in Comparative Example 2, and a composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set to 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for ⑤ minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame-retardant grades of the 1.6 mm and 3.2 mm samples were without UL94 grade.

[0146] Comparative Example 8 Polyamide PA66, iron dihexylphosphate prepared in Comparative Example 3, and a composite antioxidant were mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:20:0.4. The temperature was set to 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grades of the 1.6 mm and 3.2 mm samples were without UL94 grade.

[0147] Comparative Example 9 Polyamide PA66, aluminum diethylphosphate, aluminum dibutylphosphate prepared in Comparative Example 1, and a composite antioxidant were added to and mixed in a mixer with a rotation speed of 50 rpm / min at a weight ratio of 79.6:17.3:2.7:0.4 (where the molar ratio of aluminum diethylphosphate to aluminum dibutylphosphate is 9:1). The temperature was set to 280 °C, taken out after 5 minutes, cooled, and dried. Then, it was filled into a mold, preheated in a flat vulcanizer at 280 °C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut out and tested. The flame retardant grade of the 1.6 mm sample was without UL94 grade.

[0148] According to Comparative Examples 4 - 8, when used alone, aluminum diethylphosphate, zinc diethylphosphate, aluminum dibutylphosphate, aluminum dihexylphosphate, and iron dihexylphosphate have low flame retardant efficiency for polyamide. In Comparative Example 6, there is a very large amount of dust, which is disadvantageous for operation. According to Comparative Example 9, it can be seen that when the molar ratio of aluminum diethylphosphate to aluminum dibutylphosphate is too high, the flame retardant efficiency of the composition for polyamide decreases.

[0149] According to Examples 4-15, the dialkylphosphate composition described in the present invention has excellent flame retardancy efficiency for polyamide, and it can be seen that the drawbacks of low flame retardancy efficiency for polymer materials when diethylphosphate and long-chain dialkylphosphate are used alone can be overcome. In the use process, Examples 10-12 show that there is significantly more dust than in Examples 4-9, indicating that the coprecipitation composition ratio is more environmentally friendly in the operating environment compared to the physical composition.

[0150] The above description is only some examples of the present invention and does not limit the present invention. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention. Within the scope of the technical means of the present invention, any changes or modifications made by those skilled in the art based on the above technical content are equivalent to equivalent embodiments and are all included within the scope of the present invention.

Claims

1. A dialkylphosphate composition, wherein the dialkylphosphate composition comprises Component A and Component B, Component A is at least one selected from compounds having a chemical formula represented by formula (I), Component B is at least one selected from compounds having a chemical formula represented by formula (II), (In the formula, M and N are central atoms, and R １ , R ２ are each independently selected from alkyl groups of C ４ -C １２ , and when R １ , R ２ are simultaneously isobutyl groups, there is no such case, M and N are each independently selected from metal elements, and the metal element is at least one selected from Group IIA, IIIA, IVA, VA metal elements, transition metal elements, and lanthanoid metal elements, m and n are the valences of metals M and N, respectively, m and n are each independently selected from 2, 3 or 4. )

2. The dialkylphosphate composition according to claim 1, wherein the molar ratio of Component A to Component B is 1 - 4.5:4.5 - 1.

3. The at least one Group IIA metal element is selected from at least one of Be, Mg, Ca, Sr, Ba, the Group IIIA metal element is Al, the Group IVA metal element is Sn, the Group VA metal element is Sb, the transition metal element is at least one selected from Fe, Zn, Cu, Ti, Zr, Mn, The dialkylphosphate composition according to claim 1, wherein the lanthanoid metal element is Ce.

4. The dialkylphosphate composition according to claim 1, wherein both M and N are Al, and m = n = 3.

5. A method for preparing the dialkylphosphate composition according to any one of claims 1 to 4, reacting a material containing diethylphosphinic acid having an anion in the chemical formula of formula (I) and / or its alkali metal salt, dialkylphosphinic acid having an anion in the chemical formula of formula (II) and / or its alkali metal salt, a metal element M source and a metal element N source in an aqueous phase to carry out Reaction I to obtain the dialkylphosphate composition, or mixing Component A and Component B to obtain the dialkylphosphate composition, The preparation method is characterized in that Component A is selected from Component A according to claim 1, and Component B is selected from Component B according to claim 1.

6. The preparation method according to claim 5, wherein Reaction I is carried out under the condition that the pH is 0 - 4.

7. The preparation method according to claim 5, wherein the conditions of the reaction I are characterized in that the temperature is 0 - 250 °C, the pressure is 0.1 MPa - 10 MPa, and the time is 0.01 - 20 h.

8. The metal element M source is at least one selected from salts of the metal element M, The metal element N source is at least one selected from salts of the metal element N, Preferably, the salt of the metal element M is at least one selected from nitrates, sulfates, hydrochlorides, acetates, and oxides of the metal element M, The preparation method according to claim 5, wherein the salt of the metal element N is at least one selected from nitrates, sulfates, hydrochlorides, acetates, and oxides of the metal element N.

9. A flame retardant, which is at least one selected from the dialkylphosphinate compositions according to any one of claims 1 to 4 and the dialkylphosphinate compositions prepared by the method according to any one of claims 5 to 8.

10. A flame-retardant material containing a flame retardant P and a thermoplastic polymer material, The flame-retardant material, wherein the flame retardant P is at least one selected from the flame retardants according to claim 9.

11. The flame-retardant material according to claim 10, wherein the mass content of the flame retardant P in the flame-retardant material is 1 - 35%.

12. The flame-retardant material further contains a functional additive, The functional additive is at least one selected from a reinforcing agent, a dripping inhibitor, a stabilizer, a pigment, a dye, a carbon generation catalyst, a dispersant, a nucleating agent, an inorganic filler, and an antioxidant, Preferably, the flame-retardant material according to claim 10, wherein the mass content of the functional additive in the flame-retardant material is 5 - 40%.

13. The flame-retardant material further contains a flame retardant Q, The flame-retardant material according to claim 12, wherein the flame retardant Q is at least one selected from a nitrogen-based flame retardant and a boron-based flame retardant.

14. The flame-retardant material according to claim 13, wherein the mass content of the flame retardant Q in the flame-retardant material is 0.5 - 20%.

15. The flame-retardant material according to claim 10, wherein the thermoplastic polymer material is at least one selected from polyamide and polyester.

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