Phosphate ester and use thereof

Abstract

The present invention relates to the technical field of organic synthesis, and in particular relates to a phosphate ester and the use thereof. The phosphate ester has a structure represented by formula (IV) or formula (V), and is obtained by means of an acidolysis reaction of P(O)-OH with a carbonate compound, wherein the P(O)-OH has a general structural formula as represented by formula (I). In formula (I), R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C18 alkyl group, and a substituted or unsubstituted C6-C24 aromatic group, and the substituted substituent is selected from at least one of an alkyl group, an aromatic group, a carbonate group, a hydroxyl group, a heteroatom, and a heterocyclic ring; 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. The phosphate ester provided above has high flame retardancy.

Description

Phosphonate and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic synthesis, and particularly relates to a phosphonate 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] SUMMARY

[0005] Therefore, the purpose of the present application is to provide a phosphonate and application thereof. The phosphonate provided by the present application has high flame retardance.

[0006] The present application provides a preparation method of a phosphonate, comprising the following steps:

[0007] P(O)-OH and carbonate compound are subjected to acidolysis reaction to generate carbon dioxide and phosphonate.

[0008] Specifically, P(O)-OH and carbonate compound are mixed, and at least one carbonate functional group in the carbonate compound and P(O)-OH are subjected to acidolysis reaction to generate carbon dioxide and phosphonate.

[0009] The P(O)-OH has a general structure as shown in formula (I);

[0010] In formula (I), R1and R2are 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;

[0011] a and b are independently selected from 0 or 1, and when a = b = 0, R1and R2are both hydrogen atoms or neither is a hydrogen atom.

[0012] The phosphoric acid ester is a product obtained by acidolysis of at least one carbonate group of the carbonate compound and the phosphoric acid ester group. The acidolysis reaction simultaneously produces CO2. Structurally, when the carbonate is an acyclic carbonate, the phosphoric acid 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. When the carbonate is a cyclic carbonate, the phosphoric acid 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 phosphoric acid ester group. Before becoming a hydroxyl group or a phosphoric acid ester group, the other end can first polymerize itself, and then become a hydroxyl group or a phosphoric acid ester group.

[0013] wherein R 100 , R 101 , R 102 are organic moieties, and R 103 is H or a phosphoric acid group. n is a natural number greater than or equal to 1.

[0014] Optionally, R1and R2are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, and p-methylphenyl, and when a = b = 0, R1and R2are both hydrogen atoms or neither is a hydrogen atom.

[0015] Optionally, R1and R2are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, and p-methylphenyl, and at least one of a and b is 0, and when a = b = 0, R1and R2are both hydrogen atoms or neither is a hydrogen atom.

[0016] Optionally, R1, R2 are 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.

[0017] Optionally, R1, R2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, phenyl, p-methylphenyl, and a = b = 0.

[0018] Optionally, the P(O)-OH compound is selected from the group consisting of 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 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.

[0019] 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.

[0020] Optionally, the carbonate compound has a structure as shown in formula (II);

[0021] In formula (II), R3, R4 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, amino, nitro, halogen, C1-C 18 ester group, C1-C 18 alkoxy, C1-C 18 ether group, C1-C 18 thioether group, and mercapto.

[0022] Optionally, R3, R4 are independently selected from at least one of methyl, ethyl, propyl, isopropyl, isobutyl, phenyl, benzyl, and 4-methylphenyl.

[0023] Optionally, R3 and R4 are independently selected from at least one of methyl, ethyl, propyl, isopropyl, isobutyl and phenyl.

[0024] In one embodiment of the invention, the carbonate compound has a structure as shown in formula (Ⅲ);

[0025] In equation (Ⅲ), R5 and R6 are independently selected from C1 to C2. 18 Alkyl group, or at least one substituent substituted C1-C2 18 Alkyl groups, C6-C 24 The aromatic group or at least one substituent substituted C6-C 24 The aromatic group; the substituent is selected from C1 to C2. 18 Alkyl groups, C6-C 24 Aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy groups, C1-C 18 ether group, C1-C 18 One or more of the thioether group and the mercapto group.

[0026] Optionally, R5 and R6 are independently selected from one or more of hydrogen atoms, -CH3, -CH2CH3, -CH2OH, phenyl and -CH2OC(=O)OCH3.

[0027] In one embodiment of the invention, the carbonate compound simultaneously comprises carbonate compound molecules having the structure shown in Formula (II) and carbonate compound molecules having the structure shown in Formula (III). For example, glycerol carbonate obtained directly by the transesterification reaction of dimethyl carbonate and glycerol includes carbonate compound molecules having the structure shown in Formula (II) and carbonate compound molecules having the structure shown in Formula (III).

[0028] In one embodiment of the invention, the carbonate compound includes at least one of a carbonate compound having the structure shown in Formula (II) and a carbonate compound having the structure shown in Formula (III). Specifically, the carbonate compound may be a single compound or a mixture of multiple carbonate compounds. For example, the carbonate compound may be a carbonate compound having the structure shown in Formula (II) or a carbonate compound having the structure shown in Formula (III); it may also simultaneously include a carbonate compound having the structure shown in Formula (II) and a carbonate compound having the structure shown in Formula (III).

[0029] 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, polycarbonate of bisphenol A, 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, a product obtained by transesterification of glycerol and a diaryl carbonate.

[0030] In certain embodiments of the present application, when the phosphate ester is P(O)-OH and the carbonate compound having the structure of formula (II) is subjected to acidolysis reaction, the product has the structure of formula (IV):

[0031] In formula (IV), a, b are the same as the definitions of a, b in formula (I);

[0032] R 20 is selected from R3or R4in formula (II);

[0033] R 1a , R 2b are independently selected from R 20 or R1, R2in formula (I); and only when R1= H, a = 1 in formula (I), R 1a = H or R 20 ; and / or, R2= H, b = 1 in formula (I), R 2b = H or R 20 .

[0034] Optionally, a, b are independently selected from 0 or 1.

[0035] R 20 is 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 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 18alkoxy groups, C1-C 18 ether group, C1-C 18 The thioether group or mercapto group.

[0036] Optionally, R 20 It is selected from methyl, ethyl, propyl, isopropyl, isobutyl, phenyl, benzyl or 4-methylphenyl.

[0037] Optionally, R 20 It is selected from methyl, ethyl, propyl, isopropyl, isobutyl or phenyl.

[0038] R 1a R 2b Independently selected from R 20 Hydrogen, C1~C 18 Alkyl group, or at least one substituent substituted C1-C2 18 Alkyl groups, C6-C 24 The aromatic group or at least one substituent substituted C6-C 24 The aromatic group; the substituent is selected from C1 to C2. 18 Alkyl groups, C6-C 24 It contains at least one of the following groups: aromatic group, carbonate group, hydroxyl group, amino group, nitro group, mercapto group, and heterocyclic group.

[0039] Optionally, R 1a R 2b Independently selected from R 20 Hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl or p-methylphenyl.

[0040] In one embodiment of the present invention, when a product is obtained by acidolysis of a phosphate ester of type P(O)-OH and a carbonate compound having the structure shown in formula (Ⅲ), it has the structure shown in formula (V):

[0041] In equation (V), a and b have the same definitions as a and b in equation (I);

[0042] The selection of R5 and R6 is the same as described in equation (Ⅲ), and will not be repeated here.

[0043] m is a natural number greater than or equal to 1;

[0044] R7 is H or a group having the structure shown in formula (VI);

[0045] In equation (VI), the selection of R1, R2, a, and b is the same as described in equation (I), and will not be repeated here;

[0046] R 1a R 2bindependently selected from the group consisting of -(CHR5-CHR6-O)-, -C(O)-, -S(O)2- and -NR7-; m R7, R1in formula (I) or R2in formula (I); and only when R1in formula (I) = H, a = 1, R 1a = H or -(CHR5-CHR6-O)- m R7, and / or R2= H, b = 1, R 2b = H or -(CHR5-CHR6-O)- m R7.

[0047] Optionally, R 1a , R 2b independently selected from the group consisting of -(CHR5-CHR6-O)-, -C(O)-, -S(O)2- and -NR7-; m R7, 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 the group consisting of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, mercapto group and heterocycle.

[0048] Optionally, R 1a , R 2b independently selected from the group consisting of -(CHR5-CHR6-O)-, -C(O)-, -S(O)2- and -NR7-; m R7, hydrogen, hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, hydroxyethyl group, hydroxypropyl group, benzyl group, phenyl group and p-methylphenyl group.

[0049] When the P(O)-OH is subjected to acidolysis 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 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.

[0050] The mixing manner 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.

[0051] 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 speed 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.

[0052] The acidolysis reaction can be carried out at normal pressure, or at positive pressure or negative pressure.

[0053] 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.

[0054] 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.

[0055] Preferably, the acidolysis reaction is carried out without a solvent. The case without a solvent includes the case where an excess of raw material is used as a solvent.

[0056] 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, organic tin, or sulfonic acids.

[0057] Preferably, the acidolysis reaction is carried out without a catalyst.

[0058] 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, alkali washing, acid washing, water washing, and drying. 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, and diethyl phenyl phosphinate is obtained.

[0059] Preferably, the acidolysis reaction is used directly without additional purification. The additional purification here refers to the separation means using extraction, column chromatography, alkali washing, acid washing, etc. It does not include the method of removing the excess reactants or by-products after the reaction by water washing, normal pressure or vacuum distillation. In some embodiments of the present application, the acidolysis reaction is followed by vacuum distillation.

[0060] In some embodiments of the present application, a phosphate ester and a method for preparing the same are provided. The phosphate ester is the product of an acidolysis reaction of at least one carbonate group of a carbonate compound and P(O)-OH, wherein the P(O)-OH has the structure of Formula (I) and the carbonate compound has the structure of Formula (VII); and the corresponding phosphate ester has the structure of Formula (VIII).

[0061] 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.

[0062] 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.

[0063] Optionally, R 10 and R 11 , one is selected from hydrogen atom, and the other is selected from -CH2OH or -CH2OC(O)OCH3.

[0064] In Formula (VIII), a and b are the same as the definitions of a and b in Formula (I).

[0065] R 12 and R 13 are independently selected from R 10R8in formula (VIII) is H or a group of formula (VI) 11 R8in formula (VIII) is H or a group of formula (VI) 10 R8in formula (VIII) is H or a group of formula (VI) 11 .

[0066] s is a natural number greater than or equal to 1 ; R8is H or a group of formula (VI).

[0067] 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. In this paragraph s has the same meaning as s in formula (VIII).

[0068] Optionally, a = b = 0.

[0069] 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 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 mercapto group.

[0070] 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 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 18Alkyl groups, C6-C 24 Aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy groups, C1-C 18 ether group, C1-C 18 One or more of the thioether group and the mercapto group.

[0071] Optionally, a = b = 0, and R1 and R2 are independently selected from C1 to C2. 18 Alkyl group, or at least one substituent substituted C1-C2 18 Alkyl groups; the substituents are selected from C1 to C2. 18 Alkyl groups, C6-C 24 Aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy groups, C1-C 18 ether group, C1-C 18 One or more of the thioether group and the mercapto group.

[0072] Optionally, a = b = 0, and R1 and R2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, isohexyl, isohexyl, or isooctyl.

[0073] In equation (VIII), R 12 R 13 R, independently selected from equation (VII) 10 R in equation (VII) 11 R replaced by equation (VI) 10 Or R replaced by equation (VI) 11 The replacement here refers to the original R. 10 R 11 The H on the hydroxyl group in formula (VII) is replaced by a group having the structure shown in formula (VI). For example, R in formula (VII) 10 If it is -CH2OH, then R in equation (VIII) 12 or R 13 It can be -CH2OR9, where R9 is H or a group with the structure shown in formula (VI).

[0074] In equation (VIII), when s is greater than 1, R in each repeating unit inside parentheses 12 Or R 13 They can be the same or different. For example, in a repeating unit, R 12 The R9 can be -CH2OR9, where R9 = H; while the other repeating unit can be -CH2OR9, where R9 is not equal to H, and the specific R9 is determined by the reaction.

[0075] Optionally, the phosphate ester has a structure represented by Formula (VIII');

[0076] wherein * indicates the position of attachment of the substituent in the compound.

[0077] wherein R h , R h are independently selected from hydrogen, ethyl, hydroxyl-substituted methyl, Formula (R h -1), Formula (R h -2), or Formula (R h -3); R h are independently selected from hydroxyl-substituted methyl, Formula (R h -1), Formula (R h -2), or Formula (R h -3).

[0078] Optionally, the phosphate ester has at least one of the structures represented by Formula Vlll-1 to Formula Vlll-6.

[0079] The method for preparing a phosphate ester having a structure represented by Formula (VIII) comprises the following steps:

[0080] subjecting P(O)-OH and a carbonate compound to an acidolysis reaction to generate carbon dioxide and a phosphate ester having a structure represented by Formula (VIII);

[0081] The carbonate compound has a structure represented by Formula (VII);

[0082] or the carbonate compound is obtained by subjecting an alcohol having a structure represented by Formula (IX) and a dialkyl carbonate to an ester exchange reaction (ester exchange reaction product);

[0083] or the carbonate compound is obtained by subjecting an alcohol having a structure represented by Formula (IX) and diphenyl carbonate to an ester exchange reaction (ester exchange reaction product);

[0084] In Formula (IX), R 14 , R 15 are the same as the selection of R 10 , R 11 in Formula (VII).

[0085] When the alcohol having the structure shown in formula (IX) and the dialkyl carbonate or diphenyl carbonate are subjected to the transesterification reaction, the generated carbonate compound (transesterification reaction product) can have two or more of the structural features of the carbonate molecules of formula (II) and (VII) in its molecular structure. For example, the transesterification of trihydroxypropane and dimethyl carbonate directly obtains a carbonate structure in which there are cyclic carbonate molecules and linear carbonate molecules.

[0086] The P(O)-OH has the structure shown in formula (I), which is not described in detail here.

[0087] When the P(O)-OH and the carbonate compound are subjected to the 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.

[0088] The temperature of the acidolysis reaction is 0-300°C. Alternatively, the reaction temperature is 50-250°C, 100-250°C, 150-250°C, 150-240°C, 180-240°C.

[0089] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0090] The time of the acidolysis reaction is 0.1-30h. For example, 0.2-25h, 0.3-20h, 0.4-18h, 0.5-15h, 1-15h, 1-12h, or 1-10h.

[0091] 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.

[0092] Preferably, the acidolysis reaction is carried out without a solvent. The case without a solvent includes the case where an excess of the raw material is used as the solvent.

[0093] 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, organotin compounds, or sulfonic acids.

[0094] Preferably, the acidolysis reaction is carried out without a catalyst.

[0095] Preferably, after the acid hydrolysis reaction is completed, the phosphate ester with the structure shown in formula (VIII) obtained does not need to be purified by conventional methods such as extraction, distillation, column chromatography, alkali washing, acid washing, etc., and can be used directly.

[0096] In one embodiment of the present invention, a phosphate ester is provided having the structure shown in formula (XI):

[0097] Among them, R 21 Selected from the remaining group after a polyol loses two terminal hydroxyl groups;

[0098] R 22 R 23 Independently selected from the structure shown in H or formula (VI), and R 22 and R 23 Not both H;

[0099] x1 is a natural number.

[0100] In equation (VI), the constraints of R1, R2, a, and b are the same as above, and will not be repeated here.

[0101] Optionally, R 21 It can 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-, and -(CH2CH2OCH2CH2)4-.

[0102] Preferably, R 21 It is the group remaining after removing the two terminal hydroxyl groups from bisphenol A, bisphenol F, bisphenol S, and 4,4'-dihydroxybiphenyl.

[0103] Optionally, in equation (XI), a = b = 0.

[0104] Optionally, R1 and R2 are independently selected from C1 to C2. 18 Alkyl group, or at least one substituent substituted C1-C2 18 Alkyl groups, C6-C 24 The aromatic group or at least one substituent substituted C6-C 24C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 18 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 24 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle.

[0105] Optionally, a = b = 0, and R1, R2are independently selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 18 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 18 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 18 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 24 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle.

[0106] Optionally, a = b = 0, and R1, R2are independently selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle.

[0107] In some embodiments of the present application, the phosphate-based flame retardant comprises at least one of the structures shown in Formula (XI-1) and Formula (XI-2); optionally, the phosphate-based flame retardant comprises both Formula (XI-1) and Formula (XI-2).

[0108] In some embodiments of the present application, the phosphate-based flame retardant comprises at least one of the structures shown in Formula (XI-1), Formula (XI-2), Formula (XI-3), Formula (XI-4), Formula (XI-5), and Formula (XI-6); optionally, the phosphate-based flame retardant comprises both Formula (XI-1), Formula (XI-2), Formula (XI-3), Formula (XI-4), Formula (XI-5), and Formula (XI-6).

[0109] The method for preparing the phosphate comprises the following steps:

[0110] The acidolysis reaction of P(O)-OH and polycarbonate compound produces carbon dioxide and phosphate.

[0111] The phosphate is the product of the acidolysis reaction of at least one carbonate functional group in P(O)-OH and polycarbonate compound. The acidolysis reaction produces CO2.

[0112] The P(O)-OH has a structure shown in Formula (I).

[0113] In Formula (I), R1and R2are independently selected from the group consisting of hydrogen, C1-C10alkyl, C6-C10aryl, at least one substituent-substituted C1-C10alkyl, at least one substituent-substituted C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 18 C6-C10aryl; the substituents are selected from the group consisting of C1-C10alkyl, C6-C10aryl, carbonate, hydroxyl, amino, nitro, thiol, and heterocycle. 18Alkyl groups, C6-C 24 The aromatic group or at least one substituent substituted C6-C 24 The aromatic group; the substituent is selected from C1 to C2. 18 Alkyl groups, C6-C 24 At least one of the aromatic group, carbonate group, hydroxyl group, amino group, nitro group, mercapto group and heterocyclic group;

[0114] a and b are independently selected from 0 or 1; when a = b = 0, R1 and R2 are either both hydrogen atoms or neither of them are hydrogen atoms.

[0115] Optionally, R1 and R2 are independently selected from hydrogen atoms, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, and p-methylphenyl, and when a = b = 0, R1 and R2 are either both hydrogen atoms or neither of them are hydrogen atoms.

[0116] Optionally, R1 and R2 are independently selected from hydrogen atoms, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, and p-methylphenyl, and at least one of a and b is 0, and when a = b = 0, R1 and R2 are either both hydrogen atoms or neither of them are hydrogen atoms.

[0117] Optionally, R1 and R2 are independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl, and p-methylphenyl, and a = b = 0.

[0118] Optionally, R1 and R2 are independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, phenyl, and p-methylphenyl, and a = b = 0.

[0119] Optionally, 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, phenyl monophenyl phosphate, phenyl monomethyl phosphate, phenyl monoethyl phosphate, methyl monophenyl phosphate, methyl monomethyl phosphate, methyl monoethyl phosphate, dimethyl hypophosphite, methyl ethyl hypophosphite, diethyl hypophosphite, dipropyl hypophosphite, diisopropyl hypophosphite, ethyl propyl hypophosphite, di-n-butyl hypophosphite, diisobutyl hypophosphite, propyl butyl hypophosphite, ethyl butyl hypophosphite, methyl phenyl hypophosphite, ethyl phenyl hypophosphite, dibenzyl hypophosphite, di(3-chloropropyl) hypophosphite, di(3-bromopropyl) hypophosphite, di(2-chloropropyl) hypophosphite, di(2-bromopropyl) hypophosphite, and diphenyl hypophosphite.

[0120] The polycarbonate has the structure shown in formula (X);

[0121] Among them, R21 selected from the remaining portion after the loss of two terminal hydroxyl groups of a polyol;

[0122] x is a natural number greater than 1.

[0123] The generated phosphate ester has a structure shown in formula (XI);

[0124] wherein R 21 with the definition in formula (X), R 22 , R 23 are each independently selected from H or having a structure shown in formula (VI), and R 22 and R 23 cannot be H at the same time.

[0125] x1 is a natural number, and x1 is less than x in formula (X).

[0126] Optionally, the degree of polymerization x of the polycarbonate is a natural number greater than 3, 5, 10, 20, 30, 40, 50.

[0127] 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.

[0128] The acidolysis reaction temperature 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.

[0129] 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.

[0130] The acidolysis reaction is carried out in a solvent or without a solvent. Preferably, the acidolysis reaction is carried out without an external solvent.

[0131] 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.

[0132] Preferably, the phosphonate having the structure shown in formula (XI) obtained after the acidolysis reaction can be directly used without purification by extraction, distillation, column chromatography, alkaline washing, acid washing, and the like.

[0133] In some embodiments of the present application, the P(O)-OH is dialkyl phosphinic 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 the mixture of vinylidene phosphate esters is abbreviated as VPE.

[0134] In formula (XII), R1and R2are selected in the same manner as in formula (I);

[0135] R 61 is H, methyl, or phenyl;

[0136] R 62 is H or a group shown in formula (VI), and a = b = 0 in formula (VI);

[0137] t is a natural number greater than or equal to 1.

[0138] Optionally, in formula (XII), R1and R2are independently selected from C1-C6 alkyl or C1-C6 alkyl substituted with at least one substituent;

[0139] The substituent is selected from C1-C6 alkyl.

[0140] In some embodiments of the present application, the phosphate ester includes structures shown in formula (XII-1) to formula (XII-2);

[0141] The method for preparing the phosphate ester having the structure shown in formula (XII) includes the following steps:

[0142] The dialkyl phosphinic acid is subjected to acidolysis reaction with the carbonate compound to generate carbon dioxide and the phosphate ester having the structure shown in formula (XII);

[0143] The carbonate compound is one or more of vinyl carbonate, 1,2-propanediol carbonate, and styrene carbonate.

[0144] The molar ratio of the dialkyl phosphinic acid 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 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.

[0145] 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 or 180-240°C.

[0146] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] Preferably, the acidolysis reaction is carried out without a catalyst.

[0152] Preferably, after the acidolysis reaction, the obtained mixture of vinylidene phosphonate having the structure shown in formula (XII) is directly used without purification by extraction, distillation, column chromatography, base washing, acid washing or other conventional methods.

[0153] 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 a product of transesterification of glycerol and dialkyl carbonate; or the carbonate compound is a product of transesterification of glycerol and diphenyl carbonate; and the corresponding phosphoric acid ester includes structures shown in Formula (XIII) to (XIV), which is referred to as glycerol phosphoric acid ester mixture.

[0154] wherein R1and R2are selected as in Formula (I).

[0155] Optionally, R1and R2are C1-C6 alkyl or C1-C6 alkyl substituted with at least one substituent selected from C1-C6 alkyl.

[0156] Optionally, the phosphoric acid ester includes structures shown in Formula (X-1) to (X-4).

[0157] In the glycerol phosphoric acid ester mixture, the phosphoric acid ester consisting of structures shown in Formula (XIII) to (XIV) accounts for at least 60% to 80%, such as 60%, 70%, 80% of the total phosphoric acid ester moles.

[0158] The method for preparing the glycerol phosphoric acid ester mixture comprises:

[0159] subjecting dialkyl phosphinic acid to acidolysis with a carbonate compound to produce carbon dioxide and a phosphoric acid ester including structures shown in Formula (XIII) to (XIV);

[0160] The carbonate compound is glycerol carbonate; or the carbonate compound is a product of transesterification of glycerol and dialkyl carbonate; or the carbonate compound is a product of transesterification of glycerol and diphenyl carbonate.

[0161] When the dialkyl phosphinic acid is subjected to acidolysis 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-. The molar ratio of P-OH in the dialkyl phosphinic acid to -OC(=O)O- in the carbonate compound 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.

[0162] The acidolysis reaction is carried out at a temperature of 0-300°C. Alternatively, the reaction is carried out at a temperature of 50-250°C, 100-250°C, 150-250°C, 150-240°C, or 180-240°C.

[0163] The acidolysis reaction can be carried out under normal pressure, or under positive or negative pressure.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] Preferably, the acidolysis reaction is carried out without a catalyst.

[0169] Preferably, after the acidolysis reaction, the obtained glycerophosphonate mixture having the structure shown in formula (XIII)-(XIV) is directly used without being purified by extraction, distillation, column chromatography, base washing, acid washing, or the like.

[0170] The glycerophosphonate mixture prepared by the present application using a carbonate compound instead of an epoxide compound not only avoids the use of toxic glycidol, but also greatly avoids oligomeric phosphonates generated by the ring-opening self-polymerization of glycidol, which have low phosphorus content and are not conducive to flame retardation. Furthermore, the preparation of the glycerophosphonate mixture by acidolysis of the product generated by the transesterification of glycerol and dialkyl carbonate or diphenyl carbonate and dialkyl phosphinic acid can further reduce the cost.

[0171] The present application also provides the use of the above-mentioned phosphonate as a flame retardant. The phosphonate provided by the present application has high flame retardation performance.

[0172] The present application also provides a flame-retardant high polymer material. The flame-retardant high polymer material comprises a flame retardant and a high polymer material, wherein the flame retardant comprises the phosphate ester prepared by the method described above.

[0173] Preferably, the flame-retardant high polymer material comprises 0.1 wt% to 50 wt% of the flame retardant and 50 wt% to 99.9 wt% of the high polymer material.

[0174] 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%.

[0175] Preferably, the flame-retardant high polymer material further comprises a functional additive.

[0176] Preferably, the functional additive is selected from at least one of a reinforcing agent, an anti-dripping agent, a stabilizer, a pigment, a dye, a char-forming catalyst, a dispersant, a nucleating agent, an inorganic filler, an organic filler, and an antioxidant.

[0177] Preferably, the mass content of the functional additive in the flame-retardant high polymer material is 5% to 40%, for example, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 28%, 30%, 33%, 35%, 38%, or 40%.

[0178] Preferably, the flame-retardant high polymer material further comprises a flame retardant Q.

[0179] Preferably, the flame retardant Q is selected from at least one of a phosphorus-based flame retardant, a nitrogen-based flame retardant, or a boron-based flame retardant.

[0180] Preferably, the mass content of the flame retardant Q in the flame-retardant high polymer material is 0.5% to 20%, for example, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, or 20%.

[0181] Preferably, the high polymer material is selected from a thermoplastic resin or a thermosetting resin.

[0182] 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.

[0183] Preferably, the thermosetting resin is selected from at least one of vinyl polyphenyl 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.

[0184] Preferably, the thermosetting resin is at least one of polyurethane resin and epoxy resin. Particularly preferably, the thermosetting resin is epoxy resin.

[0185] 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.

[0186] 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.

[0187] The high molecular material according to the present application includes, but is not limited to, the products available on the market.

[0188] Preferably, the flame-retardant high molecular material comprises 0.1wt% to 30wt% of phosphate ester and 70wt% to 99.9wt% of high molecular material.

[0189] Preferably, the mass content of the phosphate ester in the flame-retardant high molecular material is any value or a range value between any two values selected from 0.1%, 0.5%, 1%, 2%, 3%, 3.5%, 4%, 5%, 6%, 8%, 10%, 15% and 20%. Advantages:

[0190] The preparation method of the phosphate ester provided by the present application has the following advantages:

[0191] 1) The raw materials are widely available and have wide applicability.

[0192] 2) The process is simple and can be carried out by heating only, without the need for solvents and catalysts, and is economical.

[0193] 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.

[0194] 4) Carbonate 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

[0195] FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of diethyl phenyl phosphinate according to Example 1 of the present application;

[0196] Figure 2 is a nuclear magnetic resonance hydrogen spectrum of trimethylolpropane- diethylphosphite in Example 13 of the present application;

[0197] Figure 3 is a nuclear magnetic resonance hydrogen spectrum of bisphenol A diethyl phosphite hemiester in Example 15 of the present application. DETAILED DESCRIPTION

[0198] 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 some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0199] The raw materials used in the examples are as follows:

[0200] Diethyl phosphite (DEPA): Jiangsu Lisi New Material Co., Ltd.

[0201] Dipropyl phosphite (DPPA): Jiangsu Lisi New Material Co., Ltd.

[0202] Diisobutyl phosphite (DBPA): prepared according to CN101010372

[0203] Diphenyl phosphite (DPhPA): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0204] Phenyl phosphonic acid (PhPA): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0205] Diphenyl phosphate (DPP): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0206] Diphenyl carbonate (DPC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0207] Dimethyl carbonate (DMC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0208] Ethylene carbonate (EC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0209] Di-n-butyl carbonate (DBC): Shanghai Macklin Biochemical Technology Co., Ltd.

[0210] Glycerol (Gly): National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0211] Glycerol carbonate (GC): Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0212] Trimethylolpropane (THMP): Shanghai Macklin Biochemical Technology Co., Ltd.

[0213] E44 epoxy resin: Shanghai Macklin Biochemical Science and Technology Co., Ltd.

[0214] 4,4'-diaminodiphenyl methane (DDM): Shanghai Macklin Biochemical Science and Technology Co., Ltd.

[0215] The tests used in the examples correspond to the following standards:

[0216] Vertical burning test (UL94): GB / T2408-2008

[0217] Limiting oxygen index test (LOI): GB / T2406.2-2009

[0218] Bending test: GB / T9341-2008

[0219] Compression test: GB / T1041-2008.

[0220] Example 1

[0221] Preparation of phenyl diethylphosphite (PDEP)

[0222] In a 500 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet and outlet, 220.0 g (1.02 mol) of diphenyl carbonate (DPC) and 139.0 g (1.14 mol) of diethyl phosphite were mixed. The mixture was heated to 180°C under nitrogen and reacted at normal 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 under 8-10 mmHg. The temperature was then increased to 190°C for distillation under reduced pressure, and 182.0 g of colorless transparent liquid product, phenyl diethylphosphite, was obtained. The yield was 89.6%. Its structure is shown in formula IV-1 (corresponding to the aforementioned structural formula IV):

[0223] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of phenyl diethylphosphite in Example 1 of the present application.

[0224] After testing, 1 H NMR, CDCl3as solvent: 7.0-7.4 ppm (Ph-H, 5H), 1.8 ppm (-CH2-, 4H), 1.2 ppm (-CH3, 6H).

[0225] Example 2

[0226] Preparation of phenyl diethylphosphite (PDEP)

[0227] 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 hypophosphite 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 190°C and the product, diethyl hypophosphite phenyl ester, 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):

[0228] 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).

[0229] Example 3

[0230] Preparation of diisobutyl hypophosphite phenyl ester (DIBP)

[0231] 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 diisobutyl hypophosphite 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, diisobutyl hypophosphite phenyl ester, 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):

[0232] 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).

[0233] Example 4

[0234] Preparation of diisobutyl hypophosphite phenyl ester (DIBP)

[0235] In a 25 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet-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 reacted at normal pressure. After 1 h, the reaction of diphenyl carbonate was completed. Subsequently, phenol was removed by distillation under reduced pressure at 170-180°C under 8-10 mmHg. Further heating to 200°C under reduced pressure gave 4.7 g of colorless transparent liquid product, phenyl diphenylphosphinite. Yield 66.0%. Its structure is shown in formula IV-3 (corresponding to the above formula IV):

[0236] Upon examination, 1 H NMR, CDC13as solvent: 7.0-7.4 ppm (Ph-H, 5H), 2.2 ppm (-CH-, 2H), 1.8 ppm (-CH2-, 4H), 1.1 ppm (-CH3, 12H).

[0237] Example 5

[0238] Preparation of phenyl diphenylphosphinite (PDPhP)

[0239] 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 diphenylphosphinic 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 solution was dissolved in toluene, and excess diphenylphosphinic acid and phenol were washed away with 0.5 wt% aqueous sodium hydroxide and deionized water, respectively. Finally, toluene was removed by distillation under reduced pressure at 80°C under 8-10 mmHg to give 2.2 g of white solid product, phenyl diphenylphosphinite. Yield 53.5%. Its structure is shown in formula IV-4 (corresponding to the above formula IV):

[0240] Upon examination, 1 H NMR, CDC13as 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).

[0241] Example 6

[0242] Preparation of phenyl phosphonate (PPhP)

[0243] In a 100 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet and outlet, 10.0 g (0.06 mol) of phenylphosphonic 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 under 8-10 mmHg to obtain 14.1 g of a light yellow solid product, phenyl phenylphosphonate (monoester: diester = 1 : 1.2). The yield was 63.9%. The structure is shown in Formula IV-5-1 and Formula IV-5-2 (corresponding to the aforementioned structural formula IV):

[0244] 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).

[0245] 31 P NMR, CDC13 as solvent: 18.0 ppm (monoester, 45.8%), 11.6 ppm (diester, 54.2%).

[0246] Example 7

[0247] Preparation of triphenyl phosphate (TPP)

[0248] 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 reaction of diphenyl carbonate was completed. Subsequently, the reaction solution was dissolved in toluene, and excess diphenyl phosphate and phenol were removed by washing with 0.5 wt% sodium hydroxide aqueous solution and deionized water, respectively. Finally, toluene was removed by distillation under reduced pressure at 80°C under 8-10 mmHg to obtain 3.6 g of a light yellow liquid product, triphenyl phosphate. The yield was 27.6%. The structure is shown in Formula IV-6 (corresponding to the aforementioned structural formula IV):

[0249] Upon examination, 1 H NMR, CDC13 as solvent: 7.0-7.5 ppm (Ph-H, 15H).

[0250] Example 8

[0251] Preparation of n-butyl diethylphosphite (BDEP)

[0252] In a 50 mL four-necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 5.0 g (0.04 mol) of diethylphosphinic acid and 3.6 g (0.02 mol) of di-n-butyl carbonate were mixed. The mixture was heated to 230°C under nitrogen and the reaction was carried out 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 diethylphosphinic acid was washed out with water. Finally, toluene was removed by rotary evaporation and vacuum drying to obtain 1.2 g of light yellow liquid product, di-n-butyl phosphite. The yield was 34.3%. Its structure is shown in formula IV-7 (corresponding to the previous structure IV):

[0253] 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).

[0254] Example 9

[0255] Preparation of diethylphosphinic acid ethylene glycol ester (EG-DEP) mixture

[0256] 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 diethylphosphinic 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 ethylene carbonate was completely reacted. Without post-treatment, 12.2 g of liquid product, diethylphosphinic acid ethylene glycol ester, was obtained. The yield was 72.2%. Its main component structure is shown in formula XII-1 and formula XII-2 (corresponding to the previous structure formula XII), in which the molar ratio of monoester (formula XII-1) to diester (formula XII-2) is 3:1, and the molar ratio of phosphorus to total phosphorus is >93%.

[0257] Upon testing, 1 H NMR, CDCl3as 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).

[0258] Example 10

[0259] Preparation of diethylphosphinic acid ethylene glycol ester (EG-DEP) mixture

[0260] In a 50 mL four-necked flask equipped with a thermometer, a mechanical stirrer, and a nitrogen inlet-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 reacted at normal pressure. After 3 h, the diethyl phosphinic acid was completely reacted. The excess ethylene carbonate was removed by distillation under reduced pressure at 180°C and 8-10 mmHg, obtaining 11.8 g of liquid product, ethylene glycol diethyl phosphinate. The yield was 73.9%. The main component structures thereof were shown in Formula XII-1 and Formula XII-2 (corresponding to the aforementioned Formula XII), wherein the molar ratio of monoester (Formula XII-1) to diester (Formula XII-2) was 6.8:1, and the molar ratio of phosphorus in both to the total phosphorus was >94%.

[0261] It was detected that the main component structures thereof were shown in Formula X-1, Formula X-2, Formula X-3, and Formula X-4 (corresponding to the aforementioned Formula XIII-XVI), wherein the molar ratio of phosphorus in the four structures to the total phosphorus was >91%. 1 H NMR, CDCl3as 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).

[0262] Example 11

[0263] Preparation of glycerol diethyl phosphinate (GDEP) from glycerol

[0264] 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 diethyl phosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and reacted at normal pressure. After 4 h, the reaction was completed. Without post-treatment, 26.2 g of yellow transparent liquid product, glycerol diethyl phosphinate, was obtained, with a yield of 78.6%, and the main component structures thereof were shown in Formula X-1, Formula X-2, Formula X-3, and Formula X-4 (corresponding to the aforementioned Formula XIII-XVI), wherein the molar ratio of phosphorus in the four structures to the total phosphorus was >91%.

[0265] It was detected that the main component structures thereof were shown in Formula X-1, Formula X-2, Formula X-3, and Formula X-4 (corresponding to the aforementioned Formula XIII-XVI), wherein the molar ratio of phosphorus in the four structures to the total phosphorus was >91%. 1 H NMR, CDCl3as 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).

[0266] Example 12

[0267] Preparation of glycerol diethyl phosphinate (GDEP) from glycerol

[0268] In a 100 mL four-necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and 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 atmosphere at normal pressure with 0.2 mol% DBDL as catalyst. After 18 h, the reaction of di-n-butyl carbonate was completed and a mixture of glycerol carbonate was obtained (denoted as Gly-C). Then 13.2 g (0.11 mol) of diethyl phosphinic acid was added and the reaction was carried out at 190-200 °C under normal pressure. After 4 h, the reaction of glycerol carbonate was completed. The product diethyl phosphinic acid glycerol ester was obtained in 17.7 g with a yield of 83.1%. Its main component structures are shown in formula X-1, formula X-2, formula X-3, formula X-4 (corresponding to the above-mentioned structures XIII-XVI), and the molar ratio of the phosphate esters of these four structures to the total phosphorus is >71%.

[0269] 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).

[0270] Example 13

[0271] Preparation of trimethylolpropane-diethyl phosphinic acid ester (THMP-DEP)

[0272] Trimethylolpropane carbonation: In a 100 mL four-necked flask equipped with a thermometer, mechanical stirrer, nitrogen inlet and outlet, 10.0 g (0.07 mol) of trimethylolpropane and 0.07 g (0.5 mol%) of dibutyltin dilaurate were mixed. The mixture was heated to 140 °C under nitrogen, and 25.0 g (0.28 mol) of dimethyl carbonate was added dropwise in batches through a constant pressure dropping funnel, and the reaction was carried out under normal pressure. After 18 h, the residual methanol and dimethyl carbonate were removed by vacuum distillation at 8-10 mmHg and room temperature, and trimethylolpropane carbonate was obtained, denoted as THMP-C. Then 8.5 g (0.07 mol) of diethyl phosphinic acid was added, and the reaction was continued at 190 °C under normal pressure. After 9 h, the reaction of diethyl phosphinic acid was completed. No purification was needed. 15.0 g of light yellow liquid product trimethylolpropane-diethyl phosphinic acid ester was obtained with a yield of 86.2%. Denoted as THMP-DEP, its main structures are shown in formula VIII-1, formula VIII-2, formula VIII-3, formula VIII-4, formula VIII-5, formula VIII-6 (corresponding to the above-mentioned structure formula VIII):

[0273] Figure 2 is a proton nuclear magnetic resonance spectrum of trimethylolpropane- diethylphosphite according to Example 13 of the present application.

[0274] Upon testing, 1 H NMR, CDC13 as 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).

[0275] Example 14

[0276] Preparation of bisphenol A diethylphosphite (BPA-DEP)

[0277] 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 and 9.61 g (0.08 mol) of diethylphosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and reacted at normal pressure. After 3 h, the bisphenol A polycarbonate reacted completely. Without post-treatment, 21.0 g of yellow transparent semi-solid product, bisphenol A diethylphosphite monoester, was obtained with a yield of 82.0%. Its main component structures include Formula (XI-1) and Formula (XI-2):

[0278] Upon testing, 1 H NMR, CDC13 as 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).

[0279] Example 15

[0280] Preparation of bisphenol A diethylphosphite hemiester (BPA-0.5DEP)

[0281] 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 and 9.61 g (0.08 mol) of diethylphosphinic acid were mixed. The mixture was heated to 180°C under nitrogen and reacted at normal pressure. After 3 h, the bisphenol A polycarbonate reacted completely. Without post-treatment, 21.0 g of yellow transparent semi-solid product, bisphenol A diethylphosphite monoester, was obtained with a yield of 82.0%. Its main component structures include Formula (XI-1) and Formula (XI-2): Upon testing,

[0282] Figure 3 is a nuclear magnetic resonance hydrogen spectrum of the bisphenol A diethyl phosphinate hemiester of Example 15.

[0283] 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).

[0284] Referring to Tables 1-3, which are summary tables of the synthesis of the examples of the present application.

[0285] Table 1 Summary of phenyl phosphate synthesis

[0286] Table 2 Summary of alkyl diethyl phosphinate synthesis

[0287] Table 3 Summary of bisphenol A phosphate synthesis

[0288] Example 1

[0289] Flame retardant applications of ethylene glycol diethyl phosphinate (EG-DEP, prepared in Example 9) in epoxy resins:

[0290] Sample preparation: all samples were prepared in the same way, using 3 wt% EP / EG-DEP as an example: 79.6 parts of epoxy resin DGEBA was heated at 80°C, and after it was fully softened, 17.4 parts of 4,4-diaminodiphenyl methane (DDM) was added, and the DDM was dissolved by rapid stirring; after most of the DDM was dissolved, 3 parts of EG-DEP (prepared in Example 9) was added, and the mixture was stirred for 1 min to form a uniform mixture; the mixture was poured into a mold preheated to 80°C while it was still hot, and after it was left to stand for 10 min, it was pre-cured at 120°C for 2 h, and then cured at 170°C for 4 h. After it was naturally cooled to room temperature, an EP / EG-DEP composite material with an addition amount of 3 wt% was obtained. The thickness of the sample was 3.2 mm.

[0291] The vertical burning (UL94) test results of the EP / EG-DEP composite materials are shown in Table 4.

[0292] Table 4 Vertical burning (UL94) test results of EP / EG-DEP composite materials

[0293] As can be seen from Table 4, EG-DEP showed extremely high flame retardant performance in epoxy resins, and only 3 wt% addition amount passed the UL94 test.

[0294] Application Example 2

[0295] Flame-retardant application of trimethylolpropane-diethyl phosphite (THMP-DEP, prepared in Example 13) in epoxy resin:

[0296] Sample preparation: All sample preparation methods are the same, take the EP / THMP-DEP with 4wt% addition amount as an example: 78.8 parts of epoxy resin DGEBA is heated at 80°C, after being fully softened, 17.2 parts of 4,4-diaminodiphenyl methane (DDM) is added, and fast stirring is promoted to facilitate the dissolution of DDM; after most of the DDM is dissolved, 4 parts of THMP-DEP (prepared in Example 13) is added, and stirring is continued for 1 min to form a uniform mixture; the mixture is poured into a mold preheated at 80°C while hot, and after standing for 10 min, the temperature is raised to 120°C for pre-curing for 2 h, and then the temperature is raised to 170°C for curing for 4 h. Natural cooling to room temperature, to obtain an EP / THMP-DEP composite material with an addition amount of 4wt%. The thickness of the sample is 3.2mm.

[0297] The vertical burning (UL94) test results of the EP / THMP-DEP composite material are shown in Table 5.

[0298] Table 5 Vertical burning (UL94) test results of EP / THMP-DEP composite material

[0299] As can be seen from Table 5, THMP-DEP shows extremely high flame-retardant performance in epoxy resin, and only 5wt% addition amount can pass the UL94 test, and 4wt% addition amount can also reach V1 level.

[0300] Application Example 3

[0301] Application of phenyl diethyl phosphite (PDEP, Example 1) in polyurethane foam:

[0302] Sample preparation: The catalyst, polyether, flame retardant, water, blowing agent, amine catalyst, silicone oil are added into a 200mL beaker according to the ingredient table 5 in order, pre-mixed by stirring for 60s, then MDI is added and stirred for 10s, and then the mixture is poured into a mold. Room temperature curing for 20h. Finally, the sample is cut into corresponding shape as needed for testing.

[0303] Table 6 Ingredient table of application example 3

[0304] The obtained samples are subjected to limiting oxygen index (LOI) test and bending test, and the results are shown in Table 7.

[0305] Table 7 Limiting oxygen index (LOI) test and bending test results of samples

[0306] From Table 7, it can be seen that in the limiting oxygen index (LOI) test, the oxygen index of phenyl diethyl phosphite is close to that of the general flame retardant tris (2-chloropropyl) phosphate (TCPP); in the bending test, the increase of the TCPP addition amount leads to the decrease of the physical properties of the foam; the increase of the phenyl ester addition amount leads to little decrease of the physical properties. Thus, it can be seen that the performance of phenyl diethyl phosphite is superior to that of the general flame retardant TCPP.

[0307] Application Example 4

[0308] Application of bisphenol A-diethyl phosphite (BPA-DEP, Example 14) in polyurethane foam:

[0309] Sample preparation: the catalyst, polyether, flame retardant, water, blowing agent, amine catalyst, silicone oil are added into a 200 ml beaker according to the ingredient table 7 in sequence, pre-mixed by fast stirring for 60 s, then MDI is added and stirred for 10 s, and then the mixture is poured into a mold. After curing at room temperature for 20 h, the sample is cut into a corresponding shape according to the need for testing.

[0310] Table 8 Ingredient table of raw materials of application example 4

[0311] The obtained samples are subjected to limiting oxygen index (LOI) test and bending and compression test, and the results are shown in Table 9.

[0312] Table 9 Limiting oxygen index (LOI) test and bending and compression test results of samples

[0313] From Table 9, it can be seen that in the limiting oxygen index (LOI) test, the results of BPA-DEP are close to those of TCPP; in the bending and compression test, BPA-DEP is used in polyurethane foam, the bending performance of the sample is close to that of the pure sample, and with the increase of the addition amount, the bending and compression performance changes little. Overall, bisphenol A-diethyl phosphite has good flame retardant performance in polyurethane foam, and has little effect on the physical properties of the foam.

[0314] From the above examples, it can be seen that by directly reacting P(O)-OH compounds with carbonate compounds, the desired phosphoric acid esters can be obtained without catalyst and solvent. For example, alkyl phosphoric acid aromatic esters, hydroxy phosphoric acid esters, etc. can be obtained simply and quickly, with high efficiency, less by-products, low process requirements and little pollution.

[0315] The phosphate ester obtained by the preparation method has good flame retardant performance and high application value. For example, trimethylolpropane-diethyl phosphite in epoxy resin only needs 5wt% dosage to pass the flame retardant test; bisphenol A-diethyl phosphite in TPU only needs 5wt% to pass the UL94@1.6mm test; diethyl phosphite phenyl ester and bisphenol A-diethyl phosphite have good flame retardant and mechanical performance in polyurethane foam.

[0316] The above description of the examples is only to help understand the method of the present application and its core idea. Various modifications of the 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 the 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 shown in formula (IV): wherein R 20 Selected from C1 to C 18 Alkyl group, or at least one substituent substituted C1-C2 18 Alkyl groups, C6-C 24 The aromatic group or at least one substituent substituted C6-C 24 The aromatic group; the substituent is selected from C1 to C2. 18 Alkyl groups, C6-C 24 Aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy groups, C1-C 18 ether group, C1-C 18 The thioether group or the mercapto group; R 1a , R 2b are independently selected from R 20 , 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 at least one of 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.

2. The phosphate ester according to claim 1, characterized in that, R 20 is selected from methyl, ethyl, propyl, isopropyl, isobutyl, phenyl, benzyl or 4-methylphenyl; R 1a , R 2b is independently selected from R 20 , hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hydroxyethyl, hydroxypropyl, benzyl, phenyl or p-methylphenyl.

3. A phosphate ester having the structure shown in formula (V): wherein R 1a , R 2b are independently selected from the group consisting of -(CHR5-CHR6-O-) m R7, 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 is selected from the group consisting of C1-C 18 alkyl, C6-C 24 aromatic group, carbonate group, hydroxyl group, amino group, nitro group, thiol group and heterocycle; R5, R6are independently selected from the group consisting of C1-C 18 alkyl, C6-C 18 aryl or C6-C 24 aryl substituted with at least one substituent selected from the group consisting of C1-C 24 alkyl, C6-C 18 aryl, carbonate, hydroxyl, amino, nitro, halogen, C1-C 24 alkyl, C6-C 18 ester group, C1-C 18 alkoxy groups, C1-C 18 ether group, C1-C 18 One or more of the thioether group and the mercapto group; m is a natural number equal to or greater than 1; R7 is H or a group having the structure shown in formula (VI); R1and R2are independently selected from the group consisting of hydrogen, C1-C 18 alkyl, C1-C 18 alkyl substituted with at least one substituent selected from the group consisting of C1-C 24 aromatic group, or C6-C 24 aromatic group substituted with at least one substituent selected from the group consisting of 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, and when a = b = 0, R1, R2 are both hydrogen atoms or neither is a hydrogen atom.

4. The phosphate ester according to claim 3, characterized in that, R 1a , R 2b is independently selected from the group consisting of -(CHR5-CHR6-O-) m R7, at least one of a hydrogen, 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; R5, R6 are independently selected from one or more of a hydrogen atom, -CH3, -CH2CH3, -CH2OH, phenyl, and -CH2OC(=O)OCH3.

5. The phosphate ester according to any one of claims 1 to 4, characterized in that, The phosphate ester is obtained from P(O)-OH and a carbonate compound by acidolysis reaction; The carbonate compound has a structure as shown in formula (II) or has a structure as shown in formula (III); R3, R4in formula (II) are 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 is 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; In formula (III), R5, R6are independently selected from C1-C 18 alkyl, C1-C 18 alkyl, C6-C 24 aromatic group or C6-C 24 aromatic group substituted with at least one substituent; The substituent is selected from C1 to C2. 18 Alkyl groups, C6-C 24 Aromatic group, carbonate group, hydroxyl group, amino group, nitro group, halogen, C1-C 18 ester group, C1-C 18 alkoxy groups, C1-C 18 ether group, C1-C 18 One or more of the thioether group and the mercapto group.

6. The phosphate ester according to claim 5, characterized in that it is, 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; R5, R6 are independently selected from one or more of a hydrogen atom, -CH3, -CH2CH3, -CH2OH, phenyl, and -CH2OC(=O)OCH3.

7. The phosphate ester according to claim 5, characterized in that, The carbonate compound includes 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), glycerol and alkyl carbonate obtained by transesterification, glycerol and diaryl ester obtained by transesterification.

8. The phosphate ester of claim 5, wherein, The P(O)-OH has a general structural formula 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, R2 are both hydrogen atoms or neither is a hydrogen atom.

9. The phosphate ester of claim 5, wherein, R1, 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, or a p-methylphenyl group.

10. The phosphate ester of claim 5, wherein, R1, 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, or a p-methylphenyl group; and at least one of a and b is 0.

11. The phosphate ester of claim 5, wherein, R1, R2 are independently selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a benzyl group, a phenyl group, or a p-methylphenyl group; and a = b = 0.

12. The phosphate ester of claim 5, wherein, The P(O)-OH compounds include at least one of phosphoric acid, diphenyl phosphorochloridate, dimethyl phosphorochloridate, diethyl phosphorochloridate, methyl phosphorochloridate, ethyl phosphorochloridate, propyl phosphorochloridate, benzyl phosphorochloridate, phenyl phosphorochloridate, phenyl phosphorochloridate monophenyl ester, phenyl phosphorochloridate monomethyl ester, phenyl phosphorochloridate monoethyl ester, methyl phosphorochloridate monophenyl ester, methyl phosphorochloridate monomethyl ester, methyl phosphorochloridate monoethyl ester, dimethyl phosphorochloridite, methyl ethyl phosphorochloridite, diethyl phosphorochloridite, dipropyl phosphorochloridite, diisopropyl phosphorochloridite, ethyl propyl phosphorochloridite, di-n-butyl phosphorochloridite, diisobutyl phosphorochloridite, propyl butyl phosphorochloridite, ethyl butyl phosphorochloridite, methyl phenyl phosphorochloridite, ethyl phenyl phosphorochloridite, dibenzyl phosphorochloridite, di(3-chloropropyl) phosphorochloridite, di(3-bromopropyl) phosphorochloridite, di(2-chloropropyl) phosphorochloridite, di(2-bromopropyl) phosphorochloridite, and diphenyl phosphorochloridite.

13. Use of the phosphoric acid ester according to any one of claims 1 to 12 as a flame retardant.

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