CN115093544A - Schiff base structure syringaldehyde-based epoxy resin and preparation method thereof - Google Patents
Schiff base structure syringaldehyde-based epoxy resin and preparation method thereof Download PDFInfo
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- CN115093544A CN115093544A CN202210634491.XA CN202210634491A CN115093544A CN 115093544 A CN115093544 A CN 115093544A CN 202210634491 A CN202210634491 A CN 202210634491A CN 115093544 A CN115093544 A CN 115093544A
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- 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 schiff base structure syringaldehyde-based epoxy resin and a preparation method thereof, and belongs to the technical field of bio-based high polymer materials. Taking syringaldehyde as a raw material of a bio-based compound, firstly converting aldehyde group in the syringaldehyde into a bisphenol monomer with a Schiff base structure, and then reacting the bisphenol monomer with the Schiff base structure with epichlorohydrin under the action of a phase transfer catalyst to finally obtain a syringaldehyde-based epoxy resin precursor with the Schiff base structure. The thermosetting epoxy resin obtained by curing the prepared schiff base structure syringaldehyde epoxy monomer can replace the existing petroleum-based related products, and the preparation method has the advantages of high efficiency, convenient operation, good controllability, production by utilizing the existing chemical equipment, high yield and purity, suitability for large-scale industrial production, and application in the high and new technical fields of aerospace and the like.
Description
Technical Field
The invention belongs to the technical field of bio-based polymer materials, and particularly relates to syringaldehyde-based epoxy resin with a Schiff base structure and a preparation method thereof.
Background
Epoxy resin is a thermosetting resin which is most widely applied, and has the advantages of good adhesion, electrical insulation, chemical corrosion resistance, good processability, low curing shrinkage and the like, so that the epoxy resin is widely applied to the fields of coatings, adhesives, electronic packaging, composite materials and the like. However, the epoxy resins currently available are basically prepared from petroleum-based raw materials, and the bisphenol a type epoxy resin, which is prepared from bisphenol a and epichlorohydrin, accounts for more than 85% of the total epoxy resin production. Although epichlorohydrin can be obtained by conversion from glycerol, which is a bio-based raw material, bisphenol a can be prepared only from petroleum-based raw materials, and petroleum resources are consumed and exhausted increasingly, so that the petroleum price is soared, and meanwhile, a series of severe environmental problems are brought about, which bring great pressure to the development of epoxy resins which take 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. Therefore, 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 corresponding bio-based epoxy resin is further prepared to effectively solve the problems.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the syringyl aldehyde-based epoxy resin with the Schiff base structure, which is obtained by converting biomass syringaldehyde, accords with the concept of green and environment-friendly sustainable development, and has the advantages of simple preparation method and easiness in implementation, and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a syringaldehyde-based epoxy resin with Schiff base structure has the following structure:
wherein the R group is:
A preparation method of the schiff base structure syringaldehyde-based epoxy resin with the structure specifically comprises the following steps:
s1, a syringaldehyde bisphenol monomer containing a Schiff base structure: dissolving an amino compound into absolute ethyl alcohol, adding an absolute ethyl alcohol solution of syringaldehyde, adding the amino compound and the syringaldehyde according to the molar ratio of 1: 1-4, heating the system to 80-100 ℃, reacting for 3-10 h, pouring into distilled water, extracting with ethyl acetate, separating, drying an ethyl acetate layer, distilling under reduced pressure, removing a solvent, washing with ethanol for 3-6 times, and drying under vacuum to obtain a schiff base structure syringaldehyde bisphenol monomer;
s2, a syringaldehyde-based epoxy monomer containing a Schiff base structure: adding a Schiff base ring structure syringomyl bisphenol monomer of S1, a phase transfer catalyst and epoxy chloropropane according to a molar ratio of 1: 0.001-0.5: 10-100, heating to 50-100 ℃, reacting for 2-8 h under a nitrogen atmosphere, dropwise adding a sodium hydroxide solution with a concentration of 25-45 wt% (w/w) into the system, wherein the molar ratio of the sodium hydroxide to the Schiff base ring structure syringomyl bisphenol monomer is 2-4: 1, 25-100 ℃, reacting for 1-5 h under the nitrogen atmosphere, performing suction filtration, extracting, drying an organic layer, performing reduced pressure distillation, removing the solvent, and drying the product in a vacuum oven to obtain the Schiff base structure syringomyl epoxy monomer with an epoxy value of 0.29-0.31;
s3, syringaldehyde-based epoxy resin with Schiff base structure: and (3) uniformly mixing the syringomyl epoxy monomer containing the Schiff base structure prepared in the step (S2) with a curing agent, defoaming in vacuum, pouring the system into a mold after no bubbles exist, and carrying out thermosetting molding to obtain a bio-based epoxy resin cured product, namely the syringomyl epoxy resin containing the Schiff base structure.
Preferably, in S1, the amino compound is one of 4,4' -diaminodiphenylmethane, 4' -diaminodiphenyl ether, or 4,4' -diaminodiphenyl sulfone.
Preferably, in S2, the phase transfer catalyst is one of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetrabutylammonium hydrogen sulfate.
Preferably, in S3, the curing agent is one or a mixture of two or more selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, isophoronediamine, N-aminoethylpiperazine, bis (4-aminocyclohexyl) methane, trioctylmethylamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, pyromellitic anhydride, phenonetetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexenyltetracarboxylic dianhydride, and trimellitic anhydride.
Preferably, in S3, the syringyl aldehyde group-containing epoxy monomer with Schiff base structure and the curing agent are mixed according to the molar ratio of 1: 0.15-2.
Preferably, in S3, the system is poured into a mould, and is insulated for 1-4 hours at 60-100 ℃, and then is insulated for 2-6 hours at 100-130 ℃ for thermosetting molding.
Compared with the prior art, the invention has the beneficial effects that:
1. the syringaldehyde-based epoxy resin with Schiff base structure provided by the invention is obtained by completely converting syringaldehyde-based bio-based monomers, and is a novel epoxy resin; the problem that the petroleum-based epoxy resin excessively depends on petrochemical resources at present can be solved, the aims of saving the petrochemical resources, protecting the environment and developing sustainability are met, and the development of bio-based materials is promoted.
2. The method for preparing the Schiff base structure-containing compound from the biobased raw material syringaldehyde provided by the invention develops a preparation method of the Schiff base structure biobased compound, and has important significance for constructing a high-performance biobased high polymer material.
3. The thermosetting epoxy resin obtained by finally curing the schiff base structure syringaldehyde epoxy resin provided by the invention can be used as a high-performance epoxy resin to be applied to the high and new technical fields of aerospace and the like.
4. The preparation method disclosed by the invention is efficient, convenient to operate, good in controllability, capable of realizing production by adopting the existing chemical equipment, high in product yield and purity and suitable for large-scale industrial production.
Drawings
FIG. 1 shows the NMR spectrum of Schiff base structure syringomyl-based epoxy resin DDM-2SH-EP of example 1.
Detailed Description
The invention will be further explained and explained with reference to the drawings and the embodiments.
Example 1
A preparation method of schiff base structure syringaldehyde group epoxy resin specifically comprises the following steps:
s1, synthesizing a Schiff base structure syringomyl bisphenol monomer (DDM-2 SH): 0.99g of 4,4' -diaminodiphenylmethane was added into a 100mL three-necked flask, nitrogen gas was used for protection, 30mL of absolute ethyl alcohol was added, mechanical stirring was carried out until the absolute ethyl alcohol was completely dissolved, and 20mL of an absolute ethyl alcohol solution of 1.82g of syringaldehyde was successively added thereto, and the system was reacted at 80 ℃ for 6 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 with water for 3 times, and carrying out vacuum drying to obtain the DDM-2SH with the yield of 95%.
S2, synthesizing a schiff base structure syringomyl epoxy monomer (DDM-2 SH-EP): 13.1g of DDM-2SH, 0.8g of tetrabutylammonium bromide and 10.6g of epichlorohydrin are sequentially added into a 500mL three-neck flask equipped 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 6 hours. Subsequently, 5mL of a 40% (w/w) aqueous NaOH solution was added dropwise to the system, and the reaction was continued at 60 ℃ for 6 hours. After the reaction, suction filtration is carried out, filtrate is extracted by distilled water, liquid separation is carried out for three times, and an organic layer is taken and added with anhydrous sodium sulfate to be dried overnight. 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 50 ℃ to obtain the syringyl aldehyde group epoxy monomer DDM-2SH-EP containing Schiff base structure with the yield of 89%.
Nuclear magnetic resonance hydrogen spectrum of obtained schiff base structure syringomyl group epoxy monomer DDM-2SH-EP 1 H-NMR is shown in FIG. 1, where the peak positions and integrated areas are completely consistent with the structure of DDM-2 SH-EP.
S3, curing the DDM-2 SH-EP: uniformly mixing the obtained DDM-2SH-EP epoxy monomer and curing agent DDM according to the one-to-one molar ratio of epoxy to NH, defoaming in vacuum, pouring the system into a mold after no bubbles exist, preserving heat at 80 ℃ for 2h, and preserving heat at 110 ℃ for 4h to obtain the thermosetting epoxy resin.
Example 2
A preparation method of syringaldehyde-based epoxy resin with Schiff base structure specifically comprises the following steps:
s1, synthesizing a syringaldehyde bisphenol monomer (DDE-2SH) containing a Schiff base structure: 1g of 4,4' -diaminodiphenyl ether is added into a 100mL three-neck flask, nitrogen is protected, 30mL of absolute ethyl alcohol is added, mechanical stirring is carried out until the absolute ethyl alcohol is completely dissolved, 20mL of absolute ethyl alcohol solution of 1.82g of syringaldehyde is added into the three-neck flask successively, and the system is reacted for 6h at 80 ℃. 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 with water for 3 times, and carrying out vacuum drying to obtain DDE-2SH with the yield of 96%.
S2, synthesizing a syringaldehyde epoxy monomer (DDE-2SH-EP) containing a Schiff base structure: 13.2g of DDM-2SH, 0.8g of tetrabutylammonium bromide and 10.6g of epichlorohydrin are sequentially added into a 500mL three-neck flask equipped 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 6 hours. Subsequently, 5mL of a 40% (w/w) aqueous NaOH solution was added dropwise to the system, and the reaction was continued at 60 ℃ for 6 hours. After the reaction, suction filtration is carried out, filtrate is extracted by distilled water, liquid separation is carried out for three times, and an organic layer is taken and added with anhydrous sodium sulfate to be dried overnight. And (3) carrying out suction filtration, taking filtrate, removing the solvent through reduced pressure distillation, and drying the product in a vacuum oven at 50 ℃ to obtain the syringaldehyde epoxy monomer DDE-2SH-EP containing the Schiff base structure with the yield of 88%.
S3, curing of DDE-2 SH-EP: uniformly mixing the obtained DDE-2SH-EP epoxy monomer and curing agent DDM according to the one-to-one molar ratio of epoxy to NH, defoaming in vacuum, pouring the system into a mold after no bubbles exist, preserving heat at 80 ℃ for 2h, and preserving heat at 110 ℃ for 4h to obtain the thermosetting epoxy resin.
Example 3
A preparation method of schiff base structure syringaldehyde group epoxy resin specifically comprises the following steps:
s1, synthesizing a syringyl aldehyde bisphenol monomer (DDS-2SH) containing a Schiff base structure: 1.24g of 4,4' -diaminodiphenyl sulfone is added into a 100mL three-neck flask, nitrogen is protected, 30mL of absolute ethyl alcohol is added, mechanical stirring is carried out until the absolute ethyl alcohol is completely dissolved, 20mL of absolute ethyl alcohol solution of 1.82g of syringaldehyde is added into the three-neck flask successively, and the system is reacted for 6h at 80 ℃. 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 with water for 3 times, and carrying out vacuum drying to obtain the DDM-2SH with the yield of 93%.
S2, synthesizing a syringomyl epoxy monomer (DDS-2SH-EP) containing a Schiff base structure: 13.2g of DDS-2SH, 0.8g of tetrabutylammonium bromide and 10.6g of epoxy chloropropane are sequentially added into a 500mL 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 ℃ in a nitrogen atmosphere to react for 6 h. Subsequently, 5mL of a 40% (w/w) aqueous NaOH solution was added dropwise to the system, and the reaction was continued at 60 ℃ for 6 hours. After the reaction, suction filtration is carried out, filtrate is extracted by distilled water, liquid separation is carried out for three times, and an organic layer is taken and added with anhydrous sodium sulfate to be dried overnight. 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 50 ℃ to obtain the syringyl aldehyde group epoxy monomer DDS-2SH-EP with the Schiff base structure, wherein the yield is 89%.
S3, curing DDS-2 SH-EP: uniformly mixing the obtained DDS-2SH-EP epoxy monomer and curing agent DDM according to the one-to-one molar ratio of epoxy to NH, defoaming in vacuum, pouring the system into a mold after no bubbles exist, preserving heat at 80 ℃ for 2h, and preserving heat at 110 ℃ for 4h to obtain the thermosetting epoxy resin.
Claims (7)
1. A Schiff base structure syringaldehyde-based epoxy resin is characterized by having the following structure:
wherein the R group is:
2. the preparation method of the schiff base structure syringaldehyde based epoxy resin as claimed in claim 1, which comprises the following steps:
s1, a syringaldehyde bisphenol monomer containing a Schiff base structure: dissolving an amino compound into absolute ethyl alcohol, adding an absolute ethyl alcohol solution of syringaldehyde, adding the amino compound and the syringaldehyde according to the molar ratio of 1: 1-4, heating to 80-100 ℃, reacting for 3-10 h, pouring into distilled water, extracting with ethyl acetate, separating liquid, drying an ethyl acetate layer, distilling under reduced pressure, removing a solvent, washing with ethanol for 3-6 times, and drying under vacuum to obtain a schiff base structure syringaldehyde bisphenol monomer;
s2, a syringaldehyde-based epoxy monomer containing a Schiff base structure: adding a Schiff base ring structure syringaldehyde bisphenol monomer of S1, a phase transfer catalyst and epoxy chloropropane according to a 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 sodium hydroxide solution with a concentration of 25-45 wt% into the system, wherein the molar ratio of the sodium hydroxide to the Schiff base ring structure syringaldehyde bisphenol monomer is 2-4: 1, 25-100 ℃, reacting for 1-5 hours in the nitrogen atmosphere, performing suction filtration, extracting, drying an organic layer, performing reduced pressure distillation, removing a solvent, and drying a product in a vacuum oven to obtain the Schiff base structure syringaldehyde epoxy monomer with an epoxy value of 0.29-0.31;
s3, syringaldehyde-based epoxy resin with Schiff base structure: and (3) uniformly mixing the syringomyl epoxy monomer containing the Schiff base structure prepared in the step (S2) with a curing agent, defoaming in vacuum, pouring the system into a mold after no bubbles exist, and carrying out thermosetting molding to obtain a bio-based epoxy resin cured product, namely the syringomyl epoxy resin containing the Schiff base structure.
3. The method for preparing the schiff base structure syringaldehyde based epoxy resin as claimed in claim 2, wherein the amino compound in S1 is one of 4,4' -diaminodiphenylmethane, 4' -diaminodiphenyl ether or 4,4' -diaminodiphenyl sulfone.
4. The method for preparing a schiff base syringaldehyde based epoxy resin as claimed in claim 2 or 3, wherein in S2, the phase transfer catalyst is one of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetrabutylammonium hydrogen sulfate.
5. A preparation method of Schiff base structure syringomyl epoxy resin according to claim 4, wherein in S3, the curing agent is one or a mixture of two or more of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, isophoronediamine, N-aminoethyl piperazine, bis (4-aminocyclohexyl) methane, trioctylmethylamine, diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexenyl tetracarboxylic dianhydride, and trimellitic anhydride.
6. The preparation method of the schiff base syringoyl epoxy resin as claimed in claim 2 or 5, wherein in S3, the schiff base syringoyl epoxy monomer and the curing agent are mixed according to a molar ratio of 1: 0.15-2.
7. The preparation method of the schiff base syringaldehyde based epoxy resin as claimed in claim 6, wherein in S3, the system is poured into a mold, and the temperature is maintained at 60-100 ℃ for 1-4 h, and then the temperature is maintained at 100-130 ℃ for 2-6 h for thermosetting molding.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143732A (en) * | 2023-04-21 | 2023-05-23 | 苏州大学 | Biomass Schiff base and polymer, photo-thermal coating and preparation method thereof |
| CN117417661A (en) * | 2023-11-17 | 2024-01-19 | 温州海慕化工有限公司 | Preparation method and application of high-flash-point low-VOC diluent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958719A (en) * | 2006-11-30 | 2007-05-09 | 复旦大学 | Schiff's base type epoxy resin of liquid crystal, preparation method and application |
| WO2016172353A1 (en) * | 2015-04-21 | 2016-10-27 | Ndsu Research Foundation | Epoxy resin derived from vanillin and thermosets therefrom |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
| CN114409873A (en) * | 2022-02-21 | 2022-04-29 | 中国民用航空飞行学院 | Vanillyl intrinsic flame-retardant epoxy resin containing aliphatic amine and preparation method thereof |
| CN114853696A (en) * | 2022-05-19 | 2022-08-05 | 厦门大学 | Bio-based intrinsic flame-retardant epoxy monomer and preparation method and application thereof |
-
2022
- 2022-06-07 CN CN202210634491.XA patent/CN115093544A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958719A (en) * | 2006-11-30 | 2007-05-09 | 复旦大学 | Schiff's base type epoxy resin of liquid crystal, preparation method and application |
| WO2016172353A1 (en) * | 2015-04-21 | 2016-10-27 | Ndsu Research Foundation | Epoxy resin derived from vanillin and thermosets therefrom |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
| CN114409873A (en) * | 2022-02-21 | 2022-04-29 | 中国民用航空飞行学院 | Vanillyl intrinsic flame-retardant epoxy resin containing aliphatic amine and preparation method thereof |
| CN114853696A (en) * | 2022-05-19 | 2022-08-05 | 厦门大学 | Bio-based intrinsic flame-retardant epoxy monomer and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEIQI XIE等: "Imine-functionalized biomass-derived dynamic covalent thermosets enabled by heat-induced self-crosslinking and reversible structures", 《CHEMICAL ENGINEERING JOURNAL》, vol. 126598, no. 404 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143732A (en) * | 2023-04-21 | 2023-05-23 | 苏州大学 | Biomass Schiff base and polymer, photo-thermal coating and preparation method thereof |
| CN117417661A (en) * | 2023-11-17 | 2024-01-19 | 温州海慕化工有限公司 | Preparation method and application of high-flash-point low-VOC diluent |
| CN117417661B (en) * | 2023-11-17 | 2024-04-09 | 温州海慕化工有限公司 | Preparation method and application of high-flash-point low-VOC diluent |
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