Phosphate ester, preparation method therefor and use thereof

Abstract

Disclosed are a phosphate ester, a preparation method therefor and a use thereof. The phosphate ester has a structure represented by formula (VIII). Also provided is a method for preparing a phosphate ester, wherein P(O)-OH and a specific carbonate compound undergo an acidolysis reaction to produce carbon dioxide and a phosphate ester; an alkylene or phenylene structure is introduced into a phosphate ester structure; and a terminal group is configured as a hydroxyl group or a phosphate ester group, such that the flame retardancy of the phosphate ester can be improved, and the phosphate ester can pass a UL94 test when the addition amount is as low as 5%. At the same time, the phosphate ester has good physical properties, and as the addition amount increases, the physical properties of the obtained flame-retardant material, especially a flexural performance, do not decrease significantly.

Description

Phosphonate, preparation method and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic synthesis, and particularly relates to a phosphonate, a preparation method and application thereof. BACKGROUND

[0002] Phosphonate compounds are widely used in the fields of biology, medicine, materials, etc. The main synthesis method is the esterification reaction of P(O)-OH and alcohol / phenol or the esterification reaction of P(O)-Cl and alcohol / phenol, etc. The reaction of phosphorus oxychloride and alcohol / phenol produces by-products such as hydrogen chloride, which is poor in environmental protection. The direct esterification method of P(O)-OH and alcohol / phenol is better in environmental protection. The difficulty of the direct esterification method varies greatly due to the influence of the substituents on phosphorus. For example, it is difficult to perform direct esterification of dialkyl hypophosphorous acid and alcohol / phenol (Org. Biomol. Chem., 2012, 10, 2011).

[0003] At present, the existing preparation methods of dialkyl hypophosphite ester include: 1) using dialkyl hypophosphite alkali metal salt and halogenated alkane to obtain the target product, and producing inorganic chloride as a by-product. 2) dialkyl hypophosphite and epoxy compound reaction, see patent application file CN111344323A, but this method is limited to epoxy compounds. 3) dialkyl hypophosphite and phenylboronic acid reaction. Preparation of diphenyl hypophosphite phenyl ester, see patent application file CN105669743A. 4) diphenyl hypophosphite and phenol in the presence of condensing agent carbonyldiimidazole to prepare phenyl ester, see patent application file CN107082789A. However, these methods have disadvantages, methods 1) and 2) are difficult to prepare dialkyl hypophosphite aryl ester, and methods 3) and 4) need expensive auxiliaries or starting materials, which are not only poor in economy, but also troublesome in purification. And the flame retardance of the prepared phosphonate needs to be improved.

[0004] In summary, it is very necessary to develop a phosphonate synthesis method which is simple in synthesis process, good in environmental protection, wide in applicability, and high in flame retardance of the prepared phosphonate.

[0005] SUMMARY

[0006] Therefore, the purpose of the present application is to provide a phosphonate, a preparation method and application thereof, which are simple, efficient, good in environmental protection, wide in applicability, and high in flame retardance of the prepared phosphonate.

[0007] The present application provides a preparation method of a phosphonate, which comprises the following steps:

[0008] P(O)-OH and carbonate compound are subjected to acidolysis reaction to generate carbon dioxide and phosphonate.

[0009] Specifically, P(O)-OH and a carbonate compound are mixed, and at least one carbonate group in the carbonate compound and P(O)-OH undergo acidolysis to produce carbon dioxide and a phosphate ester.

[0010] The P(O)-OH has a general structure as shown in formula (I);

[0011] In formula (I), R1 and R2 are independently selected from hydrogen, C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group, or C6-C 24 aromatic group substituted with at least one substituent; the substituent is selected from C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, mercapto group, and heterocycle;

[0012] a and b are independently selected from 0 or 1, and when a = b = 0, R1 and R2 are both hydrogen atoms or neither is a hydrogen atom.

[0013] The phosphate ester is a product obtained by acidolysis of at least one carbonate group in the carbonate compound and P(O)-OH. The acidolysis reaction simultaneously produces CO2. Structurally, when the carbonate is an acyclic carbonate, the phosphate ester is equivalent to a structure in which the -OH of P(O)-OH is substituted with an alkoxy or aryloxy group of the carbonate, as shown in reaction formula (1). When the carbonate is a cyclic carbonate, the structure of the phosphate ester is equivalent to a structure in which the -OH of P(O)-OH is substituted with an alkoxy or aryloxy group at one end of the cyclic carbonate group, and the other end of the cycle becomes a hydroxyl group or a phosphate ester group. Before becoming a hydroxyl group or a phosphate ester group, the other end can first polymerize itself, and then become a hydroxyl group or a phosphate ester group, as shown in reaction formula (2).

[0014] wherein R 100 , R 101 , R 102 are organic moieties, and R 103 is H or a phosphoryl group. n is a natural number greater than or equal to 1.

[0015] Alternatively, R1 and R2 are independently selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a hydroxyethyl group, a hydroxypropyl group, a benzyl group, a phenyl group, and a p-methylphenyl group, and when a = b = 0, R1 and R2 are both hydrogen atoms or neither is a hydrogen atom.

[0016] Optionally, R1, R2are independently selected from the group consisting of hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, p-methylphenyl, and at least one of a and b is 0, and when a = b = 0, both R1, R2are hydrogen atom or neither is hydrogen atom.

[0017] Optionally, R1, R2are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, p-methylphenyl, and a = b = 0.

[0018] Optionally, R1, R2are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, phenyl, p-methylphenyl, and a = b = 0.

[0019] Optionally, the P(O)-OH compound is at least one selected from the group consisting of phosphoric acid, diphenyl phosphate, dimethyl phosphate, diethyl phosphate, methyl phosphoric acid, ethyl phosphoric acid, propyl phosphoric acid, benzyl phosphoric acid, phenyl phosphoric acid, monophenyl phenyl phosphate, monomethyl phenyl phosphate, monoethyl phenyl phosphate, monophenyl methyl phosphate, monophenyl ethyl phosphate, dimethyl phosphinic acid, methyl ethyl phosphinic acid, diethyl phosphinic acid, dipropyl phosphinic acid, diisopropyl phosphinic acid, ethyl propyl phosphinic acid, di-n-butyl phosphinic acid, diisobutyl phosphinic acid, propyl butyl phosphinic acid, ethyl butyl phosphinic acid, methyl phenyl phosphinic acid, ethyl phenyl phosphinic acid, dibenzyl phosphinic acid, di(3-chloropropyl) phosphinic acid, di(3-bromopropyl) phosphinic acid, di(2-chloropropyl) phosphinic acid, di(2-bromopropyl) phosphinic acid, and diphenyl phosphinic acid.

[0020] Optionally, the carbonate compound has a carbonate group -OC(=O)O- in its structure. The carbonate is an acyclic carbonate and / or a cyclic carbonate.

[0021] Optionally, the carbonate compound has a structure as shown in formula (II);

[0022] In formula (II), R3, R4are independently selected from the group consisting of C1-C 18 alkyl, C1-C 18 alkyl substituted by at least one substituent, C6-C 24 aromatic group, or C6-C 24 aromatic group substituted by at least one substituent; the substituent is selected from the group consisting of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl, amino, nitro, halogen, C1-C 18 ester group, C1-C 18 alkoxy, C1-C 18 ether group, C1-C18 one or more of a thioether group and a mercapto group.

[0023] Optionally, R3, R4 are independently selected from at least one of a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a phenyl group, a benzyl group, and a 4-methylphenyl group.

[0024] Optionally, R3, R4 are independently selected from at least one of a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, and a phenyl group.

[0025] In an embodiment of the present application, the carbonate compound has a structure as shown in formula (III):

[0026] In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 24 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 24 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 24 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group. 18 In formula (III), R5, R6 are independently selected from at least one of a C1-C4 alkyl group, a C1-C4 alkyl group substituted with at least one substituent, a C6-C10 aryl group, a C6-C10 aryl group substituted with at least one substituent, a carbonate group, a hydroxyl group, an amino group, a nitro group, a halogen, a C1-C4 ester group, a C1-C4 alkoxy group, a C1-C4 ether group, a thioether group, and a mercapto group.

[0027] Optionally, R5, R6 are independently selected from one or more of a hydrogen atom, -CH3, -CH2CH3, -CH2OH, a phenyl group, and -CH2OC(=O)OCH3.

[0028] In an embodiment of the present application, the carbonate compound comprises both a carbonate compound molecule having a structure as shown in formula (II) and a carbonate compound molecule having a structure as shown in formula (III). For example, a glycerol carbonate directly obtained by a dimethyl carbonate and glycerol ester exchange reaction, which comprises both a carbonate compound molecule having a structure as shown in formula (II) and a carbonate compound molecule having a structure as shown in formula (III).

[0029] In certain embodiments of the present application, the carbonate compound comprises at least one of a carbonate compound having a structure according to Formula (II) and a carbonate compound having a structure according to Formula (III). Specifically, the carbonate compound can be a single compound or a mixture of carbonate compounds. For example, the carbonate compound can be a carbonate compound having a structure according to Formula (II) or a carbonate compound having a structure according to Formula (III). Alternatively, the carbonate compound can comprise both a carbonate compound having a structure according to Formula (II) and a carbonate compound having a structure according to Formula (III).

[0030] In certain embodiments of the present application, the carbonate compound is selected from at least one of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, vinyl carbonate, propylene carbonate, allyl methyl carbonate, vinylene carbonate, vinyl ethylene carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(biphenyl) carbonate, t-butyl phenyl carbonate, di(2-methoxyphenyl) carbonate, glycerol carbonate, bisphenol A polycarbonate, bisphenol A-tetramethyl bisphenol A-carbonate copolymer, carbon dioxide-ethylene oxide copolymer, carbon dioxide-propylene oxide copolymer, trimethylolpropane carbonate (or a product obtained by transesterification of trimethylolpropane and dimethyl carbonate), a product obtained by transesterification of glycerol and an alkyl carbonate, and a product obtained by transesterification of glycerol and a diaryl ester.

[0031] In certain embodiments of the present application, when the phosphate ester is P(O)-OH and the carbonate compound has a structure according to Formula (II), the product obtained by acidolysis reaction has a structure according to Formula (IV):

[0032] In Formula (IV), a and b are defined the same as a and b in Formula (I).

[0033] R 20 is selected from R3or R4in Formula (II);

[0034] R 1a , R 2b are independently selected from R 20 or R1and R2in Formula (I); and only when R1= H and a = 1 in Formula (I), R 1a = H or R 20 ; and / or, when R2= H and b = 1 in Formula (I), R 2b = H or R 20 .

[0035] In some embodiments of the present application, when the phosphate is P(O)-OH and the carbonate compound has the structure shown in formula (III), the product obtained by acidolysis reaction is a compound having the structure shown in formula (V):

[0036] In formula (V), a, b have the same definition as a, b in formula (I);

[0037] R5, R6are selected as described in formula (III), which will not be repeated here.

[0038] m is a natural number greater than or equal to 1;

[0039] R7is H or a group having the structure shown in formula (VI);

[0040] In formula (VI), R1, R2, a, b are selected as described in formula (I), which will not be repeated here;

[0041] R 1a , R 2b are independently selected from -(CHR5-CHR6-O-)mR7, R1in formula (I), or R2in formula (I); and only when R1in formula (I) = H, a = 1, R 1a = H or -(CHR5-CHR6-O-)mR7, and / or R2= H, b = 1, R 2b = H or -(CHR5-CHR6-O-)mR7.

[0042] When the P(O)-OH and the carbonate compound are subjected to acidolysis reaction, the molar ratio of the two is determined according to the molar ratio of the reactive functional groups of the two, wherein the reactive functional group of the P(O)-OH compound is P-OH, and the reactive functional group of the carbonate is -OC(=O)O-. Generally, the molar ratio of P-OH to -OC(=O)O- is 1:0.1-20. For example, 1:0.2-15, 1:0.3-12, 1:0.3-10, 1:0.3-8, 1:0.4-8, 1:0.5-8, 1:0.6-8, 1:0.6-6, 1:0.6-5, 1:0.7-5, 1:0.7-4, 1:0.7-3, 1:0.7-2, 1:0.7-1.5, 1:0.8-1.5, 1:1-1.5. If the amount of P-OH is too high, it will increase the difficulty of acid removal; if the amount is too low, the phosphorus content of the product will be low.

[0043] The mixing mode of the P(O)-OH and the carbonate compound is not limited. For example, the two can be directly mixed for reaction, or one of the raw materials can be added to the other in batches for reaction.

[0044] Optionally, the acidolysis reaction is carried out at a temperature of 0-300°C. Optionally, the reaction temperature is 50-250°C, 100-250°C, 150-250°C, 150-240°C, or 180-240°C. If the reaction temperature is too low, the reaction rate is slow, and the economy is reduced. If the reaction temperature is too high, the reaction is too violent, and the safety risk is increased.

[0045] The acidolysis reaction can be carried out at normal pressure, or at positive or negative pressure.

[0046] The reaction time of the acidolysis reaction is determined according to the selected raw materials, reaction temperature, and reaction degree. Optionally, the reaction time is 0.1-30 h. For example, 0.2-25 h, 0.3-20 h, 0.4-18 h, 0.5-15 h, 1-15 h, 1-12 h, or 1-10 h.

[0047] The acidolysis reaction can be carried out in a solvent or without a solvent. The solvent does not react with P(O)-OH and the carbonate compound. The solvent can be at least one of toluene, ethylbenzene, propylbenzene, butylbenzene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diphenylmethane.

[0048] Preferably, the acidolysis reaction is carried out without a solvent. The case without a solvent includes the case where excess raw materials are used as solvents.

[0049] The acidolysis reaction can be carried out with or without a catalyst. The catalyst is selected from inorganic bases, inorganic acids, tertiary amines, carboxylates, phosphates, titanates, organotins, or sulfonic acids.

[0050] Preferably, the acidolysis reaction is carried out without a catalyst.

[0051] After the acidolysis reaction is completed, the phosphate ester product can be directly used without purification, depending on the starting raw materials and proportions and the use. The product can also be separated by using conventional organic synthesis purification methods, such as extraction, column chromatography, alkaline washing, acid washing, water washing, drying, and the like. For example, the product obtained by reacting a slight excess of glycerol carbonate with diethyl phosphinic acid can be used without separation. After the reaction of diethyl phosphinic acid with diphenyl carbonate is completed, the byproduct phenol is removed by distillation to obtain diethyl phenyl phosphinate.

[0052] Preferably, after the acidolysis reaction is completed, the product is directly used without additional purification. The additional purification here refers to the separation means by using extraction, column chromatography, alkaline washing, acid washing, and the like conventional methods, and does not include the method of water washing, normal pressure or vacuum removal of excess reactants or byproducts after the reaction is completed. In some embodiments of the present application, after the acidolysis reaction is completed, the method further includes: vacuum distillation.

[0053] In one embodiment of the present application, a phosphate ester and a method for preparing the same are provided, wherein the phosphate ester is a product of an acidolysis reaction of at least one carbonate group of a carbonate compound with P(O)-OH, the P(O)-OH has a structure as shown in formula (I), and the carbonate compound has a structure as shown in formula (VII); and the corresponding phosphate ester has a structure as shown in formula (VIII).

[0054] In formula (VII), R 10 , R 11 are independently selected from hydrogen, C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group, or C6-C 24 aromatic group substituted with at least one substituent; and the substituent is selected from one or more of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy group, C1-C 18 ether group, C1-C 18 thioether group, and thiol group.

[0055] Optionally, R 10 and R 11 are independently selected from at least one of hydrogen atom, -CH3, -CH2CH3, -CH2OH, -CH2OC(CH2OH)3, and -CH2OC(O)OCH3.

[0056] Optionally, R 10 and R 11 , one is selected from hydrogen atom, and the other is selected from -CH2OH or -CH2OC(O)OCH3.

[0057] In formula (VIII), a and b have the same definition as a and b in formula (I).

[0058] R 12 and R 13 are independently selected from R 10 in formula (VII), R 11 in formula (VII), R 10 substituted in formula (VI), or R 11 substituted in formula (VI).

[0059] s is a natural number greater than or equal to 1; and R8 is H or a group as shown in formula (VI).

[0060] R 1a , R 2b are independently selected from the group consisting of -(CH2(R 12 )C(R 13 )CH2-O-) s R8, R1in formula (I) or R2in formula (I); and only when R1in formula (I) = H, a = 1, R 1a = H or -(CH2(R 12 )C(R 13 )CH2-O-) s R8; and / or R2= H, b = 1, R 2b = H or -(CH2(R 12 )C(R 13 )CH2-O-) s R8. s in this paragraph has the same meaning as s in formula (VIII).

[0061] Optionally, a = b = 0.

[0062] Optionally, R1, R2are independently selected from the group consisting of C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aryl, or C6-C 24 aryl substituted with at least one substituent; the substituent being selected from the group consisting of one or more of C1-C 18 alkyl, C6-C 24 aryl, carbonate, hydroxyl, amino, nitro, halogen, C1-C 18 ester, C1-C 18 alkoxy, C1-C 18 ether, C1-C 18 thioether, and thiol.

[0063] Optionally, a = b = 0, and R1, R2are independently selected from the group consisting of C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aryl, or C6-C 24 aryl substituted with at least one substituent; the substituent being selected from the group consisting of one or more of C1-C 18 alkyl, C6-C 24 aryl, carbonate, hydroxyl, amino, nitro, halogen, C1-C 18 ester, C1-C 18 alkoxy, C1-C 18 ether, C1-C 18 thioether, and thiol.

[0064] Optionally, a = b = 0, and R1, R2are independently selected from C1-C 18 alkyl, at least one substituent substituted C1-C 18 alkyl; said substituent is selected from one or more of C1-C 18 alkyl, C6-C 24 aryl, carbonate, hydroxyl, amino, nitro, halogen, C1-C 18 ester, C1-C 18 alkoxy, C1-C 18 ether, C1-C 18 thioether, and thiol.

[0065] Optionally, a = b = 0, and R1, R2are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, or isooctyl.

[0066] In formula (VIII), R 12 , R 13 are independently selected from R 10 in formula (VII), R 11 in formula (VII), R 10 substituted by formula (VI), or R 11 substituted by formula (VI). Here, the substitution means that the H in the hydroxyl group originally contained in R 10 , R 11 is replaced by a group having the structure shown in formula (VI). For example, if R 10 in formula (VII) is -CH2OH, then R 12 or R 13 in formula (VIII) can be -CH2OR9, where R9is H or a group having the structure shown in formula (VI).

[0067] In formula (VIII), when s is greater than 1, R 12 or R 13 in the repeating unit inside each bracket can or can not be the same. For example, in one repeating unit, R 12 is -CH2OR9, where R9= H; while in another repeating unit, it can be -CH2OR9, where R9is not equal to H, and the specific R9is determined by the reaction.

[0068] Optionally, the phosphate ester has the structure shown in formula (VIII');

[0069] wherein * indicates the position of attachment of the substituent in the compound.

[0070] wherein R hR h ” is independently selected from the group consisting of hydrogen, ethyl, hydroxy-substituted methyl, formula (R h -1), formula (R h -2) or formula (R h -3); R h ” is independently selected from the group consisting of hydroxy-substituted methyl, formula (R h -1), formula (R h -2) or formula (R h -3).

[0071] Optionally, the phosphate ester has at least one of the structures shown in formulae VIII-1 to VIII-6.

[0072] The method for preparing the phosphate ester having the structure shown in formula (VIII) comprises the following steps:

[0073] carrying out an acidolysis reaction on P(O)-OH and a carbonate compound to generate carbon dioxide and a phosphate ester having the structure shown in formula (VIII);

[0074] The carbonate compound has the structure shown in formula (VII).

[0075] or the carbonate compound is obtained by an ester exchange reaction on an alcohol having the structure shown in formula (IX) and a dialkyl carbonate (ester exchange reaction product);

[0076] or the carbonate compound is obtained by an ester exchange reaction on an alcohol having the structure shown in formula (IX) and a diphenyl carbonate (ester exchange reaction product);

[0077] In formula (IX), R 14 , R 15 are the same as the selection of R 10 , R 11 in formula (VII).

[0078] When an alcohol having the structure shown in formula (IX) and a dialkyl carbonate or a diphenyl carbonate are subjected to an ester exchange reaction, the generated carbonate compound (ester exchange reaction product) can have carbonate molecules with two or more structural features of formulae (II), (VII) in its molecular structure at the same time. For example, the carbonate structure directly obtained by the ester exchange reaction of trihydroxypropane and dimethyl carbonate has both cyclic carbonate molecules and linear carbonate molecules.

[0079] The P(O)-OH has the structure shown in formula (I), which is not particularly described again here.

[0080] The molar ratio of the P(O)-OH and the carbonate compound is determined according to the molar ratio of the reactive functional groups of the two compounds, wherein the reactive functional group of the P(O)-OH compound is P-OH, and the reactive functional group of the carbonate is -OC(=O)O-. Generally, the molar ratio of P-OH to -OC(=O)O- is 1:0.1-20. For example, 1:0.2-15, 1:0.3-12, 1:0.3-10, 1:0.3-8, 1:0.4-8, 1:0.5-8, 1:0.6-8, 1:0.6-6, 1:0.6-5, 1:0.7-5, 1:0.7-4, 1:0.7-3, 1:0.7-2, 1:0.7-1.5, 1:0.8-1.5, 1:1-1.5.

[0081] The acidolysis reaction is carried out at a temperature of 0-300°C. Alternatively, the reaction temperature is 50-250°C, 100-250°C, 150-250°C, 150-240°C, 180-240°C.

[0082] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0083] The acidolysis reaction is carried out for a time period of 0.1-30h. For example, 0.2-25h, 0.3-20h, 0.4-18h, 0.5-15h, 1-15h, 1-12h, or 1-10h.

[0084] The acidolysis reaction can be carried out in a solvent, or without a solvent. The solvent does not react with the P(O)-OH and the carbonate compound. The solvent can be at least one of toluene, ethylbenzene, propylbenzene, butylbenzene, dimethylbenzene, trimethylbenzene, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diphenylmethane.

[0085] Preferably, the acidolysis reaction is carried out without a solvent. The case without a solvent includes the case where excess raw material is used as a solvent.

[0086] The acidolysis reaction can be carried out with or without a catalyst. The catalyst is selected from inorganic bases, inorganic acids, tertiary amines, carboxylates, phosphates, titanates, organotins, or sulfonic acids.

[0087] Preferably, the acidolysis reaction is carried out without a catalyst.

[0088] Preferably, after the acidolysis reaction, the obtained phosphoric acid ester having the structure shown in formula (VIII) is directly used without being purified by extraction, distillation, column chromatography, alkaline washing, acid washing, or other conventional methods.

[0089] In one embodiment of the present application, a phosphate ester having the structure of formula (XI) is provided:

[0090] wherein R 21 is selected from the remaining group after the loss of two terminal hydroxyl groups of a polyol;

[0091] R 22 , R 23 are independently selected from H or the structure of formula (VI), and R 22 and R 23 are not both H;

[0092] x1 is a natural number.

[0093] In formula (VI), R1, R2, a, b are as defined above, and will not be repeated here.

[0094] Optionally, R 21 may be arbitrarily selected from at least one of -CH2CH2-, -CH2CH(CH3)-, -CH(CH2CH3)CH(CH2CH3)-, -PhC(CH3)2Ph-, -Ph-, -(CH2)4-, -(CH2)6-, -Ph(CH3)2C(CH3)2Ph(CH3)2-, -(CH2CH2OCH2CH2)2-, -(CH2CH2OCH2CH2)4-.

[0095] Preferably, R 21 is the remaining group after the loss of two terminal hydroxyl groups of bisphenol A, bisphenol F, bisphenol S, or 4,4'-dihydroxybiphenyl.

[0096] Optionally, in formula (XI), a = b = 0.

[0097] Optionally, R1, R2 are independently selected from C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group, or C6-C 24 aromatic group substituted with at least one substituent; the substituent is selected from one or more of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, thiol group, and heterocycle.

[0098] Optionally, a = b = 0, and R1, R2 are independently selected from C1-C 18 alkyl, or C1-C 18 alkyl substituted with at least one substituent; the substituent is selected from C1-C 18 alkyl, C6-C 24one or more of an alkyl group, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle.

[0099] Optionally, a = b = 0, and R1, R2are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, and isooctyl.

[0100] In an embodiment of the present application, the phosphate-based flame retardant includes at least one of structures represented by Formula (XI-1) and Formula (XI-2); optionally, includes structures represented by Formula (XI-1) and Formula (XI-2).

[0101] In an embodiment of the present application, the phosphate-based flame retardant includes at least one of structures represented by Formula (XI-1), Formula (XI-2), Formula (XI-3), Formula (XI-4), Formula (XI-5), and Formula (XI-6); optionally, includes structures represented by Formula (XI-1), Formula (XI-2), Formula (XI-3), Formula (XI-4), Formula (XI-5), and Formula (XI-6).

[0102] The method for preparing the phosphate includes the following steps:

[0103] The P(O)-OH and the polycarbonate compound are subjected to an acidolysis reaction to generate carbon dioxide and the phosphate.

[0104] The phosphate is a product obtained by subjecting at least one carbonate group of the P(O)-OH and the polycarbonate compound to an acidolysis reaction. The acidolysis reaction simultaneously generates CO2.

[0105] The P(O)-OH has a structure represented by Formula (I);

[0106] In Formula (I), R1and R2are independently selected from hydrogen, a C1-C20alkyl group, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle. 18 a C1-C20alkyl group substituted with at least one substituent, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle. 18 a C1-C20alkyl group substituted with at least one substituent, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle. 24 a C1-C20alkyl group substituted with at least one substituent, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle. 24 a C1-C20alkyl group substituted with at least one substituent, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle. 18 a C1-C20alkyl group substituted with at least one substituent, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle. 24 a C1-C20alkyl group substituted with at least one substituent, a C6-C20aromatic group, a carbonate group, a hydroxyl group, an amino group, a nitro group, a thiol group, and a heterocycle.

[0107] a, b are independently selected from 0 or 1; when a = b = 0, R1, R2are both hydrogen atoms or none of R1, R2is a hydrogen atom.

[0108] Optionally, R1, R2are independently selected from the group consisting of hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, p-methylphenyl, and when a = b = 0, R1, R2are both hydrogen atom or neither hydrogen atom.

[0109] Optionally, R1, R2are independently selected from the group consisting of hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, p-methylphenyl, and at least one of a and b is 0, and when a = b = 0, R1, R2are both hydrogen atom or neither hydrogen atom.

[0110] Optionally, R1, R2are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, p-methylphenyl, and a = b = 0.

[0111] Optionally, R1, R2are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, phenyl, p-methylphenyl, and a = b = 0.

[0112] Optionally, the P(O)-OH compound is at least one selected from the group consisting of phosphoric acid, diphenyl phosphate, dimethyl phosphate, diethyl phosphate, methyl phosphoric acid, ethyl phosphoric acid, propyl phosphoric acid, benzyl phosphoric acid, phenyl phosphoric acid, monophenyl phenyl phosphate, monomethyl phenyl phosphate, monoethyl phenyl phosphate, monophenyl methyl phosphate, monophenyl ethyl phosphate, dimethyl phosphinic acid, methyl ethyl phosphinic acid, diethyl phosphinic acid, dipropyl phosphinic acid, diisopropyl phosphinic acid, ethyl propyl phosphinic acid, di-n-butyl phosphinic acid, diisobutyl phosphinic acid, propyl butyl phosphinic acid, ethyl butyl phosphinic acid, methyl phenyl phosphinic acid, ethyl phenyl phosphinic acid, dibenzyl phosphinic acid, di(3-chloropropyl) phosphinic acid, di(3-bromopropyl) phosphinic acid, di(2-chloropropyl) phosphinic acid, di(2-bromopropyl) phosphinic acid, and diphenyl phosphinic acid.

[0113] The polycarbonate has a structure shown in formula (X);

[0114] wherein R 21 is selected from the remaining part after the polyol loses two terminal hydroxyl groups;

[0115] x is a natural number greater than 1.

[0116] The generated phosphoric acid ester has a structure shown in formula (XI);

[0117] wherein R 21 has the definition in formula (X), R 22 , R 23are each independently selected from H or have the structure shown in Formula (VI), and R 22 and R 23 cannot be H at the same time.

[0118] x1 is a natural number, and x1 is less than x in Formula (X).

[0119] Optionally, the degree of polymerization x of the polycarbonate is a natural number greater than 3, 5, 10, 20, 30, 40, 50.

[0120] The molar ratio of P-OH in P(O)-OH to -OC(=O)O- in the polycarbonate is 1:0.1-20, 1:0.2-15, 1:0.3-12, 1:0.3-10, 1:0.3-8, 1:0.4-8, 1:0.5-8, 1:0.6-8, 1:0.6-6, 1:0.6-5, 1:0.7-5, 1:0.7-4, 1:0.7-3, 1:0.7-2, 1:0.7-1.5, 1:0.8-1.5, 1:1-1.5.

[0121] The acidolysis reaction temperature is 0-300℃. Optionally, the reaction temperature is 50-250℃, 100-250℃, 150-250℃, 150-240℃, or 180-240℃.

[0122] The acidolysis reaction time is 0.1-30h, 0.2-25h, 0.3-20h, 0.4-18h, 0.5-15h, 1-15h, 1-12h, 1-10h.

[0123] The acidolysis reaction is carried out in a solvent or without a solvent. Preferably, the acidolysis reaction is carried out without an external solvent.

[0124] The acidolysis reaction can be carried out with or without a catalyst. The catalyst includes inorganic bases, inorganic acids, tertiary amines, carboxylates, phosphates, titanates, organotin, sulfonic acids, etc. Preferably, the acidolysis reaction is carried out without a catalyst.

[0125] Preferably, after the acidolysis reaction is completed, the phosphonate ester obtained having the structure shown in Formula (XI) does not need to be purified by extraction, distillation, column chromatography, alkaline washing, acid washing, etc. conventional methods, and is directly used.

[0126] In certain embodiments of the present application, the P(O)-OH is dialkyl hypophosphorous acid; the carbonate compound is one or more of vinyl carbonate, 1,2-propanediol carbonate, and styrene carbonate; the corresponding phosphate ester has the structure shown in Formula (XII); and is abbreviated as a mixture of vinylidene phosphonate.

[0127] In formula (XII), R1, R2are selected in the same way as in formula (I);

[0128] R 61 is H, methyl or phenyl;

[0129] R 62 is H or a group represented by formula (VI), and a = b = 0 in formula (VI);

[0130] t is a natural number greater than or equal to 1.

[0131] Optionally, in formula (XII), R1, R2are independently selected from C1-C6 alkyl or C1-C6 alkyl substituted with at least one substituent;

[0132] The substituent is selected from C1-C6 alkyl.

[0133] In some embodiments of the present application, the phosphate ester comprises a structure represented by formula (XII-1) to formula (XII-2);

[0134] The method for preparing the phosphate ester having a structure represented by formula (XII) comprises the following steps:

[0135] subjecting a dialkyl phosphinic acid to an acidolysis reaction with a carbonate compound to generate carbon dioxide and a phosphate ester having a structure represented by formula (XII);

[0136] The carbonate compound is one or more of ethylene carbonate, 1,2-propanediol carbonate and styrene carbonate.

[0137] When the dialkyl phosphinic acid is subjected to the acidolysis reaction with the carbonate compound, the molar ratio of the two is determined according to the molar ratio of the reactive functional groups of the two, wherein the reactive functional group of the dialkyl phosphinic acid is P-OH, and the reactive functional group of the carbonate is -OC(=O)O-. Generally, the molar ratio of P-OH to -OC(=O)O- is 1:0.1-20. For example, 1:0.2-15, 1:0.3-12, 1:0.3-10, 1:0.3-8, 1:0.4-8, 1:0.5-8, 1:0.6-8, 1:0.6-6, 1:0.6-5, 1:0.7-5, 1:0.7-4, 1:0.7-3, 1:0.7-2, 1:0.7-1.5, 1:0.8-1.5, 1:1-1.5.

[0138] The temperature of the acidolysis reaction is 0-300°C. Optionally, the reaction temperature is 50-250°C, 100-250°C, 150-250°C, 150-240°C or 180-240°C.

[0139] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0140] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0141] The acidolysis reaction can be carried out in a solvent or without solvent. The solvent does not react with P(O)-OH and the carbonate compound. The solvent can be at least one of toluene, ethylbenzene, propylbenzene, butylbenzene, dimethylbenzene, trimethylbenzene, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diphenylmethane.

[0142] Preferably, the acidolysis reaction is carried out without solvent. The case without solvent includes the case that excess raw material is used as solvent.

[0143] The acidolysis reaction can be carried out with or without catalyst. The catalyst is selected from inorganic base, inorganic acid, tertiary amine, carboxylate, phosphate, titanate, organotin, or sulfonic acid.

[0144] Preferably, the acidolysis reaction is carried out without catalyst.

[0145] Preferably, after the acidolysis reaction, the obtained vinylidene phosphate mixture having the structure shown in formula (XII) does not need to be purified by extraction, distillation, column chromatography, alkaline washing, acid washing, or other conventional methods, and can be directly used.

[0146] In some embodiments of the present application, the P(O)-OH is dialkyl phosphinic acid, and the carbonate compound is glycerol carbonate; or the carbonate compound is the product generated by transesterification of glycerol and dialkyl carbonate; or the carbonate compound is the product generated by transesterification of glycerol and diphenyl carbonate; and the corresponding phosphate ester includes the structures shown in formula (XIII) to formula (XIV), which is referred to as glycerol phosphate mixture.

[0147] wherein R1 and R2 are selected as in formula (I).

[0148] Optionally, R1 and R2 are C1-C6 alkyl or C1-C6 alkyl substituted with at least one substituent selected from C1-C6 alkyl.

[0149] Optionally, the phosphate ester includes the structures shown in formula (X-1) to formula (X-4).

[0150] The phosphoric acid ester consisting of the structures represented by formula (XIII) to formula (XIV) accounts for at least 60% to 80%, such as 60%, 70%, 80% of the total phosphoric acid ester moles in the glycerophosphoric acid ester mixture.

[0151] The method for preparing the glycerophosphoric acid ester mixture comprises:

[0152] The acidolysis reaction of the dialkyl phosphinic acid with the carbonate compound generates carbon dioxide and the phosphoric acid ester comprising the structures represented by formula (XIII) to formula (XIV);

[0153] The carbonate compound is glycerol carbonate; or the carbonate compound is generated by the transesterification reaction of glycerol and dialkyl carbonate; or the carbonate compound is generated by the transesterification reaction of glycerol and diphenyl carbonate.

[0154] The molar ratio of the dialkyl phosphinic acid to the carbonate compound in the acidolysis reaction is determined according to the molar ratio of the reactive functional groups of the two, wherein the reactive functional group of the dialkyl phosphinic acid is P-OH, and the reactive functional group of the carbonate is -OC(=O)O-. The molar ratio of P-OH in the dialkyl phosphinic acid to -OC(=O)O- in the carbonate compound is 1:0.1 to 20. For example, 1:0.2 to 15, 1:0.3 to 12, 1:0.3 to 10, 1:0.3 to 8, 1:0.4 to 8, 1:0.5 to 8, 1:0.6 to 8, 1:0.6 to 6, 1:0.6 to 5, 1:0.7 to 5, 1:0.7 to 4, 1:0.7 to 3, 1:0.7 to 2, 1:0.7 to 1.5, 1:0.8 to 1.5, 1:1 to 1.5.

[0155] The temperature of the acidolysis reaction is 0 to 300°C. Alternatively, the reaction temperature is 50 to 250°C, 100 to 250°C, 150 to 250°C, 150 to 240°C, or 180 to 240°C.

[0156] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0157] The time of the acidolysis reaction is 0.1 to 30 h. For example, 0.2 to 25 h, 0.3 to 20 h, 0.4 to 18 h, 0.5 to 15 h, 1 to 15 h, 1 to 12 h, or 1 to 10 h.

[0158] The acidolysis reaction can be carried out in a solvent, or without a solvent. The solvent does not react with P(O)-OH and the carbonate compound. The solvent can be at least one of toluene, ethylbenzene, propylbenzene, butylbenzene, dimethylbenzene, trimethylbenzene, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diphenylmethane.

[0159] Preferably, the acidolysis reaction is carried out without solvent. The case without solvent includes the case where excess raw material is used as solvent.

[0160] The acidolysis reaction can be carried out with or without catalyst. The catalyst is selected from inorganic base, inorganic acid, tertiary amine, carboxylate, phosphate, titanate, organic tin or sulfonic acid.

[0161] Preferably, the acidolysis reaction is carried out without catalyst.

[0162] Preferably, after the acidolysis reaction, the obtained glycerophosphonate mixture having the structure shown in formula (XIII) to (XIV) is directly used without purification by extraction, distillation, column chromatography, base washing, acid washing, etc.

[0163] The glycerophosphonate mixture prepared by the present application using carbonate compound instead of epoxide compound not only avoids the use of toxic glycidol, but also greatly avoids oligomer phosphonate generated by the ring opening self-polymerization of glycidol, which has low phosphorus content and is not favorable for flame retardation. Furthermore, the preparation of glycerophosphonate mixture by acidolysis of the product generated by the transesterification reaction of glycerol and dialkyl carbonate or diphenyl carbonate and dialkyl phosphinic acid can further reduce the cost.

[0164] The present application also provides the use of the above-mentioned phosphonate as flame retardant. The phosphonate provided by the present application has high flame retardation performance.

[0165] The present application also provides a flame-retardant high polymer material. The flame-retardant high polymer material comprises flame retardant and high polymer material, and the flame retardant comprises the phosphonate prepared by the above-mentioned preparation method.

[0166] Preferably, the flame-retardant high polymer material comprises 0.1wt% to 50wt% of flame retardant and 50wt% to 99.9wt% of high polymer material.

[0167] Optionally, the mass content of the flame retardant in the flame-retardant high polymer material is any value or a range value between any two values selected from 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 30%, 40% and 50%.

[0168] Preferably, the flame-retardant high polymer material further comprises functional additives.

[0169] Preferably, the functional additives are selected from at least one of reinforcing agent, anti-dripping agent, stabilizer, pigment, dye, char-forming catalyst, dispersant, nucleating agent, inorganic filler, organic filler and antioxidant.

[0170] Preferably, the functional additive is present in the flame-retardant high molecular material in an amount of 5% to 40% by mass; for example, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 28%, 30%, 33%, 35%, 38% or 40% by mass.

[0171] Preferably, the flame retardant Q is further included in the flame-retardant high molecular material.

[0172] Preferably, the flame retardant Q is selected from at least one of phosphorus-based flame retardants, nitrogen-based flame retardants or boron-based flame retardants.

[0173] Preferably, the flame retardant Q is present in the flame-retardant high molecular material in an amount of 0.5% to 20% by mass; for example, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18% or 20% by mass.

[0174] Preferably, the high molecular material is selected from thermoplastic resins or thermosetting resins.

[0175] Preferably, the thermoplastic resin is selected from at least one of polybutadiene, polyamide, thermoplastic polyurethane, polyester, polyphenylene ether, acrylonitrile-butadiene-styrene copolymer, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyimide, polyphenylene sulfide, polyether ether ketone and PC / ABS. Particularly preferably, the thermoplastic resin is selected from one of PC / ABS, thermoplastic polyurethane.

[0176] Preferably, the thermosetting resin is selected from at least one of vinyl polyphenylene ether resin, epoxy resin, cyanate ester resin, BT resin, bismaleimide resin, phenolic resin, polyurethane resin, thermosetting polyimide, unsaturated polyester resin, vinyl resin, benzoxazine resin, aryl acetylene resin and furan resin.

[0177] Preferably, the thermosetting resin is at least one of polyurethane resin and epoxy resin. Particularly preferably, the thermosetting resin is epoxy resin.

[0178] Preferably, the epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin and naphthol epoxy resin.

[0179] Preferably, when the phosphate ester is alkyl phosphate ester, the high molecular material is thermosetting resin, and when the phosphate ester is aromatic phosphate ester, the high molecular material is thermoplastic resin.

[0180] The high molecular material described in the present application includes, but is not limited to, the products currently available on the market.

[0181] Preferably, the flame-retardant high polymer material comprises 0.1wt% to 30wt% of the phosphate ester and 70wt% to 99.9wt% of the high polymer material.

[0182] Preferably, the mass content of the phosphate ester in the flame-retardant high polymer material is any value or a range value between any two values of 0.1%, 0.5%, 1%, 2%, 3%, 3.5%, 4%, 5%, 6%, 8%, 10%, 15% and 20%. Advantages:

[0183] The preparation method of the phosphate ester provided by the present application has the following advantages:

[0184] 1) The raw materials are widely sourced and have wide applicability.

[0185] 2) The process is simple and can be carried out only by heating, without the need for solvents and catalysts, and is economical.

[0186] 3) There are no by-products, or the by-products are common chemical raw materials, which can be reused, have little environmental pollution, and are environmentally friendly.

[0187] 4) Carbonic acid ester compounds are used instead of epoxy compounds, which reduces toxicity and reduces oligomer phosphate esters generated by epoxy self-polymerization, effectively increasing the phosphorus content. BRIEF DESCRIPTION OF DRAWINGS

[0188] Figure 1 is a nuclear magnetic resonance hydrogen spectrum of diethyl phenylphosphinate in Example 1 of the present application;

[0189] Figure 2 is a nuclear magnetic resonance hydrogen spectrum of trimethylolpropane-diethyl phosphite in Example 13 of the present application;

[0190] Figure 3 is a nuclear magnetic resonance hydrogen spectrum of bisphenol A diethyl phosphite hemiester in Example 15 of the present application. DETAILED DESCRIPTION

[0191] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0192] The raw materials used in the examples are as follows:

[0193] Diethyl phosphinic acid (DEPA): Jiangsu Lisi New Material Co., Ltd.

[0194] Dipropyl phosphinic acid (DPPA): Jiangsu Lisi New Material Co., Ltd.

[0195] Diisobutylphosphinic acid (DBPA): prepared according to CN101010372

[0196] Diphenylphosphinic acid (DPhPA): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0197] Phenylphosphonic acid (PhPA): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0198] Diphenylphosphate (DPP): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0199] Diphenylcarbonate (DPC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0200] Dimethylcarbonate (DMC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0201] Ethylene carbonate (EC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0202] Di-n-butylcarbonate (DBC): Shanghai Macklin Biochemical Technology Co., Ltd.

[0203] Glycerol (Gly): National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0204] Glyceryl carbonate (GC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0205] Trimethylolpropane (THMP): Shanghai Macklin Biochemical Technology Co., Ltd.

[0206] E44 epoxy resin: Shanghai Macklin Biochemical Technology Co., Ltd.

[0207] 4,4’-diaminodiphenylmethane (DDM): Shanghai Macklin Biochemical Technology Co., Ltd.

[0208] The test used in the examples corresponds to the following standards:

[0209] Vertical burning test (UL94): GB / T2408-2008

[0210] Limiting oxygen index test (LOI): GB / T2406.2-2009

[0211] Bending test: GB / T9341-2008

[0212] Compression test: GB / T1041-2008.

[0213] Example 1

[0214] Preparation of phenyl diethylphosphite (PDEP)

[0215] In a 500 mL four necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 220.0 g (1.02 mol) of diphenyl carbonate (DPC) and 139.0 g (1.14 mol) of diethyl phosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at atmospheric pressure. After 5 h, the reaction of diphenyl carbonate was complete. Subsequently, phenol and acid were removed by distillation under reduced pressure at 170-180°C and 8-10 mmHg. The temperature was increased to 190°C and the product, diethyl phenyl phosphinate, was obtained as a colorless transparent liquid. Yield 89.6%. Its structure is shown in formula IV-1 (corresponding to the previous structural formula IV):

[0216] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of diethyl phenyl phosphinate according to Example 1 of the present application.

[0217] Upon testing, 1 H NMR, CDC13 as solvent: 7.0-7.4 ppm (Ph-H, 5H), 1.8 ppm (-CH2-, 4H), 1.2 ppm (-CH3, 6H).

[0218] Example 2

[0219] Preparation of diethyl phenyl phosphinate (PDEP)

[0220] In a 50 mL four necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 10.0 g (0.05 mol) of diphenyl carbonate and 5.7 g (0.05 mol) of diethyl phosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at atmospheric pressure. After 1 h, the reaction of diphenyl carbonate was complete. Subsequently, phenol was removed by distillation under reduced pressure at 170-180°C and 8-10 mmHg. The temperature was increased to 190°C and the product, diethyl phenyl phosphinate, was obtained as a colorless transparent liquid. Yield 84.9%. Its structure is shown in formula IV-1 (corresponding to the previous structural formula IV):

[0221] Upon testing, 1 H NMR, CDC13 as solvent: 7.0-7.4 ppm (Ph-H, 5H), 1.8 ppm (-CH2-, 4H), 1.2 ppm (-CH3, 6H).

[0222] Example 3

[0223] Preparation of diethyl phenyl phosphinate (PDEP)

[0224] In a 50 mL four necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 14.3 g (0.07 mol) of diphenyl carbonate and 10.0 g (0.07 mol) of dipropylphosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at atmospheric pressure. After 2 h, the reaction of diphenyl carbonate was complete. Subsequently, phenol was removed by distillation under reduced pressure at 170-180°C and 8-10 mm Hg. The temperature was increased to 190°C and the product, phenyl dipropylphosphinate, was obtained as a colorless transparent liquid. Yield 80.3%. Its structure is shown in formula IV-2 (corresponding to the previous structural formula IV):

[0225] Upon testing, 1 H NMR, CDC13 as solvent: 7.0-7.4 ppm (Ph-H, 5H), 1.8 ppm (-CH2CH2CH3, 4H), 1.7 ppm (-CH2CH2CH3, 4H), 1.1 ppm (-CH3, 6H).

[0226] Example 4

[0227] Preparation of phenyl diisobutylphosphinate (PDBP)

[0228] In a 25 mL four necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 6.0 g (0.03 mol) of diphenyl carbonate and 5.0 g (0.03 mol) of diisobutylphosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at atmospheric pressure. After 1 h, the reaction of diphenyl carbonate was complete. Subsequently, phenol was removed by distillation under reduced pressure at 170-180°C and 8-10 mm Hg. The temperature was increased to 200°C and the product, phenyl diisobutylphosphinate, was obtained as a colorless transparent liquid. Yield 66.0%. Its structure is shown in formula IV-3 (corresponding to the previous structural formula IV):

[0229] Upon testing, 1 H NMR, CDC13 as solvent: 7.0-7.4 ppm (Ph-H, 5H), 2.2 ppm (-CH-, 2H), 1.8 ppm (-CH2-, 4H), 1.1 ppm (-CH3, 12H).

[0230] Example 5

[0231] Preparation of phenyl diphenylphosphinate (PDPhP)

[0232] In a 500 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet-outlet, 1.7 g (0.008 mol) of diphenyl carbonate and 3.0 g (0.01 mol) of diphenyl phosphinic acid were mixed. The mixture was heated to 230°C under nitrogen and reacted at normal pressure. After 26 h, the reaction of diphenyl carbonate was completed. Subsequently, the reaction mixture was dissolved in toluene, washed with 0.5 wt% sodium hydroxide aqueous solution and deionized water to remove excess diphenyl phosphinic acid and phenol, respectively, and finally distilled under reduced pressure at 80°C at 8-10 mmHg to remove toluene, to obtain 2.2 g of white solid product, diphenyl phenyl phosphonate. The yield was 53.5%. Its structure is shown in Formula IV-4 (corresponding to the aforementioned Formula IV):

[0233] Upon examination, 1 H NMR, CDC13 as solvent: 7.9 ppm (P-C-C-C-H, 4H), 7.5-7.7 ppm (P-C-C-H / P-C-C-C-C-H, 6H), 7.0-7.4 ppm (P-O-Ph-H, 5H).

[0234] Example 6

[0235] Preparation of phenyl phosphonate (PPhP)

[0236] In a 100 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet-outlet, 10.0 g (0.06 mol) of phenyl phosphonic acid and 20.1 g (0.09 mol) of diphenyl carbonate were mixed. The mixture was heated to 210-220°C under nitrogen and reacted at normal pressure. After 25 h, the reaction of diphenyl carbonate was completed. Subsequently, phenol was removed by distillation under reduced pressure at 180°C at 8-10 mmHg, to obtain 14.1 g of light yellow solid product, phenyl phosphonate (monoester: diester = 1:1.2). The yield was 63.9%. Its structure is shown in Formula IV-5-1 and Formula IV-5-2 (corresponding to the aforementioned Formula IV):

[0237] Upon examination, 1 H NMR, CDC13 as solvent: 7.7-8.1 ppm (P-C-C-C-H, 4.4H), 7.4-7.7 ppm (P-C-C-H / P-C-C-C-C-H, 6.6H), 7.0-7.3 ppm (P-O-Ph-H, 17H).

[0238] 31 P NMR, CDC13 as solvent: 18.0 ppm (monoester, 45.8%), 11.6 ppm (diester, 54.2%).

[0239] Example 7

[0240] Preparation of triphenyl phosphate (TPP)

[0241] In a 100 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet and outlet, 10.0 g (0.04 mol) of diphenyl phosphate and 4.3 g (0.02 mol) of diphenyl carbonate were mixed. The mixture was heated to 210-220 °C under nitrogen and reacted at normal pressure. After 20 h, the diphenyl carbonate was completely reacted. The reaction solution was then dissolved in toluene, and the excess diphenyl phosphate and phenol were washed away with 0.5 wt% sodium hydroxide aqueous solution and deionized water, respectively. Finally, toluene was removed by distillation at 80 °C under 8-10 mmHg pressure to obtain 3.6 g of a light yellow liquid product, triphenyl phosphate. The yield was 27.6%. Its structure is shown in Formula IV-6 (corresponding to the aforementioned structure IV):

[0242] Upon testing, 1 H NMR, CDCl3as solvent: 7.0-7.5 ppm (Ph-H, 15H).

[0243] Example 8

[0244] Preparation of n-butyl diethyl phosphite (BDEP)

[0245] In a 50 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet and outlet, 5.0 g (0.04 mol) of diethyl phosphite and 3.6 g (0.02 mol) of di-n-butyl carbonate were mixed. The mixture was heated to 230 °C under nitrogen and reacted at normal pressure. After 20 h, the di-n-butyl carbonate was completely reacted. The reaction solution was dissolved in 30 g of toluene, and the diethyl phosphite was washed away with water. Finally, toluene was removed by rotary evaporation and vacuum drying to obtain 1.2 g of a light yellow liquid product, n-butyl diethyl phosphite. The yield was 34.3%. Its structure is shown in Formula IV-7 (corresponding to the aforementioned structure IV):

[0246] Upon testing, 1 H NMR, CDCl3as solvent: 4.0 ppm (P-OCH2-, 2H), 1.7 ppm (P-CH2CH3, 4H), 1.6 ppm (-CH2CH2CH3, 2H), 1.4 ppm (-CH2CH2CH3, 2H), 1.14 ppm (P-CH2CH3, 6H), 0.9 ppm (-CH2CH2CH3, 3H).

[0247] Example 9

[0248] Preparation of ethylene glycol diethyl phosphite (EG-DEP) mixture

[0249] In a 50 mL four-necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 10.0 g (0.11 mol) of ethylene carbonate and 13.6 g (0.11 mol) of diethyl phosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at normal pressure. After 3 h, the reaction of ethylene carbonate was complete. Without any work-up, 12.2 g of liquid product, ethylene glycol diethyl phosphinate, was obtained. Yield 72.2%. Its main constituent structures are shown in formula XII-1 and XII-2 (corresponding to the aforementioned formula XII), wherein the molar ratio of mono-ester (formula XII-1) to di-ester (formula XII-2) is 3:1, and the molar ratio of phosphorus in both to the total phosphorus is >93%.

[0250] Upon testing, 1 H NMR, CDC13 as solvent: 4.0-4.2 ppm (P-O-CH2-, 10H), 3.7-3.8 ppm (P-O-CH2-CH2-OH, 6H), 1.8 ppm (-CH2CH3, 20H), 1.2 ppm (-CH3, 30H).

[0251] Example 10

[0252] Preparation of ethylene glycol diethyl phosphinate (EG-DEP) mixture

[0253] In a 50 mL four-necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 10.0 g (0.11 mol) of ethylene carbonate and 12.4 g (0.10 mol) of diethyl phosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at normal pressure. After 3 h, the reaction of diethyl phosphinic acid was complete. The excess ethylene carbonate was removed by distillation under reduced pressure at 180°C under 8-10 mmHg. 11.8 g of liquid product, ethylene glycol diethyl phosphinate, was obtained. Yield 73.9%. Its main constituent structures are shown in formula XII-1 and XII-2 (corresponding to the aforementioned formula XII), wherein the molar ratio of mono-ester (formula XII-1) to di-ester (formula XII-2) is 6.8:1, and the molar ratio of phosphorus in both to the total phosphorus is >94%.

[0254] Upon testing, 1 H NMR, CDC13 as solvent: 4.0-4.2 ppm (P-O-CH2-, 17.6H), 3.7-3.8 ppm (P-O-CH2-CH2-OH, 13.6H), 1.8 ppm (-CH2CH3, 35.2H), 1.2 ppm (-CH3, 52.8H).

[0255] Example 11

[0256] Preparation of glyceryl diethylphosphite (GDEP) from glycerol carbonate

[0257] In a 100 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet-outlet, 20.0 g (0.17 mol) of glycerol carbonate and 20.5 g (0.17 mol) of diethylphosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at normal pressure. After 4 h, the reaction was complete. Without any post-treatment, 26.2 g of yellow transparent liquid product, glyceryl diethylphosphite, was obtained with a yield of 78.6%, and its main component structures were shown as formula X-1, formula X-2, formula X-3, formula X-4 (corresponding to the aforementioned structures XIII~XVI), and the molar ratio of the phosphoric ester of these four structures to the total phosphorus was >91%.

[0258] It was detected that, 1 H NMR, CDCl3as solvent: 3.0-5.0 ppm (-CH2-, -CH-, -OH, 7H), 1.4-2.0 ppm (-CH2CH3, 4H), 1.1 ppm (-CH3, 6H).

[0259] Example 12

[0260] Preparation of glyceryl diethylphosphite (GDEP) from glycerol

[0261] In a 100 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet-outlet, 10 g (0.11 mol) of glycerol and 18.9 g (0.11 mol) of di-n-butyl carbonate were mixed. The mixture was heated to 180-190°C under nitrogen and the reaction was carried out at normal pressure with 0.2 mol% DBDL as catalyst. After 18 h, di-n-butyl carbonate was completely reacted to obtain a glycerol carbonate mixture (denoted as Gly-C). Then 13.2 g (0.11 mol) of diethylphosphinic acid was added and the reaction was carried out at 190-200°C at normal pressure. After 4 h, glycerol carbonate was completely reacted. The product, glyceryl diethylphosphite, was obtained with a yield of 83.1%. Its main component structures were shown as formula X-1, formula X-2, formula X-3, formula X-4 (corresponding to the aforementioned structures XIII~XVI), and the molar ratio of the phosphoric ester of these four structures to the total phosphorus was >71%.

[0262] It was detected that, 1 H NMR, CDCl3as solvent: 3.0-4.6 ppm (O-CH2-, -CH-, 5H), 1.3-1.8 ppm (-CH2CH3, 4H), 1.0 ppm (-CH3, 6H).

[0263] Example 13

[0264] Preparation of trimethylolpropane-diethylphosphite (THMP-DEP)

[0265] Trimethylolpropane carbonate: In a 100 mL four-necked flask equipped with a thermometer, mechanical stirrer, and nitrogen inlet and outlet, 10.0 g (0.07 mol) of trimethylolpropane was mixed with 0.07 g (0.5 mol%) of dibutyltin dilaurate. The mixture was heated to 140°C under nitrogen and 25.0 g (0.28 mol) of dimethyl carbonate was added dropwise in portions through a constant pressure dropping funnel. The reaction was carried out under normal pressure. After 18 h, trimethylolpropane carbonate, noted as THMP-C, was obtained after removal of residual methanol and dimethyl carbonate by distillation under reduced pressure at room temperature and 8-10 mmHg. Then 8.5 g (0.07 mol) of diethylphosphite was added and the reaction was continued at 190°C under normal pressure. After 9 h, the diethylphosphite reaction was complete. No purification was needed. 15.0 g of the product, trimethylolpropane-diethylphosphite, was obtained as a light yellow liquid. The yield was 86.2%. Its main structure is shown in formula VIII-1, VIII-2, VIII-3, VIII-4, VIII-5, VIII-6 (corresponding to the above formula VIII):

[0266] Figure 2 is the proton nuclear magnetic resonance spectrum of trimethylolpropane-diethylphosphite according to Example 13 of the present application.

[0267] Upon testing, 1 H NMR, CDCl3as solvent: 3.0-5.0 ppm (-O-CH2-, -OH, 8H), 1.0-1.9 ppm (C-CH2CH3, P-CH2CH3, 12H), 0.6-1.0 ppm (C-CH2CH3, 3H).

[0268] Example 14

[0269] Preparation of bisphenol A diethylphosphite (BPA-DEP)

[0270] In a 100 mL four-necked flask equipped with a thermometer, mechanical stirrer, and nitrogen inlet and outlet, 20.0 g (0.08 mol, based on repeating unit) of bisphenol A polycarbonate was mixed with 9.61 g (0.08 mol) of diethylphosphite. The mixture was heated to 180°C under nitrogen and the reaction was carried out under normal pressure. After 3 h, the bisphenol A polycarbonate reaction was complete. No post-treatment was needed. 21.0 g of the product, bisphenol A diethylphosphite monoester, was obtained as a yellow transparent semi-solid. The yield was 82.0%. Its main component structures include formula (XI-1) and (XI-2):

[0271] Upon testing, 1 H NMR, CDCl3as solvent: 6.6-7.3 ppm (Ph-H / Ph-OH, 9H), 1.9 ppm (-CH2-, 4H), 1.6 ppm (-CH3, 6H), 1.2 ppm (-CH2CH3, 6H).

[0272] Example 15

[0273] Preparation of Bisphenol A Diethyl Phosphinate Hemiesters (BPA-0.5DEP)

[0274] In a 100 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet / outlet, 20.0 g (0.08 mol, based on repeating units) of Bisphenol A polycarbonate, 4.8 g (0.04 mol) of diethyl phosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and the reaction was carried out at atmospheric pressure. After 1 h, the Bisphenol A polycarbonate reacted completely. Without further treatment, 22.3 g of yellow transparent semi-solid product Bisphenol A diethyl phosphinate hemiesters was obtained. The yield was 96.7%. The main component structures included Formula (XI-1), Formula (XI-2), Formula (XI-3), Formula (XI-4), Formula (XI-5), and Formula (XI-6):

[0275] Figure 3 is the proton nuclear magnetic resonance spectrum of Bisphenol A diethyl phosphinate hemiesters in Example 15 of the present application.

[0276] Upon testing, 1 H NMR, CDCl3as solvent: 6.6-7.3 ppm (Ph-H / Ph-OH, 17H), 1.9 ppm (-CH2-, 4H), 1.6 ppm (-CH3, 12H), 1.2 ppm (-CH2CH3, 6H).

[0277] Referring to Tables 1-3, Tables 1-3 are the synthesis summary tables of the examples of the present application.

[0278] Table 1 Synthesis summary of phenyl phosphate esters

[0279] Table 2 Synthesis summary of alkyl diethyl phosphinic acid esters

[0280] Table 3 Synthesis summary of Bisphenol A phosphate esters

[0281] Application Example 1

[0282] Flame retardant application of diethyl glycol phosphinate (EG-DEP, prepared in Example 9) in epoxy resin:

[0283] Sample preparation: All sample preparation methods are the same, for example, 3wt% EP / EG-DEP: 79.6 parts of epoxy resin DGEBA 80℃ heating, after softening, add 17.4 parts of 4,4-diamino diphenyl methane (DDM), fast stirring to promote the dissolution of DDM; after most of the DDM dissolved, add 3 parts of EG-DEP (Example 9), continue to stir for 1 min, form a uniform mixture; hot mixture into 80℃ preheated mold, after 10 min, pre-cured to 120℃ 2h, then heated to 170℃ curing 4h. Natural cooling to room temperature, get 3wt% EP / EG-DEP composite. The sample thickness is 3.2mm.

[0284] The vertical combustion (UL94) test results of EP / EG-DEP composite are shown in Table 4.

[0285] Table 4 Vertical combustion (UL94) test results of EP / EG-DEP composite

[0286] From Table 4, EG-DEP shows very high flame retardant performance in epoxy resin, only 3wt% of the addition amount can pass UL94 test.

[0287] Application Example 2

[0288] Flame retardant application of trimethylolpropane-diethyl phosphite (THMP-DEP, prepared in Example 13) in epoxy resin:

[0289] Sample preparation: All sample preparation methods are the same, for example, 4wt% EP / THMP-DEP: 78.8 parts of epoxy resin DGEBA 80℃ heating, after softening, add 17.2 parts of 4,4-diamino diphenyl methane (DDM), fast stirring to promote the dissolution of DDM; after most of the DDM dissolved, add 4 parts of THMP-DEP (Example 13), continue to stir for 1 min, form a uniform mixture; hot mixture into 80℃ preheated mold, after 10 min, pre-cured to 120℃ 2h, then heated to 170℃ curing 4h. Natural cooling to room temperature, get 4wt% EP / THMP-DEP composite. The sample thickness is 3.2mm.

[0290] The vertical combustion (UL94) test results of EP / THMP-DEP composite are shown in Table 5.

[0291] Table 5 Vertical combustion (UL94) test results of EP / THMP-DEP composite

[0292] From Table 5, it can be seen that THMP-DEP exhibits very high flame retardant performance in epoxy resin, and can pass UL94 test with only 5wt% addition amount, and can reach V1 level with 4wt% addition amount.

[0293] Application Example 3

[0294] Application of phenyl diethylphosphite (PDEP, Example 1) in polyurethane foam:

[0295] Sample preparation: catalyst, polyether, flame retardant, water, blowing agent, amine catalyst, silicone oil were added into a 200ml beaker according to the ingredient table 5 in order, pre-mixed for 60s, then MDI was added and stirred for 10s, then the mixture was poured into a mold. Room temperature curing for 20h. Finally, the sample was cut into corresponding shape for testing as needed.

[0296] Table 6 Ingredient table of raw materials of application example 3

[0297] The obtained samples were subjected to limiting oxygen index (LOI) test and bending test, and the results are shown in Table 7.

[0298] Table 7 Limiting oxygen index (LOI) test and bending test results of samples

[0299] From Table 7, it can be seen that in the limiting oxygen index (LOI) test, the oxygen index of phenyl diethylphosphite is close to that of the general flame retardant tris(2-chloropropyl) phosphate (TCPP); in the bending test, the addition amount of TCPP increases, and the physical properties of the foam decrease; the addition amount of phenyl ester increases, and the physical properties decrease slightly. Therefore, the performance of phenyl diethylphosphite is better than that of the general flame retardant TCPP.

[0300] Application Example 4

[0301] Application of bisphenol A-diethylphosphite (BPA-DEP, Example 14) in polyurethane foam:

[0302] Sample preparation: catalyst, polyether, flame retardant, water, blowing agent, amine catalyst, silicone oil were added into a 200ml beaker according to the ingredient table 7 in order, pre-mixed for 60s, then MDI was added and stirred for 10s, then the mixture was poured into a mold. Room temperature curing for 20h. Finally, the sample was cut into corresponding shape for testing as needed.

[0303] Table 8 Ingredient table of raw materials of application example 4

[0304] The obtained samples were subjected to limiting oxygen index (LOI) test and bending, compression test, and the results are shown in Table 9.

[0305] Table 9 Results of limiting oxygen index (LOI) test and bending, compression test of samples

[0306] From Table 9, it can be seen that in the limiting oxygen index (LOI) test, the result of BPA-DEP is close to that of TCPP; in the bending and compression test, the bending performance of the sample using BPA-DEP for polyurethane foam is close to that of the pure sample, and the bending and compression performance changes little with the increase of the addition amount. Overall, bisphenol A-diethyl phosphite has good flame-retardant performance in polyurethane foam and has little effect on the physical performance of the foam.

[0307] From the above examples, it can be seen that by directly reacting P(O)-OH compounds with carbonate compounds, the desired phosphates can be obtained without catalyst and solvent. For example, alkyl phosphoric acid aromatic esters, hydroxy phosphates, etc. can be obtained simply and quickly, with high efficiency, few by-products, low process requirements, and little pollution.

[0308] The phosphates obtained by the preparation method of the present application have good flame-retardant performance and high application value. For example, trimethylolpropane-diethyl phosphite in epoxy resin requires only 5wt% dosage to pass the flame-retardant test; bisphenol A-diethyl phosphite in TPU requires only 5wt% to pass the UL94@1.6mm test; diethyl phosphite, bisphenol A-diethyl phosphite in polyurethane foam has good flame-retardant and mechanical performance.

[0309] The above examples are only used to help understand the method of the present application and its core idea. Various modifications to these examples will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other examples without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these examples shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A phosphate ester having the structure of formula (VIII) ###0001### (VIII) wherein, a and b are independently selected from 0 or 1; R 12 R 13 Independently selected from R 10 R 11 R replaced by formula (VI) 10 Or, R replaced by formula (VI) 11 ; R 10 , R 11 are independently selected from the group consisting of hydrogen, C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group, or C6-C 24 aromatic group substituted with at least one substituent; the substituents being selected from one or more of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate, hydroxyl, amino, nitro, halogen, C1-C 18 ester, C1-C 18 alkoxy, C1-C 18 ether, C1-C 18 thioether, and thiol; s is a natural number equal to or greater than 1; R8 is H or formula (VI); R 1a , R 2b is independently selected from -(CH2(R 12 )C(R 13 )CH2-O-) s R8, R1or R2; and only when R1= H, a = 1, R 1a = H or -(CH2(R 12 )C(R 13 )CH2-O-) s R8; and / or R2= H, b = 1, R 2b = H or -(CH2(R 12 )C(R 13 )CH2-O-) s R8; R1, R2are independently selected from the group consisting of C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group or C6-C 24 aromatic group substituted with at least one substituent; said substituent being selected from the group consisting of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy group, C1-C 18 ether group, C1-C 18 thioether group and thiol group.

2. The phosphate ester according to claim 1, characterized in that, The phosphate ester has a structure represented by formula (VIII'); wherein * indicates the position of attachment of the substituent in the compound; R h R h ” are independently selected from hydrogen, ethyl, hydroxy substituted methyl, formula (R h -1), formula (R h -2) or (R h -3); R h ”’ are independently selected from hydroxy substituted methyl, formula (R h -1), formula (R h -2) or (R h -3).

3. The phosphate ester of claim 1, wherein, The phosphate ester has at least one of the structures shown in Formulas VIII-1 to VIII-6.

4. A method for preparing a phosphate ester, comprising the steps of: subjecting a P(O)-OH compound and a carbonate compound to an acidolysis reaction to produce carbon dioxide and a phosphate ester; the carbonate compound has a structure represented by formula (VII); or the carbonate compound is obtained by transesterification of an alcohol having the structure of Formula (IX) and a dialkyl carbonate; or the carbonate compound is obtained by transesterification of an alcohol having the structure of Formula (IX) and diphenyl carbonate; The phosphate ester has a structure represented by formula (VIII); wherein a and b are independently selected from 0 or 1; R 12 , R 13 is independently selected from R 10 , R 11 , R 10 substituted with R 11 ; R 10 , R 11 , R 14 , R 15 are independently selected from hydrogen, C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group or C6-C 24 aromatic group substituted with at least one substituent; said substituent being selected from one or more of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy group, C1-C 18 ether group, C1-C 18 thioether group and thiol group; s is a natural number equal to or greater than 1; R8 is H or formula (VI); R 1a , R 2b are independently selected from -(CH2(R 12 )C(R 13 )CH2-O-) s R8, R1or R2; and only when R1= H, a = 1, R 1a = H or -(CH2(R 12 )C(R 13 )CH2-O-) s R8; and / or R2= H, b = 1, R 2b = H or -(CH2(R 12 )C(R 13 )CH2-O-) s R8; R1, R2are independently selected from the group consisting of C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent, C6-C 24 aromatic group or C6-C 24 aromatic group substituted with at least one substituent; said substituent being selected from the group consisting of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy group, C1-C 18 ether group, C1-C 18 thioether group and thiol group.

5. The production method according to claim 4, characterized by, R 10 , R 11 is independently selected from at least one of a hydrogen atom, -CH3, -CH2CH3, -CH2OH, -CH2OC(CH2OH)3, and -CH2OC(O)OCH3.

6. The preparation method according to claim 4, characterized in that, R 10 and R 11 one is selected from a hydrogen atom and the other is selected from -CH2OH or -CH2OC(O)OCH3.

7. The preparation method according to claim 4, characterized in that, a = b = 0 and R1, R2are independently selected from C1-C 18 alkyl, at least one substituent substituted C1-C 18 alkyl; said substituent is selected from C1-C 18 alkyl, C6-C 24 aryl, carbonate, hydroxyl, amino, nitro, halogen, C1-C 18 ester, C1-C 18 alkoxy, C1-C 18 ether, C1-C 18 thioether and mercapto.

8. The preparation method according to claim 4, characterized in that, a = b = 0, and R1, R2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, or isooctyl.

9. The preparation method according to claim 4, characterized in that, The P(O)-OH has a structure as shown in formula (I); In formula (I), R1and R2are independently selected from hydrogen, C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent selected from C1-C 24 aromatic group, or C6-C 24 aromatic group substituted with at least one substituent selected from C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, thiol group, and heterocycle. a and b are independently selected from 0 or 1; when a = b = 0, R1 and R2 are both hydrogen atoms or neither is a hydrogen atom.

10. The method of claim 9, wherein, the P(O)-OH compound is selected from at least one of phosphoric acid, diphenyl phosphate, dimethyl phosphate, diethyl phosphate, methyl phosphoric acid, ethyl phosphoric acid, propyl phosphoric acid, benzyl phosphoric acid, phenyl phosphoric acid, monophenyl phenyl phosphate, monomethyl phenyl phosphate, monoethyl phenyl phosphate, monophenyl methyl phosphate, monophenyl ethyl phosphate, dimethyl hypophosphorous acid, methyl ethyl hypophosphorous acid, diethyl hypophosphorous acid, dipropyl hypophosphorous acid, diisopropyl hypophosphorous acid, ethyl propyl hypophosphorous acid, di-n-butyl hypophosphorous acid, diisobutyl hypophosphorous acid, propyl butyl hypophosphorous acid, ethyl butyl hypophosphorous acid, methyl phenyl hypophosphorous acid, ethyl phenyl hypophosphorous acid, dibenzyl hypophosphorous acid, di(3-chloropropyl) hypophosphorous acid, di(3-bromopropyl) hypophosphorous acid, di(2-chloropropyl) hypophosphorous acid, di(2-bromopropyl) hypophosphorous acid, and diphenyl hypophosphorous acid.

11. The preparation method according to claim 4, characterized in that, the molar ratio of P-OH in the P(O)-OH compound to -OC(=O)O- in the carbonate compound is 1:0.1-20.

12. The method of claim 4, wherein, the acidolysis reaction is carried out at a temperature of 0-300°C for a time period of 0.1-30 h.

13. The preparation method according to claim 4, characterized in that, when the acidolysis reaction is carried out in the presence of a solvent, the solvent comprises at least one of toluene, ethylbenzene, propylbenzene, butylbenzene, dimethylbenzene, trimethylbenzene, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diphenylmethane.

14. The method of claim 4, wherein, the acidolysis reaction is carried out in the absence of a solvent.

15. The preparation method according to claim 4, characterized in that, when the acidolysis reaction is carried out in the presence of a catalyst, the catalyst comprises an inorganic base, an inorganic acid, a tertiary amine, a carboxylate, a phosphate, a titanate, an organotin, or a sulfonic acid.

16. The method of claim 4, wherein, the acidolysis reaction is carried out in the absence of a catalyst.

17. Use of the phosphate ester of any one of claims 1-3 or prepared by the method of any one of claims 4-16 as a flame retardant.

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