CN111825829A - Triazine ring structure-containing bio-based epoxy resin and preparation method thereof - Google Patents
Triazine ring structure-containing bio-based epoxy resin and preparation method thereof Download PDFInfo
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- CN111825829A CN111825829A CN202010015156.2A CN202010015156A CN111825829A CN 111825829 A CN111825829 A CN 111825829A CN 202010015156 A CN202010015156 A CN 202010015156A CN 111825829 A CN111825829 A CN 111825829A
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- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
Abstract
The invention discloses a triazine ring structure-containing bio-based epoxy resin and a preparation method thereof, belonging to the technical field of bio-based high polymer materials. The method comprises the steps of taking a biology-based compound containing aldehyde group as a raw material, firstly converting the aldehyde group into cyano, and then realizing cyano trimerization reaction under the catalysis of trifluoromethanesulfonic acid to prepare the triphenol monomer of the all biology-based carbon source containing triazine ring structure, which can be used for polymer synthesis. The bio-based monomer can react with epoxy chloropropane to finally obtain a bio-based epoxy resin precursor containing a triazine ring structure. After being cured, the prepared triazine ring structure-containing bio-based epoxy resin shows more excellent thermal stability, mechanical property and flame retardant property than petroleum-based bisphenol A epoxy resin, and has the possibility of replacing the existing petroleum-based related products.
Description
Technical Field
The invention belongs to the technical field of bio-based high polymer materials, and particularly relates to a triazine ring structure-containing bio-based epoxy resin and a preparation method thereof.
Background
Epoxy resin is a thermosetting resin which is most widely applied, and has the advantages of good adhesion, mechanical property, electrical insulation, chemical corrosion resistance, good processability, low curing shrinkage and the like, so that the epoxy resin has wide application in various fields such as coatings, adhesives, electronic packaging, composite materials and the like.
However, the epoxy resins currently available are mostly prepared from petroleum-based raw materials, and the bisphenol a type epoxy resin, which is prepared from bisphenol a and epichlorohydrin, accounts for 85% or more of the total epoxy resin production. While epichlorohydrin has been obtained by conversion of glycerol, a bio-based feedstock, bisphenol a is currently only produced from petroleum-based feedstocks. At present, petroleum resources are greatly consumed and are increasingly exhausted, so that the petroleum price is increased dramatically, and meanwhile, a series of severe environmental problems are brought, and great pressure is brought to the development of epoxy resin taking the petroleum resources as main raw materials. In addition, bisphenol a is an endocrine disrupter, poses a great threat to human health and the environment, and has been banned by most countries for materials that come into direct contact with food and human bodies. This also greatly limits the further applications and developments of epoxy resins.
Renewable biomass resources are developed and utilized to prepare a novel bio-based monomer capable of replacing the traditional petroleum-based monomer bisphenol A, and the problems can be effectively solved by further preparing the corresponding bio-based epoxy resin. At present, domestic and foreign research on the aspect has made great progress. For example, Cardanol, Chrysanthos, M, Galy J.preparation and precursors of the Chem, Nie X.Synthesis and Application of the polysaccharide carbohydrate Reactive derivative for Epoxy Resin [ J ]. ACS Sustainable Chemistry & Engineering,2015,3, 1164. 1171. isosorbide, Ma, S, Liu X.Synthesis and precursors of the bio-based epoxide polyol derivative for Polymer [ J ]. 2011,52, 3611. isosorbide, starch, S, Liu X.Synthesis and precursors of the bio-based epoxide polyol derivative for polyurethane Resin [ J ]. 10, 9, J.S. synthesis and precursors of the bio-based epoxide Resin for polyurethane Resin [ J ]. 12, 9, 62, 9, 7, 9, 5. A. B. synthesis and Application of the polysaccharide carbohydrate Reactive Resin, 2. A. synthesis and Application of the aforementioned compounds for formaldehyde, 2. A. supplement, D. A. 2015,5,15930-15939, the bio-based compounds such as furandicarboxylic acid and the like directly react with epichlorohydrin to prepare the bio-based epoxy resin. However, the overall performance of these bio-based epoxy resins is generally lower than bisphenol a type epoxy resins. There have also been some studies on the preparation of bio-based monomers in combination with terephthaloyl chloride in Wan, J, Gan B.A novel bio-based Epoxy Resin with High mechanical stability and reactivity [ J ]. Journal of materials Chemistry A,2015,3, 21907. terephthalic acid chloride, Wan, J, ZoJ. ultrastibia biocompatible Epoxy Resin with High Tg and Low permeability from food Synthesis Properties [ J ]. ACS stable Chemistry & Engineering,2016,4, 2869. melamine 2880. melamine chloride, S, M. variable-modified High viscosity Resin, polystyrene Resin with High reactivity [ J ]. 12. Epoxy Resin, polystyrene. Although the comprehensive performance of the bio-based epoxy resin is greatly improved, the bio-based content of the system is reduced due to the introduction of part of petroleum-based compounds. Therefore, the current research on the bio-based epoxy resin cannot meet the development target of high bio-based content and high performance of the bio-based epoxy resin in scientific research and practical application.
So far, no document or patent reports that the epoxy resin containing the triazine ring structure full-bio-based carbon source is prepared from bio-based monomers through corresponding structure transformation. The introduction of the triazine ring structure can effectively improve the heat resistance, the mechanical property and the flame retardant property of the epoxy resin. The epoxy resin containing the triazine ring structure prepared from the bio-based raw materials can effectively solve the problem that the epoxy resin excessively depends on petroleum-based raw materials, meets the requirements of sustainable development and energy conservation, and is favorable for promoting the further development of the bio-based epoxy resin.
Disclosure of Invention
The invention aims to provide a triazine ring structure-containing bio-based epoxy resin and a preparation method thereof. The bio-based epoxy resin provided by the invention is obtained by converting bio-based raw materials, and accords with the concept of environmental protection and sustainability. Compared with the traditional bisphenol A type and tetraglycidyl amine type epoxy resin, the thermal stability, the mechanical property and the flame retardant property are obviously improved. The preparation method provided by the invention is simple, easy to implement and suitable for large-scale industrial production.
The technical scheme of the invention is as follows:
a triazine ring structure-containing bio-based epoxy resin has the following structure:
wherein the R groups are as follows:
wherein, is a substituent connected with oxygen, and is a substituent connected with triazine ring.
A preparation method of bio-based epoxy resin containing triazine ring structure comprises the following steps:
(1) dissolving anhydrous ferric trichloride into anhydrous DMF, and adding an aldehyde group-containing bio-based compound and hydroxylamine hydrochloride into a reaction system, wherein the anhydrous DMF is prepared according to the weight ratio of 1g of anhydrous ferric trichloride: 5-80 ml of anhydrous DMF is added according to the molar ratio, and the reaction raw materials are anhydrous ferric trichloride according to the molar ratio: aldehyde group-containing bio-based compounds: adding hydroxylamine hydrochloride in a ratio of 1: 1-4: 2-6; then heating the system to 120-160 ℃, and reacting for 3-10 hours; after the reaction is finished, pouring the system into distilled water, extracting with ethyl acetate, separating liquid, drying an ethyl acetate layer, distilling under reduced pressure, removing the solvent, washing with water for 3-6 times, and drying in vacuum to obtain a cyano-containing bio-based compound;
(2) dissolving the cyano-containing bio-based compound prepared in the step (1) in a solvent, wherein the concentration of the cyano-containing bio-based compound is maintained between 5% and 30% g/ml, placing the system in an ice-water bath, and dropwise adding trifluoromethanesulfonic acid into the ice-water bath, wherein the molar ratio of the cyano-containing bio-based compound to the system is as follows: 1: 1.5-4 of trifluoromethanesulfonic acid, after the dropwise addition is completed, slowly heating the system to 25-60 ℃, and reacting for 10-48 hours in a nitrogen atmosphere; after the reaction is finished, settling the system in ice water, dropwise adding ammonia water into the ice water to adjust the pH value to be neutral, performing suction filtration, and washing the obtained product for three times to obtain the triazine ring structure containing bio-based triphenol monomer, wherein the structural formula is as follows:
wherein the R groups are as follows:
wherein, is a substituent connected with oxygen, and is a substituent connected with a triazine ring;
(3) adding the triazine ring structure-containing bio-based triphenol monomer prepared in the step (2), a phase transfer catalyst and epoxy chloropropane into a reaction container according to the molar ratio of 1: 0.001-0.5: 10-100, heating to 50-100 ℃, reacting for 2-8 hours in a nitrogen atmosphere, dropwise adding a 25-45 wt% (w/w) sodium hydroxide aqueous solution into the system, wherein the molar ratio of the sodium hydroxide to the triazine ring structure-containing bio-based triphenol monomer is 2-4: 1, and continuously reacting for 1-5 hours in the nitrogen atmosphere at the temperature of 50-100 ℃; after the reaction is finished, carrying out suction filtration, extracting and separating filtrate for 3-6 times by using distilled water, drying an organic layer, then carrying out reduced pressure distillation, removing a solvent, and drying a product in a vacuum oven to obtain the bio-based epoxy resin containing the triazine ring structure, wherein the epoxy value of the bio-based epoxy resin is 0.2-0.56;
(4) and (3) uniformly mixing the triazine ring structure-containing bio-based epoxy resin prepared in the step (3) with a curing agent, pouring the system into a mold after vacuum defoaming, and performing thermosetting molding to obtain a bio-based epoxy resin cured product, namely the triazine ring structure-containing bio-based epoxy resin.
The aldehyde group-containing bio-based compound in the step (1) is vanillin, o-vanillin, syringaldehyde, salicylaldehyde or hydroxymethylfurfural.
The solvent used in step (2) is dichloromethane, dichloroethane or chloroform.
The phase transfer catalyst used in the step (3) is benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetrabutylammonium hydrogen sulfate.
The curing agent in the step (4) comprises polyamine and acid anhydride, and is one or a mixture of more than two of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diethylaminopropylamine, ethylenediamine, isophorone diamine, N-aminoethyl piperazine, bis (4-aminocyclohexyl) methane, m-xylylenediamine, diaminodiphenyl methane, diaminodiphenyl sulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexenyl tetracarboxylic dianhydride and trimellitic anhydride.
Mixing the triazine ring structure-containing bio-based epoxy resin and a curing agent in a molar ratio of 1: 0.15-3, heating and melting at 150-200 ℃ in a vacuum oven, uniformly stirring, defoaming in vacuum, pouring the system into a mold after no bubbles exist, preserving heat at 100-140 ℃ for 1-3 hours, preserving heat at 160-180 ℃ for 1-5 hours, preserving heat at 190-210 ℃ for 1-5 hours, and preserving heat at 230-250 ℃ for 1-3 hours.
The invention has the beneficial effects that:
(1) the invention provides a method for preparing a compound containing a triazine ring structure from bio-based raw materials, develops a preparation method of a full-rigid bio-based compound containing aromatic heterocycles, and has important significance for constructing a high-performance bio-based high polymer material.
(2) The thermosetting epoxy resin product obtained after final curing of the triazine ring structure-containing bio-based epoxy resin provided by the invention has excellent heat resistance, mechanical properties and flame retardance. Compared with the traditional petroleum-based bisphenol A type and tetraglycidyl amine type epoxy resin, the comprehensive performance is obviously improved. Can be used as high-performance epoxy resin to be applied to the high and new technical fields of aerospace and the like.
(3) The preparation method is simple and efficient, convenient to operate, good in controllability, capable of producing by utilizing the existing chemical equipment, high in yield and purity and suitable for large-scale industrial production.
(4) The triazine ring structure-containing bio-based epoxy resin provided by the invention is completely obtained by converting aldehyde group-containing bio-based monomers and is an epoxy resin of a full bio-based carbon source. The problem that the petroleum-based epoxy resin excessively depends on petrochemical resources at present can be solved, and the development targets of saving the petrochemical resources, being green, environment-friendly and sustainable are met. And has great promotion effect on the development of the bio-based material.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
(1) Synthesis of bio-based 4-hydroxy-3-methoxybenzonitrile: 0.81g of anhydrous ferric trichloride and 50ml of anhydrous DMF were charged in a 100ml three-necked flask, and after being mechanically stirred to be completely dissolved, 1.52g of vanillin and 0.83g of hydroxylamine hydrochloride were successively added thereto, and the system was reacted at 140 ℃ for 5 hours. After completion of the reaction, the reaction mixture was poured into 100mL of distilled water, extracted with ethyl acetate, separated, and the ethyl acetate layer was dried over anhydrous sodium sulfate overnight. And then, carrying out suction filtration, carrying out reduced pressure distillation on the filtrate to remove the solvent to obtain a solid product, washing the obtained product for 3 times, and carrying out vacuum drying to obtain the bio-based monomer 4-hydroxy-3-methoxybenzonitrile with the yield of 93%.
(2) Synthesizing a triazine ring structure-containing bio-based triphenol monomer THMT: in a 500ml three-neck flask equipped with a mechanical stirring, condensing reflux and nitrogen introduction device, 15.66g of 3-hydroxy-4-methoxybenzonitrile and 300ml of dichloromethane were added, mechanically stirred to be fully dissolved, then the system was placed in an ice water bath, 57.37g of trifluoromethanesulfonic acid was dropwise added, and after completion of the dropwise addition, the system was slowly raised to 25 ℃ and reacted for 12 hours under a nitrogen atmosphere. And after the reaction is finished, pouring the system into 500ml of ice water, adjusting the system to be neutral by using ammonia water, performing suction filtration, washing the filtered solid product with water for three times, and performing vacuum drying to obtain the triazine ring structure-containing bio-based triphenol monomer THMT with the yield of 91%.
(3) Synthesizing triazine ring structure-containing bio-based epoxy resin THMT-EP: 29.55g of THMT-EP,1.68g of benzyltriethylammonium chloride and 580g of epichlorohydrin are sequentially added into a 1L three-neck flask provided with a mechanical stirring device, a condensing reflux device and a nitrogen introducing device, and the temperature is raised to 80 ℃ under the nitrogen atmosphere for reaction for 3 hours. Subsequently, 20ml of a 40% (w/w) aqueous NaOH solution was added dropwise to the system, and the reaction was continued at 80 ℃ for 1 hour. After the reaction, the reaction solution was filtered, the filtrate was extracted with distilled water, and the solution was separated three times, and the organic layer was dried overnight with anhydrous sodium sulfate. And (3) carrying out suction filtration, removing the solvent from the filtrate through reduced pressure distillation, and drying the product in a vacuum oven at 55 ℃ to obtain the triazine ring structure-containing bio-based epoxy resin THMT-EP with the yield of 87%.
Nuclear magnetic resonance hydrogen spectrum of obtained triazine ring structure-containing bio-based epoxy resin THMT-EP1H-NMR is shown in FIG. 1, and the peak positions and the integrated areas on the graph are completely consistent with the THMT-EP structure.
(4) Curing of THMT-EP: uniformly mixing the obtained THMT-EP epoxy resin and a curing agent DDS according to a one-to-one molar ratio of epoxy to NH, putting the mixture into a vacuum oven, heating and melting the mixture at 180 ℃, vacuumizing the mixture, defoaming the mixture until no bubbles are generated, pouring the system into a mold coated with a release agent, then putting the mold into a muffle furnace, and curing the mixture according to a curing procedure of heat preservation at 135 ℃ for 2 hours, heat preservation at 165 ℃ for 2 hours, heat preservation at 200 ℃ for 2 hours and heat preservation at 230 ℃ for 2 hours. The performance of the bio-based triazine ring structure-containing epoxy resin THMT-EP curing system is as follows: the 5 percent thermal weight loss temperature under the nitrogen atmosphere is 394 ℃, the carbon residue rate at 700 ℃ is 47.6 percent, the glass transition temperature is 300 ℃, the flexural modulus is 4137MPa, and the flame retardant self-extinguishing performance reaches the V-0 grade of UL-94 test.
Example 2
(1) Synthesis of bio-based 4-hydroxy-3, 5-dimethoxybenzonitrile: 0.97g of anhydrous ferric trichloride and 50ml of anhydrous DMF were charged in a 100ml three-necked flask, and after being mechanically stirred to be completely dissolved, 1.82g of syringaldehyde and 1.09g of hydroxylamine hydrochloride were successively added thereto, and the system was reacted at 140 ℃ for 5 hours. After completion of the reaction, the reaction mixture was poured into 100ml of distilled water, extracted with ethyl acetate, separated, and the ethyl acetate layer was dried over anhydrous sodium sulfate overnight. And then, carrying out suction filtration, carrying out reduced pressure distillation on the filtrate to remove the solvent to obtain a solid product, washing the obtained product for 3 times, and carrying out vacuum drying to obtain the bio-based monomer 4-hydroxy-3, 5-dimethoxybenzonitrile with the yield of 89%.
(2) Synthesizing a triazine ring structure-containing bio-based triphenol monomer THMT-2: in a 500ml three-necked flask equipped with a mechanical stirring, condensing reflux and nitrogen introduction device, 17.91g of 4-hydroxy-3, 5-dimethoxybenzonitrile and 300ml of dichloromethane were added, mechanically stirred to be sufficiently dissolved, then the system was placed in an ice water bath, 68.83g of trifluoromethanesulfonic acid was dropwise added, after completion of the dropwise addition, the system was slowly raised to 25 ℃ and reacted for 12 hours under a nitrogen atmosphere. After the reaction is finished, pouring the system into 500ml of ice water, adjusting the system to be neutral by using ammonia water, performing suction filtration, washing the filtered solid product with water for three times, and performing vacuum drying to obtain the triazine ring structure-containing bio-based triphenol monomer THMT-2 with the yield of 85%.
(3) Synthesis of triazine ring structure-containing bio-based epoxy resin THMT-2-EP: 29.55g of THMT-EP,1.59g of benzyltriethylammonium chloride and 550g of epichlorohydrin are sequentially added into a 1000ml three-neck flask provided with a mechanical stirring device, a condensing reflux device and a nitrogen introducing device, and the temperature is raised to 100 ℃ under the nitrogen atmosphere for reaction for 3 hours. Subsequently, 18ml of a 40% (w/w) aqueous NaOH solution was added dropwise to the system, and the reaction was continued at 100 ℃ for 1 hour. After the reaction, the reaction solution was filtered, the filtrate was extracted with distilled water, and the solution was separated three times, and the organic layer was dried overnight with anhydrous sodium sulfate. And (3) carrying out suction filtration, removing the solvent from the filtrate through reduced pressure distillation, and drying the product in a vacuum oven at 55 ℃ to obtain the triazine ring structure-containing bio-based epoxy resin THMT-2-EP with the yield of 82%.
(4) Curing of THMT-2-EP: uniformly mixing the obtained THMT-2-EP epoxy resin and a curing agent DDS according to a one-to-one molar ratio of epoxy to NH, putting the mixture into a vacuum oven, heating and melting the mixture at 175 ℃, vacuumizing the mixture, defoaming the mixture until no bubbles are generated, pouring the system into a mold coated with a release agent, then putting the mold into a muffle furnace, and curing the mixture according to a curing procedure of heat preservation at 135 ℃ for 2 hours, heat preservation at 165 ℃ for 2 hours, heat preservation at 200 ℃ for 2 hours and heat preservation at 230 ℃ for 2 hours. The performance of the bio-based triazine ring structure-containing epoxy resin THMT-2-EP curing system is as follows: the 5 percent thermal weight loss temperature under the nitrogen atmosphere is 380 ℃, the carbon residue rate at 700 ℃ is 45.3 percent, the glass transition temperature is 290 ℃, the flexural modulus is 3919MPa, and the flame retardant self-extinguishing performance reaches the V-0 level of UL-94 test.
Claims (10)
1. The bio-based epoxy resin containing the triazine ring structure is characterized by having the following structure:
wherein the R groups are as follows:
wherein, is a substituent connected with oxygen, and is a substituent connected with triazine ring.
2. The preparation method of the triazine ring structure-containing bio-based epoxy resin is characterized by comprising the following steps:
(1) dissolving anhydrous ferric trichloride into anhydrous DMF, and adding an aldehyde group-containing bio-based compound and hydroxylamine hydrochloride into a reaction system, wherein the anhydrous DMF is prepared according to the weight ratio of 1g of anhydrous ferric trichloride: 5-80 ml of anhydrous DMF is added according to the molar ratio, and the reaction raw materials are anhydrous ferric trichloride according to the molar ratio: aldehyde group-containing bio-based compounds: adding hydroxylamine hydrochloride in a ratio of 1: 1-4: 2-6; then heating the system to 120-160 ℃, and reacting for 3-10 hours; after the reaction is finished, pouring the system into distilled water, extracting with ethyl acetate, separating liquid, drying an ethyl acetate layer, distilling under reduced pressure, removing the solvent, washing with water for 3-6 times, and drying in vacuum to obtain a cyano-containing bio-based compound;
(2) dissolving the cyano-containing bio-based compound prepared in the step (1) in a solvent, wherein the concentration of the cyano-containing bio-based compound is maintained between 5% and 30% g/ml, placing the system in an ice-water bath, and dropwise adding trifluoromethanesulfonic acid into the ice-water bath, wherein the molar ratio of the cyano-containing bio-based compound to the system is as follows: 1: 1.5-4 of trifluoromethanesulfonic acid, after the dropwise addition is completed, slowly heating the system to 25-60 ℃, and reacting for 10-48 hours in a nitrogen atmosphere; after the reaction is finished, settling the system in ice water, dropwise adding ammonia water into the ice water to adjust the pH value to be neutral, performing suction filtration, and washing the obtained product for three times to obtain the triazine ring structure containing bio-based triphenol monomer, wherein the structural formula is as follows:
wherein the R groups are as follows:
wherein, is a substituent connected with oxygen, and is a substituent connected with a triazine ring;
(3) adding the triazine ring structure-containing bio-based triphenol monomer prepared in the step (2), a phase transfer catalyst and epoxy chloropropane into a reaction container according to the molar ratio of 1: 0.001-0.5: 10-100, heating to 50-100 ℃, reacting for 2-8 hours in a nitrogen atmosphere, dropwise adding a 25-45 wt% (w/w) sodium hydroxide aqueous solution into the system, wherein the molar ratio of the sodium hydroxide to the triazine ring structure-containing bio-based triphenol monomer is 2-4: 1, and continuously reacting for 1-5 hours in the nitrogen atmosphere at the temperature of 50-100 ℃; after the reaction is finished, carrying out suction filtration, extracting and separating filtrate for 3-6 times by using distilled water, drying an organic layer, then carrying out reduced pressure distillation, removing a solvent, and drying a product in a vacuum oven to obtain the bio-based epoxy resin containing the triazine ring structure, wherein the epoxy value of the bio-based epoxy resin is 0.2-0.56;
(4) and (3) uniformly mixing the triazine ring structure-containing bio-based epoxy resin prepared in the step (3) with a curing agent, pouring the system into a mold after vacuum defoaming, and performing thermosetting molding to obtain a bio-based epoxy resin cured product, namely the triazine ring structure-containing bio-based epoxy resin.
3. The preparation method of the triazine ring structure-containing bio-based epoxy resin as claimed in claim 2, wherein the triazine ring structure-containing bio-based epoxy resin in the step (4) is mixed with a curing agent according to a molar ratio of 1: 0.15-3, the mixture is heated and melted at 150-200 ℃ in a vacuum oven and then uniformly stirred, vacuum defoamed, and after no bubble is generated, the system is poured into a mold, and is subjected to heat preservation at 100-140 ℃ for 1-3 hours, then at 160-180 ℃ for 1-5 hours, then at 190-210 ℃ for 1-5 hours, and finally at 230-250 ℃ for 1-3 hours.
4. The method for preparing the triazine ring structure-containing bio-based epoxy resin according to claim 2 or 3, wherein the aldehyde group-containing bio-based compound in the step (1) is vanillin, o-vanillin, syringaldehyde, salicylaldehyde or hydroxymethylfurfural.
5. The method for preparing a triazine ring structure-containing bio-based epoxy resin according to claim 4, wherein the solvent used in the step (2) is dichloromethane, dichloroethane or chloroform.
6. The method for preparing a triazine ring structure-containing bio-based epoxy resin according to claim 2,3 or 5, wherein the phase transfer catalyst used in the step (3) is benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetrabutylammonium hydrogen sulfate.
7. The method for preparing a triazine ring structure-containing bio-based epoxy resin according to claim 4, wherein the phase transfer catalyst used in the step (3) is benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetrabutylammonium hydrogen sulfate.
8. The method for preparing a triazine ring structure-containing bio-based epoxy resin according to claim 2,3, 5 or 7, wherein the curing agent in the step (4) is one or a mixture of two or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, isophoronediamine, N-aminoethylpiperazine, bis (4-aminocyclohexyl) methane, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, pyromellitic anhydride, phenylketotetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexyltetracarboxylic dianhydride, trimellitic anhydride.
9. The method for preparing a triazine ring structure-containing bio-based epoxy resin according to claim 4, wherein the curing agent in the step (4) is one or a mixture of two or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, isophoronediamine, N-aminoethylpiperazine, bis (4-aminocyclohexyl) methane, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, pyromellitic anhydride, phenylketotetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexyltetracarboxylic dianhydride, and trimellitic anhydride.
10. The method for preparing a triazine ring structure-containing bio-based epoxy resin according to claim 5, wherein the curing agent in the step (4) is one or a mixture of two or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, isophoronediamine, N-aminoethylpiperazine, bis (4-aminocyclohexyl) methane, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, pyromellitic anhydride, phenylketotetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexyltetracarboxylic dianhydride, and trimellitic anhydride.
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| CN113788823A (en) * | 2021-09-13 | 2021-12-14 | 长春工业大学 | Vanillin-based bio-based epoxy resin and preparation method thereof |
| CN114573790A (en) * | 2022-03-17 | 2022-06-03 | 宁波锋成先进能源材料研究院有限公司 | Bio-based degradable epoxy resin, preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788823A (en) * | 2021-09-13 | 2021-12-14 | 长春工业大学 | Vanillin-based bio-based epoxy resin and preparation method thereof |
| CN113788823B (en) * | 2021-09-13 | 2024-01-19 | 长春工业大学 | Biological-based epoxy resin based on vanillin and preparation method thereof |
| CN114573790A (en) * | 2022-03-17 | 2022-06-03 | 宁波锋成先进能源材料研究院有限公司 | Bio-based degradable epoxy resin, preparation method and application thereof |
| CN114573790B (en) * | 2022-03-17 | 2023-11-17 | 宁波锋成绿能环保科技有限公司 | Bio-based degradable epoxy resin, preparation method and application thereof |
| CN115246643A (en) * | 2022-05-16 | 2022-10-28 | 大连理工大学 | Preparation method of biological-based polyatomic co-doped porous carbon material |
| CN115028789A (en) * | 2022-06-10 | 2022-09-09 | 哈尔滨理工大学 | Preparation and application of covalent organic framework material containing Salen group |
| CN115894466A (en) * | 2023-03-08 | 2023-04-04 | 东营市赫邦化工有限公司 | Preparation method of epoxy resin |
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