CN111116663A - Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof - Google Patents
Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof Download PDFInfo
- Publication number
- CN111116663A CN111116663A CN201911265070.9A CN201911265070A CN111116663A CN 111116663 A CN111116663 A CN 111116663A CN 201911265070 A CN201911265070 A CN 201911265070A CN 111116663 A CN111116663 A CN 111116663A
- Authority
- CN
- China
- Prior art keywords
- flame
- aromatic
- curing agent
- retardant
- phenylenediamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65814—Cyclic phosphazenes [P=N-]n, n>=3 n = 3 or 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
Abstract
The invention belongs to the field of flame-retardant additives of epoxy resin, and discloses a flame-retardant curing agent containing a phosphazene/aromatic imine composite structure and a preparation method thereof. The invention successfully prepares the flame-retardant curing agent with the compound structure of the phosphorus nitrile/aromatic imine, the end of which contains polyfunctional active amino groups, by utilizing the substitution and condensation reaction of hexachlorocyclotriphosphazene with aldehydes containing hydroxyl and aromatic diamines in sequence. The whole preparation process has the characteristics of mild reaction conditions, controllable and adjustable reaction process, high yield and the like, and is suitable for expanded production. The flame-retardant curing agent prepared by the invention can introduce a flame-retardant structure through chemical reactions such as curing crosslinking and the like of the contained active amino group and the matrix epoxy resin and directly participate in forming a polymer network three-dimensional structure, so that the polymer material has excellent flame-retardant performance.
Description
Technical Field
The invention relates to the field of flame retardant processing aids, in particular to a flame retardant curing agent containing a phosphazene and aromatic imine composite structure and a preparation method thereof.
Background
Epoxy resin is a thermosetting material with wide application, has the remarkable characteristics of good cohesiveness, corrosion resistance, strength, stability, heat resistance and the like, and is widely applied to the fields of coatings, adhesives, electronic packaging, aerospace, ship transportation and the like. However, common epoxy resin belongs to flammable materials, the limiting oxygen index is only about 20%, a large amount of black smoke is released during combustion, and other flammable matters can be continuously ignited along with the melting and dripping phenomena, so that uncontrollable potential safety hazards are caused. Therefore, the active development and research on the flame retardant modification of epoxy resin materials have very important theoretical and practical significance for effectively preventing or controlling the material combustion or the fire development. At present, the flame-retardant modification method of epoxy resin is generally to add a proper amount of flame retardant into a matrix. In order to ensure an ideal flame-retardant effect, the traditional flame retardant is usually added with a large amount of flame retardant to improve the proportion of single flame-retardant elements. But the compatibility of the additive flame retardant and epoxy resin is poor, and the introduction of weak chemical bonds can reduce the comprehensive performance of the material.
Disclosure of Invention
The invention aims to provide a flame-retardant curing agent containing a phosphazene and aromatic imine composite structure and a preparation method thereof, and the principle is as follows: taking hexachlorocyclotriphosphazene and aromatic aldehyde containing hydroxyl as raw materials, and carrying out substitution reaction on phenolic hydroxyl and P-Cl of hexachlorocyclotriphosphazene at a certain temperature under the condition of an acid-binding agent to generate an aldehyde-terminated intermediate product with hexafunctionality; further generates an aromatic imine structure with aromatic diamine monomers to obtain the end capping containing a plurality of active amino groups. The flame-retardant structure is introduced into the polymer network through the further curing and crosslinking reaction of the contained active amine group and the matrix epoxy resin, so that the material has excellent flame-retardant performance.
The purpose of the invention is realized by the following technical scheme:
a flame-retardant curing agent containing a phosphazene/aromatic imine composite structure is composed of cyclotriphosphazene, aromatic imine and active amino, and the structural formula of the flame-retardant curing agent is as follows:
wherein R is1Is an aromatic ether, or one or more hydrogen atoms on the benzene ring of the aromatic ether are substituted by alkoxy, oxygen atom, amino or nitro, wherein R1The O atom in (1) is connected with the P atom; r2Is an aromatic hydrocarbon, or one or more hydrogen atoms on the benzene ring of the aromatic hydrocarbon are substituted by an alkoxy group, an oxygen atom, an amino group or a nitro group.
Preferably, said R is1Is any one of the following structures (wherein R is1Wherein the O atom and the P atom are bonded):
preferably, said R is2Is any one of the following structures:
preferably, the preparation method of the flame retardant curing agent comprises the following steps:
(1) adding hexachlorocyclotriphosphazene and a solvent into a reactor under the protection of inert gas (nitrogen or argon), then adding aromatic aldehyde containing hydroxyl and an acid-binding agent, and stirring and reacting for 8-60 hours at 30-100 ℃ to obtain a reaction solution; purifying to obtain an intermediate product;
(2) dissolving the intermediate product in a solvent, adding the dissolved intermediate product into an aromatic diamine solution, and stirring and reacting for 0.5-24 hours at the temperature of 30-100 ℃; purifying to obtain the target product.
Preferably, the ratio of hexachlorocyclotriphosphazene to solvent in step (1) is 1 g: 0.5-10 ml; the molar ratio of the aromatic aldehyde to the hexachlorocyclotriphosphazene is 6-10: 1; the mole ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is 6-10: 1.
preferably, the ratio of the intermediate product to the solvent in step (2) is 1 g: 0.5-10 ml; the molar ratio of the aromatic diamine to the intermediate product is 10-20: 1.
preferably, the reaction temperature in the step (1) is 65-90 ℃, and the reaction time is 12-48 h; in the step (2), the reaction temperature is 60-85 ℃, and the reaction time is 6-24 h.
Preferably, the aromatic aldehyde containing hydroxyl groups is any one or more of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, o-hydroxybenzaldehyde (salicylaldehyde), 4-hydroxy-2-methyl-benzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, ethyl vanillin, syringaldehyde, vanillin, 4-hydroxy-3, 5-dimethylbenzaldehyde, 3-methylsalicylaldehyde, 3-tert-butylsalicylaldehyde, 3-methoxysalicylaldehyde, 4, 6-dimethoxysalicylaldehyde, 3-ethoxysalicylaldehyde, 4-diethylaminosalicylaldehyde, 2-hydroxy-3-nitrobenzaldehyde, and 2-hydroxynaphthaldehyde.
Preferably, the solvent is any one or more of methanol, ethanol, isopropanol, acetone, butanone, toluene, xylene, chlorobenzene, dichlorobenzene, methyl acetate, propyl acetate, ethyl acetate, dichloromethane, dichloroethane, chloroform, dioxane, tetrahydrofuran and dimethyl sulfoxide.
Preferably, the acid-binding agent is one or more of triethylamine, ethylenediamine, pyridine, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, imidazole, N-diisopropylethylamine, triethanolamine, tetrabutylammonium bromide, sodium acetate, dipotassium hydrogen phosphate, potassium carbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, the aromatic diamine is any one or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2, 3-diaminotoluene, 2, 6-diaminotoluene, 2,4, 6-trimethyl-1, 3-phenylenediamine, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 2, 3-diaminopyridine, 2-nitro-1, 4-phenylenediamine, N-methyl-1, 2-phenylenediamine, 3,4' -diaminodiphenyl ether, 1, 8-diaminonaphthalene, 2, 7-diaminofluorene, 2, 6-diaminoanthraquinone, and 9, 10-diaminophenanthrene.
The invention successfully prepares the flame-retardant curing agent containing the phosphazene/aromatic imine composite structure with the end containing the polyfunctional active amino group by utilizing the substitution and addition reaction of hexachlorocyclotriphosphazene with the aldehyde containing hydroxyl and the aromatic diamine in sequence. The flame-retardant curing agent prepared by the invention can introduce a flame-retardant structure through chemical reactions such as curing crosslinking and the like of the contained active amino group and the matrix epoxy resin and directly participate in forming a polymer network three-dimensional structure, so that the polymer material has excellent flame-retardant performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention synthesizes a reactive flame retardant curing agent containing a cyclotriphosphazene and aromatic imine composite structure, and an active amino group can participate in the crosslinking curing reaction of epoxy resin to introduce a flame retardant structure into a polymer network, so that the polymer material has excellent intrinsic flame retardant property.
(2) The flame-retardant curing agent structure has high flame-retardant element (phosphorus and nitrogen) content and P-N synergistic function, and the dosage of the flame-retardant curing agent required when the same flame-retardant effect is achieved is greatly reduced compared with that of the traditional reaction type flame retardant.
(3) The whole preparation process has the advantages of mild reaction conditions, controllable and adjustable reaction process, high yield and the like, and is suitable for expanded production.
Drawings
FIG. 1 shows the product obtained in example 11H-NMR spectrum.
FIG. 2 shows the product obtained in example 131P-NMR spectrum.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The preparation steps of the intermediate product are as follows: 130g of p-hydroxybenzaldehyde, 100g of triethylamine, 54g of hexachlorocyclotriphosphazene and 300mL of 1, 4-dioxane are added into a 1L three-neck round-bottom flask with magnetic stirring, a condensation reflux device, a constant-pressure dropping funnel and nitrogen protection, the temperature is raised to 90 ℃ after complete dissolution, the reaction is continued for 12 hours, and the reaction is cooled to room temperature. Then pouring the mixture into 1L of deionized water for precipitation after filtration and rotary evaporation concentration, stirring the mixture for 1 hour at room temperature, filtering the mixture, washing the mixture for multiple times by using 300ml of ethanol, and drying the mixture in vacuum to obtain a crude product. Purification by recrystallization from ethyl acetate gave 116.2g of intermediate product in 90.3% yield.
The preparation method of the flame-retardant curing agent comprises the following steps: 75g of p-phenylenediamine and 100mL of 1, 4-dioxane are added into a 500mL three-neck round-bottom flask with a magnetic stirring device, a condensation reflux device and a constant pressure dropping funnel, the temperature is raised to 85 ℃, after the p-phenylenediamine and the 1, 4-dioxane are completely dissolved, 50mL of 1, 4-dioxane solution containing 10g of intermediate product (11.6mmol) is added within 1 hour, the reaction is continued for 12 hours, the reaction system is cooled to room temperature, and the reaction system is changed from clear to turbid. Then directly filtered, washed with ethanol for many times and dried in a vacuum drying oven at 50 ℃ for 12h to obtain 15.1g of a yellow solid powder product with a yield of 91.1%.
The flame-retardant curing agent comprises the following elements in percentage by mass: 66.80% of C, 4.74% of H, 6.84% of O, 6.63% of P and 14.98% of N; the nuclear magnetic spectrum data is as follows:1H NMR(DMSO-d6)：8.73-8.44ppm(s，1H，-CH＝N-)，6.40-8.00ppm(m，8H，Ph-H)，5.42-5.00ppm(s，2H，-NH2-)；31P NMR(DMSO-d6)：8.73ppm(s)。
5g of the flame-retardant curing agent from example 1 was dissolved in 100g of ordinary bisphenol A glycidyl ether (NPEL-128, south Asia), preheated at 70 ℃ and then cured by adding 24.40g of diaminodiphenylmethane (DDM) in the stoichiometric ratio (equimolar amount of the functional groups), the performance parameters of which are shown in Table 1. Comparative example (NPEL-128/DDM cured product) preparation method: 100g of NPEL-128 was preheated at 70 ℃ and 26.5g of DDM were added in a metered ratio, stirred for about 15min to homogeneous and degassed, and then cast in a mold preheated at 100 ℃. The curing procedure was: at 100 ℃ for 1h, at 150 ℃ for 2h, and naturally cooling to room temperature after curing.
Example 2
130g of salicylaldehyde, 41g of sodium hydroxide, 54g of hexachlorocyclotriphosphazene and 300mL of tetrahydrofuran are put into a 1L three-neck round-bottom flask with magnetic stirring, a condensation reflux device, a constant-pressure dropping funnel and nitrogen protection, and after the salicylaldehyde, the temperature is raised to 65 ℃ after the salicylaldehyde is completely dissolved, the reaction is carried out for 48 hours, and then the reaction is cooled to room temperature. Then concentrating by rotary evaporation, pouring into 1L deionized water for reversed phase precipitation, stirring for 1 hour at room temperature, filtering, washing with 300ml ethanol for multiple times, and vacuum drying to obtain a crude product. Purification by recrystallization from ethyl acetate gave 113.6g of intermediate product in 85% yield.
Adding 80g of 2, 3-diaminopyridine and 200mL of tetrahydrofuran into a 500mL three-neck round-bottom flask with a magnetic stirring device, a condensation reflux device and a constant-pressure dropping funnel, heating to 60 ℃, adding 50mL of tetrahydrofuran solution containing 10g of intermediate (11.6mmol) within 1 hour after the 2, 3-diaminopyridine and 200mL of tetrahydrofuran are completely dissolved, reacting for 24 hours, cooling to room temperature, and enabling the reaction system to become turbid from clear. Then directly filtered, washed with ethanol for many times and dried in a vacuum drying oven at 50 ℃ for 12h to obtain 14.6g of a light yellow solid powder product with a yield of 89.2%.
5g of the flame-retardant curing agent of example 2 was dissolved in 100g of ordinary bisphenol A glycidyl ether (NPEL-128 in south Asia), preheated at 70 ℃ and then cured by adding 24.5g of diaminodiphenylmethane (DDM) in the stated ratio, the performance parameters being shown in Table 1.
Example 3
100g of 3-ethoxy-4-hydroxybenzaldehyde (ethyl vanillin), 27g of sodium hydroxide and 200mL of tetrahydrofuran are added into a 500mL three-neck round-bottom flask with magnetic stirring, a condensation reflux device, a constant-pressure dropping funnel and nitrogen protection, the temperature is raised to 65 ℃, 80mL of tetrahydrofuran solution containing 35g of hexachlorocyclotriphosphazene is added within 1 hour after complete dissolution, and the mixture is cooled to room temperature after 24 hours of reaction. Then the mixture is concentrated by rotary evaporation and poured into 1L of deionized water for precipitation, stirred for 1 hour at room temperature and filtered, washed for a plurality of times by 300ml of ethanol, and dried in vacuum to obtain a crude product. Recrystallization from ethyl acetate gave 102.3g of intermediate product with a yield of 90.1%.
70g of p-phenylenediamine is added into a 500mL three-neck round-bottom flask with a magnetic stirring device, a condensation reflux device and a constant pressure dropping funnel, the temperature is raised to 60 ℃, after the p-phenylenediamine is completely dissolved, 50mL of tetrahydrofuran solution containing 10.5g of intermediate product (9.3mmol) is added within 1 hour, the reaction is continued for 12 hours, the reaction system is cooled to room temperature, and the reaction system is changed from clear to turbid. Then directly filtered, washed with ethanol several times and dried in a vacuum oven at 50 ℃ for 12h to obtain 14.2g of a yellow solid powder product with a yield of 91.6%.
5g of the flame-retardant curing agent of example 3 was dissolved in 100g of ordinary bisphenol A glycidyl ether (NPEL-128 in south Asia), preheated at 70 ℃ and then cured by adding 24.8 diaminodiphenylmethane (DDM) in the stoichiometric ratio, the performance parameters of which are shown in Table 1.
Example 4
195g syringaldehyde, 41g sodium hydroxide and 400mL tetrahydrofuran are put into a 1L three-neck round-bottom flask with magnetic stirring, a condensation reflux device, a constant pressure dropping funnel and nitrogen protection, the temperature is raised to 65 ℃, after complete dissolution, 100mL tetrahydrofuran solution containing 54g hexachlorocyclotriphosphazene is added within 1 hour, the reaction is continued for 24 hours, and the temperature is cooled to room temperature. The reaction mixture was then rotary evaporated to 1L of deionized water and stirred for 1 hour before filtration, washed several times with 300ml ethanol and dried in vacuo to give the crude product. Recrystallization from ethyl acetate gave 171.4g of intermediate product in 90.3% yield.
85g of 2, 3-diaminotoluene and 200mL of ethanol are added into a 500mL three-neck round-bottom flask with magnetic stirring, a condensation reflux device and a constant pressure dropping funnel, after complete dissolution, the temperature is raised to 70 ℃, 50mL of tetrahydrofuran solution containing 12.22g of intermediate (10mmol) is added within 1 hour, the reaction is continued for 6 hours, the temperature is cooled to room temperature, and the reaction system turns from clear to turbid. Then directly filtered, washed with ethanol several times and dried in a vacuum oven at 50 ℃ for 12h to obtain 17.5g of a yellow solid powder product with a yield of 92.2%.
5g of the flame-retardant curing agent of example 4 was dissolved in 100g of ordinary bisphenol A glycidyl ether (NPEL-128 in south Asia), preheated at 70 ℃ and then cured by adding 25.0g of diaminodiphenylmethane (DDM) in the stated ratio, the performance parameters being shown in Table 1.
Example 5
Adding 90g of 4-hydroxy-3, 5-dimethylbenzaldehyde, 66.5g of triethylamine and 150mL of 1, 4-dioxane into a 500mL three-neck round-bottom flask with magnetic stirring, a condensation reflux device, a constant-pressure dropping funnel and nitrogen protection, heating to 90 ℃, adding 60mL of 1, 4-dioxane solution containing 35g of hexachlorocyclotriphosphazene within 1 hour after complete dissolution, continuing to react for 12 hours, and cooling to room temperature. And sequentially filtering, performing rotary evaporation concentration, pouring into 1L of deionized water for precipitation, stirring at room temperature for 1 hour, filtering, washing with 300ml of ethanol for multiple times, and performing vacuum drying to obtain a crude product. Purification by recrystallization from ethyl acetate gave 85.8g of intermediate product in 90.1% yield.
80g N-methyl-1, 2-phenylenediamine is dissolved in 200mL of 1, 4-dioxane, then the solution is added into a 500mL three-neck round bottom flask with a magnetic stirring device, a condensation reflux device and a constant pressure dropping funnel, the temperature is raised to 85 ℃, after the reactants are completely dissolved, 50mL of 1, 4-dioxane solution containing 9.60g of intermediate product (9.3mmol) is added within 1 hour, the reaction is continued for 12 hours, and the reaction system is cooled to room temperature and turns from clear to turbid. Then directly filtered, washed with ethanol several times and dried in a vacuum oven at 50 ℃ for 12h to obtain 14.9g of a yellow solid powder product with a yield of 92.5%.
5g of the flame-retardant curing agent of example 5 was dissolved in 100g of ordinary bisphenol A glycidyl ether (NPEL-128 in south Asia), preheated at 70 ℃ and then cured by adding 24.7g of diaminodiphenylmethane (DDM) in the stated ratio, the performance parameters being shown in Table 1.
Example 6
Adding 110g of 3-tert-butyl salicylaldehyde, 27g of acid-binding agent sodium hydroxide and 200mL of tetrahydrofuran into a 500mL three-neck round-bottom flask with magnetic stirring, a condensation reflux device, a constant-pressure dropping funnel and nitrogen protection, heating to 65 ℃, adding 60mL of tetrahydrofuran solution containing 35g of hexachlorocyclotriphosphazene within 1 hour after complete dissolution, continuing to react for 24 hours, and cooling to room temperature. Then the crude product is obtained by rotary evaporation, adding into 1L deionized water, stirring for 1 hour at room temperature, filtering, washing with 300ml ethanol for multiple times, and vacuum drying. Purification by recrystallization from ethyl acetate gave 103g of intermediate product in 92.8% yield.
105g of 1, 8-diaminonaphthalene is dissolved in 300mL of absolute ethanol, then the solution is added into a 500mL three-neck round-bottom flask with a magnetic stirring device, a condensation reflux device and a constant pressure dropping funnel, the temperature is raised to 70 ℃ after the reactants are completely dissolved, 50mL of tetrahydrofuran solution containing 11.2g of intermediate product (9.3mmol) is added within 1 hour, the reaction is continued for 6 hours, the reaction system is cooled to room temperature, and the reaction system is changed from clear to turbid. Then directly filtered, washed with ethanol for many times and dried in a vacuum drying oven at 50 ℃ for 12h to obtain 18.2g of a yellow solid powder product with a yield of 94.1%.
5g of the flame-retardant curing agent of example 6 was dissolved in 100g of ordinary bisphenol A glycidyl ether (NPEL-128 in south Asia), preheated at 70 ℃ and then cured by adding 25.1g of diaminodiphenylmethane (DDM) in the stated ratio, the performance parameters being shown in Table 1.
TABLE 1 Properties of the epoxy resin cured with the flame retardant curing agent synthesized in each example
Remarking: tensile strength was tested according to the ASTM D638 standard, Izod impact strength (unnotched) was tested according to the ISO180 standard.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The flame-retardant curing agent containing the phosphazene/aromatic imine composite structure is characterized by having the following structural formula:
wherein R is1Is an aromatic ether, or one or more hydrogen atoms on the benzene ring of the aromatic ether are substituted by alkoxy, oxygen atom, amino or nitro, wherein R1The O atom in (1) is connected with the P atom; r2Is an aromatic hydrocarbon, or one or more hydrogen atoms on the benzene ring of the aromatic hydrocarbon are substituted by an alkoxy group, an oxygen atom, an amino group or a nitro group.
2. The flame retardant curing agent according to claim 1, wherein R is1Is any one of the following structures:
3. the flame retardant curing agent according to claim 1 or 2, wherein R is2Is any one of the following structures:
4. a method for preparing a flame retardant curing agent according to claim 1,2 or 3, comprising the steps of:
(1) adding hexachlorocyclotriphosphazene and a solvent into a reactor under the protection of inert gas, then adding aromatic aldehyde containing hydroxyl and an acid-binding agent, and stirring and reacting for 8-60 hours at 30-100 ℃ to obtain a reaction solution; purifying to obtain an intermediate product;
(2) dissolving the intermediate product in a solvent, adding the dissolved intermediate product into an aromatic diamine solution, and stirring and reacting for 0.5-24 hours at the temperature of 30-100 ℃; purifying to obtain the target product.
5. The method according to claim 4, wherein the ratio of hexachlorocyclotriphosphazene to solvent in step (1) is 1 g: 0.5-10 ml; the molar ratio of the aromatic aldehyde to the hexachlorocyclotriphosphazene is 6-10: 1; the mole ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is 6-10: 1.
6. the method according to claim 4, wherein the ratio of the intermediate product to the solvent in the step (2) is 1 g: 0.5-10 ml; the molar ratio of the aromatic diamine to the intermediate product is 10-20: 1.
7. the production method according to claim 4, 5 or 6, the aromatic aldehyde containing hydroxyl is any one or more than two of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, o-hydroxybenzaldehyde (salicylaldehyde), 4-hydroxyl-2-methyl-benzaldehyde, 4-hydroxyl-2-methoxybenzaldehyde, 4-hydroxyl-3-methoxybenzaldehyde, ethyl vanillin, syringaldehyde, vanillin, 4-hydroxyl-3, 5-dimethylbenzaldehyde, 3-methyl salicylaldehyde, 3-tert-butyl salicylaldehyde, 3-methoxy salicylaldehyde, 4, 6-dimethoxy salicylaldehyde, 3-ethoxy salicylaldehyde, 4-diethylamino salicylaldehyde, 2-hydroxyl-3-nitrobenzaldehyde and 2-hydroxynaphthaldehyde.
8. The method according to claim 4, 5 or 6, wherein the solvent is any one or more of methanol, ethanol, isopropanol, acetone, butanone, toluene, xylene, chlorobenzene, dichlorobenzene, methyl acetate, propyl acetate, ethyl acetate, dichloromethane, dichloroethane, chloroform, dioxane, tetrahydrofuran and dimethyl sulfoxide; the acid-binding agent is any one or more of triethylamine, ethylenediamine, pyridine, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, imidazole, N-diisopropylethylamine, triethanolamine, tetrabutylammonium bromide, sodium acetate, dipotassium hydrogen phosphate, potassium carbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide.
9. The production method according to claim 4, 5 or 6, wherein the aromatic diamine is any one or two or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2, 3-diaminotoluene, 2, 6-diaminotoluene, 2,4, 6-trimethyl-1, 3-phenylenediamine, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 2, 3-diaminopyridine, 2-nitro-1, 4-phenylenediamine, N-methyl-1, 2-phenylenediamine, 3,4' -diaminodiphenyl ether, 1, 8-diaminonaphthalene, 2, 7-diaminofluorene, 2, 6-diaminoanthraquinone, and 9, 10-diaminophenanthrene.
10. The preparation method according to claim 4, 5 or 6, wherein the reaction temperature in the step (1) is 65-90 ℃, and the reaction time is 12-48 h; in the step (2), the reaction temperature is 60-85 ℃, and the reaction time is 6-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911265070.9A CN111116663A (en) | 2019-12-11 | 2019-12-11 | Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911265070.9A CN111116663A (en) | 2019-12-11 | 2019-12-11 | Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111116663A true CN111116663A (en) | 2020-05-08 |
Family
ID=70498462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911265070.9A Pending CN111116663A (en) | 2019-12-11 | 2019-12-11 | Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111116663A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875648A (en) * | 2020-07-16 | 2020-11-03 | 华北科技学院 | Bio-based macromolecular flame retardant and preparation method and application thereof |
| CN111909402A (en) * | 2020-09-03 | 2020-11-10 | 华南农业大学 | Preparation method of carbon fiber reinforced thermosetting resin-based composite material and product thereof |
| CN112090413A (en) * | 2020-08-24 | 2020-12-18 | 四川大学 | Quasi-three-dimensional phosphazene covalent organic framework material and preparation method and application thereof |
| CN113402558A (en) * | 2021-06-28 | 2021-09-17 | 武汉海翎化学工业有限公司 | Phosphazene and imine composite flame retardant, flame-retardant epoxy resin material and preparation method thereof |
| CN113429629A (en) * | 2021-07-20 | 2021-09-24 | 衡阳师范学院 | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin |
| CN113621137A (en) * | 2021-08-02 | 2021-11-09 | 北京化工大学 | Preparation method of cyclophosphazenil polyimine vitrimer and application of cyclophosphazenil polyimine vitrimer in preparation of epoxy resin and polyurethane material |
| CN114133585A (en) * | 2021-10-27 | 2022-03-04 | 浙大宁波理工学院 | Bio-based intumescent flame-retardant composite material and preparation method and application thereof |
| CN114316277A (en) * | 2022-01-06 | 2022-04-12 | 齐鲁工业大学 | Solid phosphazene compound, preparation method and application |
| CN114478634A (en) * | 2022-01-20 | 2022-05-13 | 东华大学 | Aromatic Schiff base phosphazene double-base structure flame retardant and preparation method and application thereof |
| RU2776364C1 (en) * | 2021-09-14 | 2022-07-19 | Федеральное государственное бюджетное образовательное учреждение высшего образование "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method for obtaining amino-containing aryloxycyclophosphazenes in the mass of amines |
| CN114957918A (en) * | 2022-05-31 | 2022-08-30 | 安徽大学 | Epoxy resin flame-retardant material and preparation method thereof |
| CN115073686A (en) * | 2022-06-28 | 2022-09-20 | 河北大学 | Preparation method of bio-based flame-retardant smoke suppressant containing vanillin and flame-retardant epoxy resin |
| CN115232638A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Heavy oil demulsifier and preparation method and application thereof |
| CN115746322A (en) * | 2022-11-21 | 2023-03-07 | 河北工业大学 | Phosphorus-containing and pyridine nitrogen cation covalent organic framework with flame retardant property |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603800A (en) * | 2012-02-24 | 2012-07-25 | 北京工商大学 | Preparation method of phosphonitrile flame retardant |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
| CN105503957A (en) * | 2016-02-02 | 2016-04-20 | 北京工商大学 | Double base compound based on phosphonitrile and triazine group and preparation method of double base compound |
| CN106674905A (en) * | 2017-01-05 | 2017-05-17 | 北京理工大学 | Application of pyridine functional group-containing cyclotriphosphazene derivative |
| CN108976391A (en) * | 2018-07-23 | 2018-12-11 | 无锡创达新材料股份有限公司 | A kind of epoxy resin curing accelerator and its methods for making and using same based on three phosphonitrile of ring and imidazolium compounds |
-
2019
- 2019-12-11 CN CN201911265070.9A patent/CN111116663A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603800A (en) * | 2012-02-24 | 2012-07-25 | 北京工商大学 | Preparation method of phosphonitrile flame retardant |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
| CN105503957A (en) * | 2016-02-02 | 2016-04-20 | 北京工商大学 | Double base compound based on phosphonitrile and triazine group and preparation method of double base compound |
| CN106674905A (en) * | 2017-01-05 | 2017-05-17 | 北京理工大学 | Application of pyridine functional group-containing cyclotriphosphazene derivative |
| CN108976391A (en) * | 2018-07-23 | 2018-12-11 | 无锡创达新材料股份有限公司 | A kind of epoxy resin curing accelerator and its methods for making and using same based on three phosphonitrile of ring and imidazolium compounds |
Non-Patent Citations (5)
| Title |
|---|
| FATIH ASLAN ET AL.,: ""Synthesis of fluorescence organocyclotriphosphazene derivatives having functional groups such as formyl, Schiff base and both formyl and Schiff base without using Ar or N2 atmosphere"", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| MIAO-JUN XU ET AL.,: ""Synthesis of a novelflame retardant based on cyclotriphosphazene and DOPO groups and its application in epoxy resins"", 《POLYMER DEGRADATION AND STABILITY》 * |
| THATCHANAMURTHY LAKSHMIKANDHAN ET AL.,: ""Development of Phosphazene Imine-Modified Epoxy Composites for Low Dielectric, Antibacterial Activity,and UV Shielding Applications"", 《POLYMER COMPOSITES》 * |
| 丁浩: "《塑料工业实用手册 上》", 31 August 2000 * |
| 江民文等: ""环三磷腈-DOPO大分子阻燃剂的合成及阻燃环氧树脂性能"", 《高等学校化学学报》 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875648A (en) * | 2020-07-16 | 2020-11-03 | 华北科技学院 | Bio-based macromolecular flame retardant and preparation method and application thereof |
| CN112090413A (en) * | 2020-08-24 | 2020-12-18 | 四川大学 | Quasi-three-dimensional phosphazene covalent organic framework material and preparation method and application thereof |
| CN112090413B (en) * | 2020-08-24 | 2021-09-07 | 四川大学 | Quasi-three-dimensional phosphazene covalent organic framework material and preparation method and application thereof |
| CN111909402A (en) * | 2020-09-03 | 2020-11-10 | 华南农业大学 | Preparation method of carbon fiber reinforced thermosetting resin-based composite material and product thereof |
| CN111909402B (en) * | 2020-09-03 | 2021-06-29 | 华南农业大学 | Preparation method of carbon fiber reinforced thermosetting resin-based composite material and product thereof |
| CN115232638A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Heavy oil demulsifier and preparation method and application thereof |
| CN115232638B (en) * | 2021-04-22 | 2024-01-30 | 中国石油化工股份有限公司 | Thickened oil demulsifier and preparation method and application thereof |
| CN113402558A (en) * | 2021-06-28 | 2021-09-17 | 武汉海翎化学工业有限公司 | Phosphazene and imine composite flame retardant, flame-retardant epoxy resin material and preparation method thereof |
| CN113429629B (en) * | 2021-07-20 | 2023-02-28 | 衡阳师范学院 | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin |
| CN113429629A (en) * | 2021-07-20 | 2021-09-24 | 衡阳师范学院 | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin |
| CN113621137B (en) * | 2021-08-02 | 2022-10-18 | 北京化工大学 | Preparation method of cyclophosphazenitrile polyimine vitrimer and application of same in preparation of epoxy resin and polyurethane material |
| CN113621137A (en) * | 2021-08-02 | 2021-11-09 | 北京化工大学 | Preparation method of cyclophosphazenil polyimine vitrimer and application of cyclophosphazenil polyimine vitrimer in preparation of epoxy resin and polyurethane material |
| RU2776364C1 (en) * | 2021-09-14 | 2022-07-19 | Федеральное государственное бюджетное образовательное учреждение высшего образование "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method for obtaining amino-containing aryloxycyclophosphazenes in the mass of amines |
| CN114133585A (en) * | 2021-10-27 | 2022-03-04 | 浙大宁波理工学院 | Bio-based intumescent flame-retardant composite material and preparation method and application thereof |
| CN114316277B (en) * | 2022-01-06 | 2023-01-06 | 齐鲁工业大学 | Solid phosphazene compound, preparation method and application |
| CN114316277A (en) * | 2022-01-06 | 2022-04-12 | 齐鲁工业大学 | Solid phosphazene compound, preparation method and application |
| CN114478634A (en) * | 2022-01-20 | 2022-05-13 | 东华大学 | Aromatic Schiff base phosphazene double-base structure flame retardant and preparation method and application thereof |
| CN114478634B (en) * | 2022-01-20 | 2024-05-14 | 东华大学 | Aromatic Schiff base phosphazene double-base structure flame retardant, and preparation method and application thereof |
| CN114957918A (en) * | 2022-05-31 | 2022-08-30 | 安徽大学 | Epoxy resin flame-retardant material and preparation method thereof |
| CN115073686A (en) * | 2022-06-28 | 2022-09-20 | 河北大学 | Preparation method of bio-based flame-retardant smoke suppressant containing vanillin and flame-retardant epoxy resin |
| CN115073686B (en) * | 2022-06-28 | 2023-07-21 | 河北大学 | Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin |
| CN115746322A (en) * | 2022-11-21 | 2023-03-07 | 河北工业大学 | Phosphorus-containing and pyridine nitrogen cation covalent organic framework with flame retardant property |
| CN115746322B (en) * | 2022-11-21 | 2023-08-04 | 河北工业大学 | Phosphorus-containing and pyridine nitrogen cation covalent organic framework with flame retardant property |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111116663A (en) | Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof | |
| Liu et al. | Phosphorus‐containing epoxy for flame retardant. III: Using phosphorylated diamines as curing agents | |
| Chen‐Yang et al. | A flame‐retardant phosphate and cyclotriphosphazene‐containing epoxy resin: Synthesis and properties | |
| CN110510605B (en) | Nitrogen-rich group functionalized graphene, and preparation method and application thereof | |
| CN110105396B (en) | Bio-based phosphaphenanthrene flame-retardant curing agent and preparation method thereof | |
| CN104086751A (en) | DOPO-based symtriazine ring hydrogenated benzimidazole epoxy curing agent and preparation method thereof | |
| CN107400197A (en) | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof | |
| CN110511431B (en) | Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure | |
| CN109679048B (en) | Main chain type benzoxazine resin and preparation method thereof | |
| CN109467574B (en) | Reactive flame retardant based on vanillin as well as preparation and application thereof | |
| CN104478838A (en) | Phenylethynyl-containing dianhydride monomer, and synthesis method and application thereof | |
| CN104017172A (en) | Phosphaphenanthrene symtriazine anhydride epoxy hardener and preparation method thereof | |
| CN111704581B (en) | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin | |
| CN111253437A (en) | P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof | |
| CN107216354A (en) | The preparation method of the six degree of functionality epoxy resin based on the phosphonitrile of ring three | |
| CN110467747B (en) | Metal ion flame-retardant complex with Schiff base structure and preparation method thereof | |
| CN113234228B (en) | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof | |
| CN111187296B (en) | Nickel ion flame-retardant complex with Schiff base structure | |
| CN104926749A (en) | Benzoxazine monomer comprising vinyl benzene structure, and application and preparation method of benzoxazine monomer | |
| CN109503884B (en) | Tryptamine flame retardant and synthesis and application thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN108727586A (en) | A kind of structures of A containing triphenol can self-curing o-phthalonitrile resin preparation method | |
| CN110938232B (en) | Metal ion flame-retardant complex with Schiff base structure and preparation method thereof | |
| CN113929717A (en) | 2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof | |
| CN112300369B (en) | Reactive epoxy resin flame retardant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200508 |
|
| RJ01 | Rejection of invention patent application after publication |