CN114853696A - Bio-based intrinsic flame-retardant epoxy monomer and preparation method and application thereof - Google Patents
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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Abstract
The invention discloses a bio-based intrinsic flame-retardant epoxy monomer, a preparation method and application thereof, wherein the structural formula of the bio-based intrinsic flame-retardant epoxy monomer is
According to the invention, a Schiff base structure and an aromatic ether structure are introduced into an epoxy monomer, and a-C-N-bond in the Schiff base structure can be self-crosslinked at high temperature to generate a carbon-nitrogen six-membered ring, so that the polymer can form a stable crosslinking network, and excellent char formation and flame retardant properties are imparted to a high polymer material; the aromatic ether structure can be cracked and rearranged in the combustion process, and free radical segments are captured, so that the formation of carbon layers with different conjugated aromatic structures is promoted, and the flame retardant property of the polymer is improved; furthermore, the structure of the epoxy monomerTraditional flame retardant elements such as halogen, phosphorus and the like are not introduced, and a bio-based raw material is selected to replace a petroleum-based raw material, so that the environment-friendly flame retardant is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and particularly relates to a bio-based intrinsic flame-retardant epoxy monomer and a preparation method and application thereof.
Background
Epoxy resin is a commonly used thermosetting resin, and is widely applied to coatings, adhesives, electronic packaging materials and various high-performance composite materials due to excellent adhesion, mechanical properties, processability and electrical insulation properties. However, the epoxy resin has the disadvantage of flammability, which severely limits the application of the epoxy resin in the advanced fields of electronic information, aerospace and the like. The addition of flame retardant to epoxy resin is the most common modification method, but the problems of flame retardant failure and the like often occur in the use process. The epoxy resin structure is designed, and the flame-retardant structure is introduced into the epoxy monomer, so that the preparation of the intrinsic flame-retardant epoxy resin is a feasible scheme for replacing the modification by adding the flame retardant.
In addition, in recent years, with the increasing consumption of petroleum resources, problems such as resource depletion, climate change, and environmental pollution have become more serious. The development and application of renewable bio-based raw materials are an effective solution, and particularly the application of the renewable bio-based raw materials in the field of polymers can greatly relieve the energy and environmental stress. Therefore, the use of bio-based raw materials for the design of synthetic intrinsic flame retardant epoxy resins has received considerable attention from researchers.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bio-based intrinsic flame-retardant epoxy monomer.
The invention also aims to provide a preparation method of the bio-based intrinsic flame-retardant epoxy monomer.
The invention further aims to provide application of the bio-based intrinsic flame-retardant epoxy monomer.
The technical scheme of the invention is as follows:
a flame-retarding epoxy monomer with the structural formula of
R 1 is-O-or
R 2 Is composed of
In a preferred embodiment of the present invention, the compound has the formula
The preparation method of the biological basic characteristic flame-retardant epoxy monomer comprises the following steps:
(1) respectively dissolving an aromatic diamine compound and an aromatic aldehyde compound in a first organic solvent to obtain an aromatic diamine compound solution and an aromatic aldehyde compound solution, slowly dropwise adding the aromatic diamine compound solution into the aromatic aldehyde compound solution, stirring and reacting at 20-80 ℃ for 8-24h, cooling, filtering to obtain a precipitate, washing the precipitate, and performing vacuum drying to obtain an intermediate;
(2) mixing the intermediate, epoxy chloropropane and a catalyst, and stirring at 40-100 ℃ for reaction for 2-10 h;
(3) cooling the material obtained in the step (2) to 0-60 ℃, dropwise adding a sodium hydroxide solution into the material, and stirring the solution at room temperature for reaction for 1-5 hours;
(4) adding a second organic solvent into the material obtained in the step (3) for dilution, filtering to obtain a filtrate, fully washing the filtrate with deionized water for liquid separation, and then drying with anhydrous sodium sulfate for 12-48 h;
(5) and (4) dripping the material obtained in the step (4) into a precipitator, filtering the precipitate, washing the precipitate, and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer.
In a preferred embodiment of the present invention, the aromatic diamine compound is 4, 4 '-diaminodiphenyl ether or 4, 4' - (1, 4-benzenedioxy) dianiline, and the aromatic aldehyde compound is vanillin, p-hydroxybenzaldehyde, o-vanillin, ethyl vanillin, or syringaldehyde.
In a preferred embodiment of the present invention, the first organic solvent is at least one of methanol, ethanol, tetrahydrofuran, N-dimethylformamide, and 1, 4-dioxane, and the second organic solvent is at least one of dichloromethane, chloroform, and N-hexane.
In a preferred embodiment of the invention, the catalyst is tetrabutylammonium bromide and/or benzyltriethylammonium chloride.
In a preferred embodiment of the present invention, the precipitant is at least one of petroleum ether, diethyl ether and acetonitrile.
In a preferred embodiment of the present invention, the molar ratio of the aromatic diamine compound to the aromatic aldehyde compound is 1: 2-10, the ratio of the first organic solvent to the solute therein is 1-10 mL: 1g, the molar ratio of the sodium hydroxide to the intermediate is 5-10: 1, and the molar ratio of the intermediate, the epichlorohydrin and the catalyst is 1: 1-20: 0.1-1.
Further preferably, the concentration of the sodium hydroxide solution is 20 to 50%.
The application of the biological basic characteristic flame-retardant epoxy monomer in preparing the flame-retardant epoxy resin composition.
The flame-retardant epoxy resin composition is prepared by melting, mixing, degassing, heating and crosslinking and curing raw materials including the biological basic flame-retardant epoxy monomer and the curing agent 4, 4-aminodiphenylsulfone.
The invention has the beneficial effects that:
1. according to the invention, a Schiff base structure is introduced into an epoxy monomer, and a-C-N-bond in the Schiff base structure can be subjected to self-crosslinking at high temperature to generate a carbon-nitrogen six-membered ring, so that the polymer can form a stable crosslinking network, and excellent char-forming and flame-retardant properties are imparted to a high-molecular material.
2. According to the invention, an aromatic ether structure is introduced into the epoxy monomer, the aromatic ether structure can be cracked and rearranged in the combustion process, and the free radical segments are captured, so that the formation of carbon layers with different conjugated aromatic structures is promoted, and the aromatic ether structure has condensed phase and gas phase flame retardant effects, thereby improving the flame retardant property of the polymer.
3. The invention does not introduce phosphorus-containing and halogen-free elements, and selects bio-based raw materials to replace petroleum-based raw materials, and the finally obtained flame-retardant epoxy resin composition is more environment-friendly.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the intermediate of the bio-based intrinsic flame retardant structure obtained in example 1 of the present invention.
FIG. 2 is the NMR spectrum of the basic biological flame retardant epoxy monomer obtained in example 1 of the present invention.
FIG. 3 is a FT-IR spectrum of the bio-based intrinsic flame retardant structural intermediate and the bio-based intrinsic flame retardant epoxy monomer obtained in example 1 of the present invention.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the intermediate of the biological basic characteristic flame-retardant structure obtained in example 6 of the present invention.
FIG. 5 is the NMR spectrum of the basic biology flame-retardant epoxy monomer obtained in example 6 of the present invention.
FIG. 6 is a FT-IR spectrum of the bio-based intrinsic flame retardant structural intermediate and the bio-based intrinsic flame retardant epoxy monomer obtained in example 6 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Weighing 3.043g (0.02mol) of vanillin and 2.0024g (0.01mol) of 4, 4 '-diaminodiphenyl ether, respectively dissolving into 50mL of methanol, adding a vanillin solution into a reaction container, slowly dropwise adding the 4, 4' -diaminodiphenyl ether solution into the reaction container, reacting at 80 ℃ for 8h, after the reaction is finished, cooling, filtering, washing and vacuum drying to obtain a bio-based intrinsic flame-retardant structure intermediate shown in figures 1 and 3, wherein as can be seen from figure 1, each peak on the figure corresponds to a hydrogen atom on the intermediate structure one by one;
(2) 4.5168g (0.01mol) of intermediate, 18.504g (0.2mol) of epichlorohydrin and 0.32237g (0.001mol) of tetrabutylammonium bromide are sequentially weighed and added into a reaction vessel to react for 5 hours at 80 ℃;
(3) cooling the reaction solution obtained in the step (2) to room temperature, dropwise adding 5g of 40% sodium hydroxide solution, and continuing to react at room temperature for 3 hours;
(4) after the reaction is finished, adding excessive dichloromethane for dilution, filtering, washing and separating the filtrate for 5 times by deionized water, then drying the filtrate overnight by anhydrous sodium sulfate, then dropwise adding the dried solution into excessive petroleum ether for precipitation, filtering, washing and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer shown in the figures 2 and 3, wherein the structural formula of the bio-based intrinsic flame-retardant epoxy monomer is as follows:
as can be seen from FIG. 2, each peak in the figure corresponds to a hydrogen atom on the epoxy monomer structure.
(5) Heating and melting the obtained bio-based intrinsic flame-retardant epoxy monomer, adding a curing agent 4, 4' -aminodiphenylsulfone according to a proportion, stirring for dissolving, degassing, pouring into a mould, putting into an oven, and setting the programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, curing at 220 ℃ for 2h, and obtaining the flame-retardant epoxy resin composition after curing. The results of the performance test of the flame retardant epoxy resin composition are shown in table 1.
Example 2
(1) Weighing 2.4424g (0.02mol) of p-hydroxybenzaldehyde and 2.0024g (0.01mol) of 4, 4 '-diaminodiphenyl ether, respectively dissolving into 50mL of methanol, adding an o-vanillin solution into a reaction vessel, slowly dropwise adding the 4, 4' -diaminodiphenyl ether solution into the reaction vessel, reacting for 8h at 80 ℃, and after the reaction is finished, cooling, filtering, washing and vacuum drying to obtain a biological basic characteristic flame-retardant structural intermediate;
(2) 4.0846g (0.01mol) of intermediate, 18.504g (0.2mol) of epoxy chloropropane and 0.32237g (0.001mol) of tetrabutylammonium bromide are sequentially weighed and added into a reaction vessel to react for 5 hours at the temperature of 80 ℃;
(3) cooling the reaction solution obtained in the step (2) to room temperature, dropwise adding 5g of 40% sodium hydroxide solution, and continuing to react at room temperature for 3 hours;
(4) after the reaction is finished, adding excessive dichloromethane for dilution, filtering, washing and separating the filtrate for 5 times by deionized water, then drying the filtrate overnight by anhydrous sodium sulfate, then dropwise adding the dried solution into excessive petroleum ether for precipitation, filtering, washing and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer, wherein the structural formula of the bio-based intrinsic flame-retardant epoxy monomer is as follows:
(5) heating and melting the obtained bio-based intrinsic flame-retardant epoxy monomer, adding a curing agent 4, 4' -aminodiphenylsulfone according to a proportion, stirring for dissolving, degassing, pouring into a mould, putting into an oven, and setting the programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, curing at 220 ℃ for 2h, and obtaining the flame-retardant epoxy resin composition after curing. The results of the performance test of the flame retardant epoxy resin composition are shown in table 1.
Example 3
(1) Weighing 3.043g (0.02mol) of o-vanillin and 2.0024g (0.01mol) of 4, 4 '-diaminodiphenyl ether, respectively dissolving into 50mL of methanol, adding an o-vanillin solution into a reaction container, slowly dropwise adding the 4, 4' -diaminodiphenyl ether solution into the reaction container, reacting for 8 hours at 80 ℃, and after the reaction is finished, cooling, filtering, washing and vacuum drying to obtain a biological basic characteristic flame-retardant structural intermediate;
(2) 4.5168g (0.01mol) of intermediate, 18.504g (0.2mol) of epichlorohydrin and 0.32237g (0.001mol) of tetrabutylammonium bromide are sequentially weighed and added into a reaction vessel to react for 5 hours at 80 ℃;
(3) cooling the reaction solution obtained in the step (2) to room temperature, dropwise adding 5g of 40% sodium hydroxide solution, and continuing to react at room temperature for 3 hours;
(4) after the reaction is finished, adding excessive dichloromethane for dilution, filtering, washing and separating the filtrate for 5 times by deionized water, then drying the filtrate overnight by anhydrous sodium sulfate, then dropwise adding the dried solution into excessive petroleum ether for precipitation, filtering, washing and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer, wherein the structural formula of the bio-based intrinsic flame-retardant epoxy monomer is as follows:
(5) heating and melting the obtained bio-based intrinsic flame-retardant epoxy monomer, adding a curing agent 4, 4' -aminodiphenylsulfone according to a proportion, stirring for dissolving, degassing, pouring into a mould, putting into an oven, and setting the programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, curing at 220 ℃ for 2h, and obtaining the flame-retardant epoxy resin composition after curing. The results of the performance test of the flame retardant epoxy resin composition are shown in table 1.
Example 4
(1) Weighing 3.3236g (0.02mol) of ethyl vanillin and 2.0024g (0.01mol) of 4, 4 '-diaminodiphenyl ether, respectively dissolving into 50mL of methanol, adding an o-vanillin solution into a reaction vessel, slowly dropwise adding the 4, 4' -diaminodiphenyl ether solution into the reaction vessel, reacting for 8 hours at 80 ℃, and after the reaction is finished, cooling, filtering, washing and vacuum drying to obtain a biological basic characteristic flame-retardant structural intermediate;
(2) 4.9656g (0.01mol) of intermediate, 18.504g (0.2mol) of epichlorohydrin and 0.32237g (0.001mol) of tetrabutylammonium bromide are sequentially weighed and added into a reaction vessel to react for 5 hours at 80 ℃;
(3) cooling the reaction solution obtained in the step (2) to room temperature, dropwise adding 5g of 40% sodium hydroxide solution, and continuing to react at room temperature for 3 hours;
(4) after the reaction is finished, adding excessive dichloromethane for dilution, filtering, washing and separating the filtrate for 5 times by deionized water, then drying the filtrate overnight by anhydrous sodium sulfate, then dropwise adding the dried solution into excessive petroleum ether for precipitation, filtering, washing and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer, wherein the structural formula of the bio-based intrinsic flame-retardant epoxy monomer is as follows:
(5) heating and melting the obtained bio-based intrinsic flame-retardant epoxy monomer, adding a curing agent 4, 4' -aminodiphenylsulfone according to a proportion, stirring for dissolving, degassing, pouring into a mould, putting into an oven, and setting the programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, and curing at 220 ℃ for 2h to obtain the flame-retardant epoxy resin composition. The results of the performance test of the flame retardant epoxy resin composition are shown in table 1.
Example 5
(1) Weighing 3.6436g (0.02mol) of syringaldehyde and 2.0024g (0.01mol) of 4, 4 '-diaminodiphenyl ether, respectively dissolving into 50mL of methanol, adding an o-vanillin solution into a reaction vessel, slowly dropwise adding the 4, 4' -diaminodiphenyl ether solution into the reaction vessel, reacting for 8 hours at 80 ℃, and after the reaction is finished, cooling, filtering, washing and vacuum drying to obtain a biological basic characteristic flame-retardant structural intermediate;
(2) 5.2856g (0.01mol) of intermediate, 18.504g (0.2mol) of epichlorohydrin and 0.32237g (0.001mol) of tetrabutylammonium bromide are sequentially weighed and added into a reaction vessel to react for 5 hours at 80 ℃;
(3) cooling the reaction solution obtained in the step (2) to room temperature, dropwise adding 5g of 40% sodium hydroxide solution, and continuing to react at room temperature for 3 hours;
(4) after the reaction is finished, adding excessive dichloromethane for dilution, filtering, washing and separating the filtrate for 5 times by deionized water, then drying the filtrate overnight by anhydrous sodium sulfate, then dropwise adding the dried solution into excessive petroleum ether for precipitation, filtering, washing and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer, wherein the structural formula of the bio-based intrinsic flame-retardant epoxy monomer is as follows:
(5) heating and melting the obtained bio-based intrinsic flame-retardant epoxy monomer, adding a curing agent 4, 4' -aminodiphenylsulfone according to a proportion, stirring for dissolving, degassing, pouring into a mould, putting into an oven, and setting the programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, curing at 220 ℃ for 2h, and obtaining the flame-retardant epoxy resin composition after curing. The results of the performance test of the flame retardant epoxy resin composition are shown in table 1.
Example 6
(1) Weighing 3.043g (0.02mol) of vanillin and 2.9234g (0.01mol) of 4, 4 '- (1, 4-benzenedioxy) dianiline, respectively dissolving into 50mL of methanol, adding the vanillin solution into a reaction container, slowly dropwise adding the 4, 4' - (1, 4-benzenedioxy) dianiline solution into the reaction container, reacting for 8 hours at 80 ℃, after the reaction is finished, cooling, filtering, washing and vacuum drying to obtain the biological-based intrinsic flame-retardant structural intermediate shown in figures 4 and 6, wherein, as can be seen in figure 4, each peak on the figures corresponds to a hydrogen atom on the intermediate structure one by one;
(2) 5.6061g (0.01mol) of intermediate, 18.504g (0.2mol) of epoxy chloropropane and 0.32237g (0.001mol) of tetrabutylammonium bromide are sequentially weighed and added into a reaction vessel to react for 5 hours at the temperature of 80 ℃;
(3) cooling the reaction solution obtained in the step (2) to room temperature, dropwise adding 5g of 40% sodium hydroxide solution, and continuing to react at room temperature for 3 hours;
(4) after the reaction is finished, adding excessive dichloromethane for dilution, filtering, washing and separating the filtrate by deionized water for 5 times, then drying the filtrate overnight by anhydrous sodium sulfate, then dropwise adding the dried solution into excessive petroleum ether for precipitation, filtering, washing and drying in vacuum to obtain the biological basic characteristic flame-retardant epoxy monomer shown in the figures 5 and 6, wherein the structural formula of the monomer is as follows:
as can be seen from FIG. 5, each peak in the figure corresponds to a hydrogen atom on the epoxy monomer structure.
(5) Heating and melting the obtained bio-based intrinsic flame-retardant epoxy monomer, adding a curing agent 4, 4' -aminodiphenylsulfone according to a proportion, stirring for dissolving, degassing, pouring into a mould, putting into an oven, and setting the programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, curing at 220 ℃ for 2h, and obtaining the flame-retardant epoxy resin composition after curing. The results of the performance test of the flame retardant epoxy resin composition are shown in table 1.
Comparative example 1
Weighing bisphenol A epoxy resin E51, adding curing agent 4, 4' -amino diphenyl sulfone according to a proportion, stirring and dissolving at 80 ℃, degassing, pouring into a mould, putting into an oven, and setting programmed temperature rise time as follows: curing at 160 ℃ for 2h, curing at 180 ℃ for 2h, curing at 200 ℃ for 2h, curing at 220 ℃ for 2h, and obtaining the epoxy resin contrast sample after curing. The test results of the epoxy resin control are shown in table 1.
The above examples and comparative examples were subjected to flame retardant property tests, as shown in table 1. Wherein, the D band and A of disordered carbon in Raman spectrum 1g Vibration correlation, G band with E of ordered carbon 2g Vibration is correlated, I D /I G Is the ratio of the intensities of the D and G bands, I D /I G The smaller the size, the higher the graphitization degree of the carbon residue, which indicates that the flame-retardant epoxy resin composition forms a more compact carbon layer in the combustion process, and the condensed phase flame-retardant effect is better. TG-FTIR is used for characterizing the generation condition of gaseous products in the thermal cracking process of the epoxy resin, the gaseous products generated in the combustion process not only promote combustion, but also can be aggregated into dense smoke, and the peak absorption intensity released by the gaseous thermal cracking products can reflect the gas-phase flame-retardant effect.
TABLE 1 flame retardancy Performance testing of Bio-based epoxy resins and bisphenol A epoxy resins
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A biological basic flame retardant epoxy monomer is characterized in that: the structural formula is
Wherein the content of the first and second substances,
R 1 is-O-or
R 2 Is composed of
2. The bio-based flame retardant epoxy monomer of claim 1, wherein: the structural formula is
3. The preparation method of the bio-based flame retardant epoxy monomer as claimed in claim 1 or 2, wherein: the method comprises the following steps:
(1) respectively dissolving an aromatic diamine compound and an aromatic aldehyde compound in a first organic solvent to obtain an aromatic diamine compound solution and an aromatic aldehyde compound solution, slowly dropwise adding the aromatic diamine compound solution into the aromatic aldehyde compound solution, stirring and reacting at 20-80 ℃ for 8-24h, cooling, filtering to obtain a precipitate, washing the precipitate, and performing vacuum drying to obtain an intermediate;
(2) mixing the intermediate, epoxy chloropropane and a catalyst, and stirring at 40-100 ℃ for reaction for 2-10 h;
(3) cooling the material obtained in the step (2) to 0-60 ℃, dropwise adding a sodium hydroxide solution into the material, and stirring the solution at room temperature for reaction for 1-5 hours;
(4) adding a second organic solvent into the material obtained in the step (3) for dilution, filtering to obtain a filtrate, fully washing the filtrate with deionized water for liquid separation, and then drying with anhydrous sodium sulfate for 12-48 h;
(5) and (4) dripping the material obtained in the step (4) into a precipitator, filtering to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain the bio-based intrinsic flame-retardant epoxy monomer.
4. The method of claim 3, wherein: the aromatic diamine compound is 4, 4 '-diaminodiphenyl ether or 4, 4' - (1, 4-benzenedioxy) dianiline, and the aromatic aldehyde compound is vanillin, p-hydroxybenzaldehyde, o-vanillin, ethyl vanillin or syringaldehyde.
5. The method of claim 3, wherein: the first organic solvent is at least one of methanol, ethanol, tetrahydrofuran, N-dimethylformamide and 1, 4-dioxane, and the second organic solvent is at least one of dichloromethane, chloroform and N-hexane.
6. The method of claim 3, wherein: the catalyst is tetrabutylammonium bromide and/or benzyltriethylammonium chloride.
7. The method of claim 3, wherein: the precipitant is at least one of petroleum ether, diethyl ether and acetonitrile.
8. The production method according to any one of claims 3 to 7, characterized in that: the molar ratio of the aromatic diamine compound to the aromatic aldehyde compound is 1: 2-10, the ratio of the first organic solvent to the solute therein is 1-10 mL: 1g, the molar ratio of the sodium hydroxide to the intermediate is 5-10: 1, and the molar ratio of the intermediate, the epichlorohydrin and the catalyst is 1: 1-20: 0.1-1.
9. Use of a bio-based flame retardant epoxy monomer according to claim 1 or 2 in the preparation of a flame retardant epoxy resin composition.
10. A flame retardant epoxy resin composition characterized by: the flame-retardant epoxy resin is prepared by melting, mixing, degassing, heating and crosslinking and curing raw materials comprising the biological basic flame-retardant epoxy monomer and the curing agent 4, 4-aminodiphenylsulfone according to claim 1 or 2.
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| CN115093544A (en) * | 2022-06-07 | 2022-09-23 | 西北师范大学 | Schiff base structure syringaldehyde-based epoxy resin and preparation method thereof |
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