Curable phosphorus-containing compounds and their preparation methods

Abstract

This invention provides a series of novel curable phosphorus-containing compounds with a bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide structure and methods for their preparation. Through a unique dual-reactive-end design on the curable phosphorus-containing compounds, they can undergo crosslinking reactions with other vinyl-containing monomers, thus serving as reactive halogen-free flame retardants. The novel curable phosphorus-containing compounds are represented by general formula (1). General formula (1)

Description

Technical Field

[0001] The present invention provides a series of novel curable phosphorus-containing compounds having a bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide structure, and represented as in general formula (1).

[0002] General formula (1) Background Technology

[0003] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) has long been widely used as an antibacterial agent, antioxidant, colorfastness agent, and flame retardant. DOPO is a halogen-free phosphorus-based flame retardant, and its unique planar structure further enhances its flame-retardant performance. Due to increasing environmental awareness and in line with the trend of increasingly stringent environmental requirements in various countries, halogen-free flame retardants have flourished in the last decade and are gradually replacing halogen-containing flame retardants. The advantages of switching to halogen-free flame retardants also include reducing the serious environmental damage caused by the highly hazardous corrosive gases and highly toxic compounds produced during the combustion of halogen-containing flame retardant materials. In addition to protecting the surface of chemical products and isolating them from external oxygen and heat through a condensed-phase flame-retardant mechanism, phosphorus-based flame retardants can also capture and stabilize high-energy free radicals generated during combustion through a free radical scavenging mechanism to achieve a flame-retardant effect.

[0004] However, to achieve a certain effect, the amount of additive phosphorus-based flame retardants generally needs to reach more than 10% w / w. But with high addition amounts, additive flame retardants may cause compatibility problems after the finished product is made or during subsequent processing, including minor problems such as flame retardant migration to the surface of the product, or even relatively serious problems such as blooming.

[0005] To solve the above problems, it is necessary to increase the compatibility between additive phosphorus-based flame retardants and materials. Processed materials are generally high-molecular-weight compounds, so increasing the molecular weight of DOPO derivatives is one approach. Another approach is to derivatize DOPO to create structures with reactive ends, thus enabling it to function as a reactive flame retardant. By cross-linking the reactive ends of the reactive flame retardant with other reactive groups, the flame-retardant units can be directly linked to the material, thereby solving the problems associated with additive flame retardants. Summary of the Invention

[0006] To achieve the aforementioned objectives, this invention provides a novel curable phosphorus-containing compound having a bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide structure. This novel curable phosphorus-containing compound employs a dual-reactive-end design, which not only increases the molecular weight by approximately two times, thus improving compatibility with materials, but also allows the reactive ends to undergo crosslinking reactions with other crosslinkable monomers or oligomeric resins, further increasing the polymer molecular weight. Furthermore, compared to compounds with only a single reactive end, the dual-reactive-end design also offers the advantage of improved adhesion.

[0007] The curable phosphorus-containing compound of the present invention is represented by general formula (1).

[0008] General formula (1)

[0009] in,

[0010] Each A1 and A2 is independently selected from the group consisting of: hydrogen atom, hydroxyl (-OH), cyano (-CN), halogroup, alkoxy (-OR), alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl and aralkyl;

[0011] Each R1 and R2 is independently selected from the group consisting of: hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, heteroaryl groups, and aralkyl groups;

[0012] X represents a single bond, (CH2)n, CR3R4, C=O, or SO2, where R3 and R4 are selected from the group consisting of: hydrogen atom, fluorine atom, fluorinated alkyl, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl, and aralkyl, and n is an integer from 1 to 12.

[0013] Each Y represents an independent value. Where * represents the bonding position; and

[0014] Each Z represents an independent representation. or , where * represents the bonding position.

[0015] In one embodiment, the curable phosphorus-containing compound of the present invention is selected from one of the following:

[0016] .

[0017] In one embodiment, the curable phosphorus-containing compound of the present invention is selected from one of the following:

[0018] .

[0019] This invention also provides a method for preparing a curable phosphorus-containing compound having a bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide structure, comprising:

[0020] (1) A nucleophilic addition reaction is carried out between bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide and an aldehyde or ketone compound in the presence of a solvent to give a diol intermediate; and

[0021] (2) The diol intermediate is subjected to an esterification reaction with an acylation reagent, a solvent, and a catalyst or an acidifier.

[0022] Steps (1) and (2) above are represented by general formula (2):

[0023]

[0024] General formula (2)

[0025] in,

[0026] Each A1 and A2 is independently selected from the group consisting of: hydrogen atom, hydroxyl, cyano, halogen, alkoxy, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl and aralkyl;

[0027] Each R1 and R2 is independently selected from the group consisting of: hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, heteroaryl groups, and aralkyl groups;

[0028] X represents a single bond, (CH2)n, CR3R4, C=O, or SO2, where R3 and R4 are selected from the group consisting of: hydrogen atom, fluorine atom, fluorinated alkyl, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl, and aralkyl, and n is an integer from 1 to 12.

[0029] Each Y represents an independent value. Where * represents the bonding position;

[0030] Each Z represents an independent representation. or Where * represents the bonding position;

[0031] R5 represents a hydrogen atom or a methyl group; and

[0032] R6 represents a chlorine atom, an acryloxy group, or a methacryloyloxy group.

[0033] In one embodiment, in the nucleophilic addition reaction of step (1), the equivalence ratio of bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide to the aldehyde or ketone compound is 1:2 to 1:10.

[0034] In one embodiment, the nucleophilic addition reaction in step (1) is carried out by a mixture comprising the bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, the aldehyde or ketone compound and the solvent at 20 to 200 °C.

[0035] In one embodiment, the solvent in the nucleophilic addition reaction of step (1) is selected from the group consisting of: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, ethyl acetate, butyl acetate, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and combinations thereof.

[0036] In one embodiment, the solvent is present in a weight percentage of 1:0.1 to 1:20 with respect to the bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide.

[0037] In one embodiment, in the esterification reaction of step (2), the equivalent ratio of the diol intermediate to the acylation agent is 1:2 to 1:10.

[0038] In one embodiment, the esterification reaction in step (2) is carried out by mixing the alcohol intermediate with the acylation agent, the solvent and the catalyst or acidifier at -20 to 150°C.

[0039] In one embodiment, the catalyst or acid-neutralizing agent in the esterification reaction of step (2) is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine (DABCO), pyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, 4-N,N'-dimethylpyridine (DMAP), and combinations thereof.

[0040] In one embodiment, the catalyst or acidifier is present in a weight percentage of 0:1 to 5:1 with respect to the diol intermediate.

[0041] In one embodiment, the solvent is present in a weight percentage of 1:0.1 to 1:2 with respect to the bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide. Attached Figure Description

[0042] Figure 1 The image shows the H-NMR spectrum of the curable phosphorus-containing compound of Example 1 of this invention.

[0043] Figure 2 The image shows the H-NMR spectrum of the curable phosphorus-containing compound of Example 2 of this invention.

[0044] Figure 3 This is the FT-IR spectrum of the curable phosphorus-containing compound of Example 2 of the present invention. Detailed Implementation

[0045] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand the advantages and effects of the present invention from the content described in this specification. The present invention can also be implemented or applied through other different embodiments, and the details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit described in the present invention.

[0046] This invention provides a curable phosphorus-containing compound as shown in general formula (1).

[0047] General formula (1)

[0048] in,

[0049] Each A1 and A2 is independently selected from the group consisting of: hydrogen atom, hydroxyl (-OH), cyano (-CN), halogroup, alkoxy (-OR), alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl and aralkyl;

[0050] Each R1 and R2 is independently selected from the group consisting of: hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, heteroaryl groups, and aralkyl groups;

[0051] X represents a single bond, (CH2)n, CR3R4, C=O, or SO2, where R3 and R4 are selected from the group consisting of: hydrogen atom, fluorine atom, fluorinated alkyl, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl, and aralkyl, and n is an integer from 1 to 12.

[0052] Each Y represents an independent value. Where * represents the bonding position; and

[0053] Each Z represents an independent representation. or , where * represents the bonding position.

[0054] In one embodiment, each A1, A2, R1, R2 in the general formula (1) is a hydrogen atom, X is CH2, and Y is... Z is For example, the compounds of the present invention represented by general formula (1) have the structure of formula (A-1):

[0055] Equation (A-1).

[0056] In one embodiment, each A1, A2, R1, R2 in the general formula (1) is a hydrogen atom, X is C(CH3)2, and Y is... Z is For example, the compounds of the present invention represented by general formula (1) have the structure of formula (A-2):

[0057] Equation (A-2).

[0058] In one embodiment, each A1, A2, R1, and R2 in the general formula (1) is a hydrogen atom, X is C(CH2)5, and Y is... Z is For example, the compounds of the present invention represented by general formula (1) have the structure of formula (A-3):

[0059] Equation (A-3).

[0060] In one embodiment, each A1, A2, R1, and R2 in the general formula (1) is a hydrogen atom, X is SO2, and Y is... Z is For example, the compounds of the present invention represented by general formula (1) have the structure of formula (A-4):

[0061] Equation (A-4).

[0062] In one embodiment, each A1, A2, R1, and R2 in the general formula (1) is a hydrogen atom, X is a single bond, and Y is a hydrogen atom. Z is For example, the compounds of the present invention represented by general formula (1) have the structure of formula (A-5):

[0063] Equation (A-5).

[0064] The present invention also provides a novel method for preparing a curable phosphorus-containing compound having a bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide structure, comprising: (1) subjecting bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide to a first-step nucleophilic addition reaction with an aldehyde or ketone compound in the presence of a solvent to obtain a diol intermediate; and (2) subjecting the diol intermediate to a second-step esterification reaction with an acylation reagent, a solvent and a catalyst (or an acidifier), wherein the specific synthetic reaction formulas of the above steps (1) and (2) are represented by general formula (2);

[0065]

[0066] General formula (2)

[0067] in,

[0068] Each A1 and A2 is independently selected from the group consisting of: hydrogen atom, hydroxyl (-OH), cyano (-CN), halogroup, alkoxy (-OR), alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl and aralkyl;

[0069] Each R1 and R2 is independently selected from the group consisting of: hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, heteroaryl groups, and aralkyl groups;

[0070] X represents a single bond, (CH2)n, CR3R4, C=O, or SO2, wherein R3 and R4 are selected from the group consisting of: hydrogen atom, fluorine atom, fluorinated alkyl, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl, and aralkyl.

[0071] Each Y represents an independent value. Where * represents the bonding position;

[0072] Each Z represents an independent representation. or Where * represents the bonding position;

[0073] R5 represents a hydrogen atom or a methyl group; and

[0074] R6 represents a chlorine atom, an acryloxy group, or a methacryloyloxy group.

[0075] In one embodiment, each A1 and A2 is a hydrogen atom and each R1 and R2 is a hydrogen atom.

[0076] In one embodiment, in the nucleophilic addition reaction of step (1), the equivalence ratio of bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide to the aldehyde or ketone compound is 1:2 to 1:10.

[0077] In one embodiment, the nucleophilic addition reaction in step (1) is carried out at a reaction temperature of 20 to 200 °C, comprising a mixture of bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide and an aldehyde or ketone compound.

[0078] In one embodiment, in the nucleophilic addition reaction of step (1), the solvent and the weight percentage of bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide is 1:0.1 to 1:20.

[0079] In one embodiment, the solvent in the nucleophilic addition reaction of step (1) is an organic solvent.

[0080] In one embodiment, in the nucleophilic addition reaction of step (1), the solvent is preferably an aprotic solvent.

[0081] In one embodiment, the aprotic solvent in step (1) is selected from dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, ethyl acetate, butyl acetate, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, acetonitrile, N, N'-dimethylformamide, N, N'-dimethylacetamide, 1-Methyl-2-pyrrolidone, dimethyl sulfoxide, and combinations thereof.

[0082] In one embodiment, in the esterification reaction of step (2), the equivalence ratio of the diol intermediate to the acylation agent (or alkylation agent) is 1:2 to 1:20.

[0083] In one embodiment, the esterification reaction in step (2) is carried out at a reaction temperature of -20 to 150°C, comprising a diol intermediate and an acylation agent (or an alkylation agent).

[0084] In one embodiment, in the esterification reaction of step (2), the weight percentage of the diol intermediate to the solvent is 1:0.1 to 1:20.

[0085] In one embodiment, the solvent in the esterification reaction of step (2) is an organic solvent.

[0086] In one embodiment, the solvent in the esterification reaction of step (2) is preferably an aprotic solvent.

[0087] In one embodiment, the aprotic solvent in step (2) is selected from dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, ethyl acetate, butyl acetate, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and combinations thereof.

[0088] In one embodiment, in the esterification reaction of step (2), the weight percentage of catalyst (or acidifier) ​​to diol intermediate is 0:1 to 5:1.

[0089] In one embodiment, in the esterification reaction of step (2), the catalyst (or acidifier) ​​is an inorganic base, an organic base, or both.

[0090] In one embodiment, in the esterification reaction of step (2), preferably, the inorganic base compound is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate.

[0091] In one embodiment, in the esterification reaction of step (2), preferably, the organic base compound is selected from the group consisting of ammonia, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso-butylamine, triethylamine, tri-n-propylamine, tri-n-buylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), pyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, and 4-N,N'-dimethylpyridine (DMAP).

[0092] Example 1

[0093] Synthesis of (methylenebis(6-oxidodibenzo[c,e][1,2]oxaphosphinine-2,6-diyl))bis(methylene)bis(2-methylacrylate), DI-DOPO-ME-MA, A1)

[0094]

[0095] 40 g of 2,2'-methylene-bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, 160 g of DMAC, and 6 g of polyoxymethylene were mixed in a reaction flask and heated to 70-80 °C for 20 hours. After the reaction was completed, 160 g of water was slowly added dropwise. After cooling to room temperature, the solid was collected by filtration, washed twice with water, and dried under vacuum to obtain 40 g of a grayish-white solid, the crude diol intermediate DI-DOPO-ME-FA, which was directly used for the next esterification reaction without purification.

[0096] 40 g of crude diol intermediate, 1.0 g of DMAP, 0.08 g of polymerization inhibitor HQ, and 40 g of DMF were mixed in a reaction flask and heated to 80-90 °C. 30.6 g of methacrylic anhydride was slowly added dropwise, and the reaction was maintained at this temperature for 8 hours after the addition was complete. The mixture was then cooled to room temperature, and the DMF was recovered under reduced pressure. 200 g of ethyl acetate was added for dilution, and the organic layer was washed several times with a 5% sodium bicarbonate aqueous solution. After separating the organic layer, the solvent was removed under vacuum to obtain 39.2 g of a grayish-white solid product. The two-step yield was approximately 68%. The product, after separation by diatomaceous earth column chromatography, yielded an analytical grade sample with a melting point of 103-105 °C. o C.

[0097] 1 H-NMR (DMSO-d6, 600 MHz) δ: 1.39 (6H, s), 4.08 (2H, s), 4.80 (2H,dd), 4.90 (2H, d), 5.23 (2H, m), 5.35 (2H, s), 7.22 (2H, d, J = 8.40 Hz),7.40 (2H, t), 7.65 (2H, td), 7.86 (2H, t), 7.98 (2H, dd), 8.21 (2H, d, J =4.38 Hz), 8.29 (2H, t) ppm

[0098] 31 P-NMR (DMSO-d6, 243 MHz) δ: 28.70 (s) ppm

[0099] Example 2

[0100] Synthesis of (propane-2,2-diylbis(6-oxidodibenzo[c,e][1,2]oxaphosphinine-2,6-diyl))bis(methylene)bis(2-methylacrylate), DI-DOPO-DM-MA, A2)

[0101]

[0102] 21.7 g of 2,2'-propane-2,2'-yl-bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, 80 g of DMAC, and 3 g of polyoxymethylene were mixed in a reaction flask and heated to 70-80 °C for 20 hours. After the reaction was completed, 80 g of water was slowly added dropwise. After cooling to room temperature, the solid was collected by filtration, washed twice with water, and dried under vacuum to obtain 21 g of a grayish-white solid, the crude diol intermediate DI-DOPO-DM-FA, which was directly used for the next esterification reaction without purification.

[0103] 21 g of crude diol intermediate, 0.5 g of DMAP, 0.04 g of polymerization inhibitor HQ, and 21 g of DMF were mixed in a reaction flask. The mixture was heated to 80-90°C, and 15.2 g of methacrylic anhydride was slowly added dropwise. After the addition was complete, the reaction was maintained at this temperature for 8 hours. The mixture was then cooled to room temperature, and the DMF was recovered under reduced pressure. 105 g of ethyl acetate was added for dilution. The organic layer was washed several times with a 5% sodium bicarbonate aqueous solution. After separating the organic layer, the solvent was removed under vacuum to obtain 18.9 g of a grayish-white solid product. The two-step yield was approximately 65%. The product could be separated into analytical grade samples by diatomaceous earth column chromatography, with a melting point of 92-95°C. o C.

[0104] 1 H-NMR (DMSO-d6, 600 MHz) δ: 1.45 (6H, s), 1.81 (6H, s), 4.82 (2H,dd), 4.92 (2H, d), 5.36 (2H, s), 5.39 (2H, s), 7.20 (2H, d, J = 8.58 Hz),7.29 (2H, m), 7.64 (2H, td, J = 7.62, 2.88 Hz), 7.84 (2H, t, J = 7.86 Hz),7.99 (2H, dd), 8.06 (2H, t, J = 2.1 Hz), 8.29 (2H, dd, J = 8.34, 5.1 Hz) ppm

[0105] 31 P-NMR (DMSO-d6, 243 MHz) δ: 28.86 (s) ppm

[0106] Example 3

[0107] Synthesis of (cyclohexane-1,1-diylbis(6-oxidodibenzo[c,e][1,2]oxaphosphinine-2,6-diyl))bis(methylene)bis(2-methylacrylate), DI-DOPO-CH-MA, A3)

[0108]

[0109] 23.1 g of 2,2'-cyclohexane-1,1'-yl-bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, 80 g of DMAC, and 3 g of polyoxymethylene were mixed in a reaction flask and heated to 70-80 °C for 20 hours. After the reaction was completed, 80 g of water was slowly added dropwise. After cooling to room temperature, the solid was collected by filtration, washed twice with water, and dried under vacuum to obtain 22 g of crude diol intermediate DI-DOPO-CH-FA, a grayish-white solid. This crude product was directly used for the next esterification reaction without purification.

[0110] 22 g of crude diol intermediate, 0.48 g of DMAP, 0.039 g of polymerization inhibitor HQ, and 22 g of DMF were mixed in a reaction flask and heated to 80-90 °C. 14.8 g of methacrylic anhydride was slowly added dropwise, and the reaction was maintained at this temperature for 8 hours after the addition was complete. The mixture was then cooled to room temperature, and the DMF was recovered under reduced pressure. 110 g of ethyl acetate was added for dilution, and the organic layer was washed several times with a 5% sodium bicarbonate aqueous solution. After separating the organic layer, the solvent was removed under vacuum to obtain 19.0 g of a grayish-white solid product. The two-step yield was approximately 59.5%. The product could be separated into analytical grade samples by diatomaceous earth column chromatography.

[0111] 1H-NMR (DMSO-d6, 600 MHz) δ: 1.36 (3H, s), 1.37 (3H, s), 1.40~1.60(6H, m), 2.40~2.60 (4H, m), 4.79 (2H, dd), 4.90 (2H, m), 5.20 (2H, m), 5.31(2H, d), 7.19 (2H, dd, J = 8.58, 1.8 Hz), 7.47 (2H, t, J = 8.22 Hz), 7.63(2H, m), 7.85 (2H, t, J = 7.8 Hz), 7.97 (2H, dd), 8.13 (2H, dd, J = 7.68,2.34 Hz), 8.36 (2H, t) ppm

[0112] 31 P-NMR (DMSO-d6, 243 MHz) δ: 28.89 (s) ppm

[0113] Example 4

[0114] Synthesis of (sulfonylbis(6-oxidodibenzo[c,e][1,2]oxaphosphinine-2,6-diyl))bis(methylene)bis(2-methylacrylate), DI-DOPO-SF-MA, A4)

[0115]

[0116] 22.3 g of 2,2'-sulfonyl-bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, 80 g of DMAC, and 3 g of polyoxymethylene were mixed in a reaction flask and heated to 70-80 °C for 20 hours. After the reaction was completed, 80 g of water was slowly added dropwise. After cooling to room temperature, the solid was collected by filtration, washed twice with water, and dried under vacuum to obtain 20.7 g of the crude diol intermediate DI-DOPO-SF-FA, a grayish-white solid. This product was directly used for the next esterification reaction without purification.

[0117] 20.7 g of crude diol intermediate, 0.47 g of DMAP, 0.038 g of polymerization inhibitor HQ, and 20.7 g of DMF were mixed in a reaction flask and heated to 80-90 °C. 14.4 g of methacrylic anhydride was slowly added dropwise, and the reaction was maintained at this temperature for 8 hours after the addition was complete. The mixture was then cooled to room temperature, and the DMF was recovered under reduced pressure. 103.5 g of ethyl acetate was added for dilution, and the organic layer was washed several times with a 5% sodium bicarbonate aqueous solution. After separating the organic layer, the solvent was removed under vacuum to obtain 17.1 g of a grayish-white solid product. The two-step yield was approximately 55%. The product could be separated into analytical grade samples by diatomaceous earth column chromatography.

[0118] 31 P-NMR (DMSO-d6, 243 MHz) δ: 28.65 (s) ppm

[0119] Example 5

[0120] Synthesis of (6,6'-dioxido-[2,2'-bidibenzo[c,e][1,2]oxaphosphinine]-6,6'-diyl)bis(methylene)bis(2-methylacrylate), DI-DOPO-MA, A5)

[0121]

[0122] 19.8 g of 2,2'-bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, 80 g of DMAC, and 3 g of polyoxymethylene were mixed in a reaction flask and heated to 70-80 °C for 20 hours. After the reaction was completed, 80 g of water was slowly added dropwise. After cooling to room temperature, the solid was collected by filtration, washed twice with water, and dried under vacuum to obtain 17.9 g of crude diol intermediate DI-DOPO-FA, a grayish-white solid. This product was directly used for the next esterification reaction without purification.

[0123] 17.9 g of crude diol intermediate, 0.46 g of DMAP, 0.037 g of polymerization inhibitor HQ, and 18 g of DMF were mixed in a reaction flask and heated to 80-90 °C. 14.1 g of methacrylic anhydride was slowly added dropwise, and the reaction was maintained at this temperature for 8 hours after the addition was complete. The mixture was then cooled to room temperature, and the DMF was recovered under reduced pressure. 105 g of ethyl acetate was added for dilution, and the organic layer was washed several times with a 5% sodium bicarbonate aqueous solution. After separating the organic layer, the solvent was removed under vacuum to obtain 14.4 g of a grayish-white solid product. The two-step yield was approximately 50%. The product could be separated into analytical grade samples by diatomaceous earth column chromatography.

[0124] 31 P-NMR (DMSO-d6, 243 MHz) δ: 28.75 (s) ppm

[0125] Example 6

[0126] The conditions were the same as in Example 1, except that DMAC was replaced with an equal amount of chlorobenzene, 1.0 g DMAP was replaced with 15.7 g pyridine, the temperature was lowered to 5 to 10 °C, and 20.7 g of methacrylamide chloride was added dropwise. Finally, 43.24 g of a white solid was obtained, with a yield of 75%.

[0127] Example 7

[0128] The conditions of Example 2 were the same, except that DMAC was replaced with an equal amount of chlorobenzene, 0.5 g DMAP was replaced with 7.8 g pyridine, the temperature was lowered to 5 to 10 °C, and 10.3 g of methacryloyl chloride was added dropwise. Finally, 20.94 g of an off-white solid was obtained, with a yield of 72%.

[0129] Example 8

[0130] The conditions of Example 3 were the same, except that DMAC was replaced with an equal amount of chlorobenzene, 0.48 g DMAP was replaced with 7.6 g pyridine, the temperature was lowered to 5 to 10 °C, and 10 g of methacrylamide chloride was added dropwise. Finally, 20.44 g of a white solid was obtained, with a yield of 64%.

[0131] Example 9

[0132] The conditions of Example 4 were the same, except that DMAC was replaced with an equal amount of chlorobenzene, 0.47 g DMAP was replaced with 7.4 g pyridine, the temperature was lowered to 5 to 10 °C, and 9.76 g of methacrylamide chloride was added dropwise. Finally, 20.94 g of a white solid was obtained, with a yield of 72%.

[0133] Example 10

[0134] The conditions of Example 5 were the same, except that DMAC was replaced with an equal amount of chlorobenzene, 0.46 g DMAP was replaced with 7.22 g pyridine, the temperature was lowered to 5 to 10 °C, and 9.56 g of methacrylamide chloride was added dropwise. Finally, 15.26 g of a white solid was obtained, with a yield of 53%.

[0135] Example 11

[0136] The conditions of Example 6 were followed, except that 17.9 g of acryloyl chloride was added dropwise. Ultimately, 38.5 g of a white solid was obtained, with a yield of 70%.

[0137] Example 12

[0138] The conditions of Example 7 were followed, except that 8.9 g of acryloyl chloride was added dropwise. Ultimately, 18.8 g of a white solid was obtained, with a yield of 68%.

[0139] Example 13

[0140] The conditions of Example 8 were followed, except that 8.7 g of acryloyl chloride was added dropwise. Ultimately, 18.3 g of a white solid was obtained, with a yield of 60%.

[0141] Example 14

[0142] The conditions of Example 9 were followed, except that 8.45 g of acryloyl chloride was added dropwise. Ultimately, 17.2 g of a white solid was obtained, with a yield of 62%.

[0143] Example 15

[0144] The conditions of Example 10 differed only in that 8.3 g of acryloyl chloride was added dropwise. Ultimately, 15.1 g of a white solid was obtained, with a yield of 55%.

Claims

1. A curable phosphorus-containing compound having a bis-6H-dibenzo[c,e][1,2]oxophosphorushexane-6-oxide structure, represented by general formula (1), General formula (1) in, Each A1 and A2 is independently selected from the group consisting of: hydrogen atom, hydroxyl, cyano, halogen, alkoxy, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl and aralkyl; Each R1 and R2 is independently selected from the group consisting of: hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, heteroaryl groups, and aralkyl groups; X represents a single bond, (CH2)n, CR3R4, C=O, or SO2, where R3 and R4 are selected from the group consisting of: hydrogen atom, fluorine atom, fluorinated alkyl, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl, and aralkyl, and n is an integer from 1 to 12. Each Y represents an independent value. Where * represents the bonding position; and Each Z represents an independent representation. or , where * represents the bonding position.

2. The curable phosphorus-containing compound according to claim 1, characterized in that... The curable phosphorus-containing compound is selected from one of the following: 。 3. The curable phosphorus-containing compound according to claim 1, characterized in that... The curable phosphorus-containing compound is selected from one of the following: 。 4. A method for preparing a curable phosphorus-containing compound having a bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide structure, comprising: (1) A nucleophilic addition reaction is carried out between bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide and an aldehyde or ketone compound in the presence of a solvent to give a diol intermediate; and (2) The diol intermediate is subjected to an esterification reaction with an acylation reagent, a solvent, and a catalyst or an acidifier. Steps (1) and (2) above are represented by general formula (2): General formula (2) in, Each A1 and A2 is independently selected from the group consisting of: hydrogen atom, hydroxyl, cyano, halogen, alkoxy, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl and aralkyl; Each R1 and R2 is independently selected from the group consisting of: hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, heteroaryl groups, and aralkyl groups; X represents a single bond, (CH2)n, CR3R4, C=O, or SO2, where R3 and R4 are selected from the group consisting of: hydrogen atom, fluorine atom, fluorinated alkyl, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aryl, heteroaryl, and aralkyl, and n is an integer from 1 to 12. Each Y represents an independent value. Where * represents the bonding position; Each Z represents an independent representation. or Where * represents the bonding position; R5 represents a hydrogen atom or a methyl group; and R6 represents a chlorine atom, an acryloxy group, or a methacryloyloxy group.

5. The preparation method according to claim 4, characterized in that, In the nucleophilic addition reaction of step (1), the equivalence ratio of bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide to the aldehyde or ketone compound is 1:2 to 1:

10.

6. The preparation method according to claim 4, characterized in that, The nucleophilic addition reaction in step (1) is carried out at 20 to 200°C by mixing a mixture containing the bis-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane-6-oxide, the aldehyde or ketone compound, and the solvent.

7. The preparation method according to claim 4, characterized in that, The solvent in the nucleophilic addition reaction of step (1) is selected from the group consisting of: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, ethyl acetate, butyl acetate, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and combinations thereof.

8. The preparation method according to claim 7, characterized in that, The solvent and the bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide have a weight percentage of 1:0.1 to 1:

20.

9. The preparation method according to claim 4, characterized in that, In the esterification reaction of step (2), the equivalent ratio of the diol intermediate to the acylation reagent is 1:2 to 1:

10.

10. The preparation method according to claim 4, characterized in that, The esterification reaction in step (2) is carried out at -20 to 150°C in a mixture containing the alcohol intermediate, the acylation agent, the solvent, and the catalyst or acidifier.

11. The preparation method according to claim 4, characterized in that, The catalyst or acid-neutralizing agent in the esterification reaction of step (2) is selected from the group consisting of: lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, pyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, 4-N,N'-dimethylpyridine and combinations thereof.

12. The preparation method according to claim 11, characterized in that, The weight percentage of the catalyst or acidifier to the diol intermediate is 0:1 to 5:

1.

13. The preparation method according to claim 4, characterized in that, The solvent used in the esterification reaction of step (2) is selected from the group consisting of: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, ethyl acetate, butyl acetate, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and combinations thereof.

14. The preparation method according to claim 13, characterized in that, The weight percentage of the solvent to the bis-6H-dibenzo[c,e][1,2]oxophosphanecyclohexane-6-oxide is 1:0.1 to 1:2.

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