CN115403766A - Kaempferol-based bio-based benzoxazine resin and preparation method thereof - Google Patents
Kaempferol-based bio-based benzoxazine resin and preparation method thereof Download PDFInfo
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- CN115403766A CN115403766A CN202210519717.1A CN202210519717A CN115403766A CN 115403766 A CN115403766 A CN 115403766A CN 202210519717 A CN202210519717 A CN 202210519717A CN 115403766 A CN115403766 A CN 115403766A
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- IYRMWMYZSQPJKC-UHFFFAOYSA-N kaempferol Chemical compound C1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 IYRMWMYZSQPJKC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 60
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- UBSCDKPKWHYZNX-UHFFFAOYSA-N Demethoxycapillarisin Natural products C1=CC(O)=CC=C1OC1=CC(=O)C2=C(O)C=C(O)C=C2O1 UBSCDKPKWHYZNX-UHFFFAOYSA-N 0.000 title claims abstract description 33
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 235000008777 kaempferol Nutrition 0.000 title claims abstract description 33
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 12
- -1 amine compounds Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 238000001723 curing Methods 0.000 abstract description 12
- 235000013824 polyphenols Nutrition 0.000 abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229960001669 kinetin Drugs 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- NJXPYZHXZZCTNI-UHFFFAOYSA-N 3-aminobenzonitrile Chemical group NC1=CC=CC(C#N)=C1 NJXPYZHXZZCTNI-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 2
- 150000005130 benzoxazines Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention belongs to the technical field of thermosetting resin, and relates to a kaempferol-based bio-based benzoxazine resin and a preparation method thereof, in particular to benzoxazine with two unreacted hydroxyl groups in a single molecule and a preparation method thereof. Mixing kaempferol, amine compounds and paraformaldehyde, adding into a round-bottom flask, adding a proper amount of organic solvent, filtering to remove precipitates after the reaction is finished, washing the filtrate with deionized water, performing rotary evaporation, and drying to obtain the bio-based benzoxazine resin. The invention has the advantages that bio-based kaempferol is used as a phenol source of the benzoxazine resin, the synthesized benzoxazine has unreacted phenolic hydroxyl protected by hydrogen bonds, the phenolic hydroxyl can weaken the intramolecular hydrogen bonds where the phenolic hydroxyl is located at lower temperature, the ring-opening curing of the benzoxazine catalyzed by dissociating hydrogen ions at low temperature is realized, the curing temperature of the resin is effectively reduced, the cured benzoxazine resin has excellent thermal and mechanical properties due to the rich hydrogen bonds, the synthesis process is easy to implement, and the method is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin, and particularly relates to a kaempferol-based bio-based benzoxazine resin and a preparation method thereof.
Background
Polybenzoxazines are a new class of high performance thermosetting resins. The precursor benzoxazine is usually obtained by a Mannich condensation reaction of a phenolic compound, a primary amine compound and formaldehyde (paraformaldehyde). Under the action of heating and/or catalyst, the benzoxazine undergoes ring-opening polymerization to form a three-dimensional network structure similar to phenolic resin, namely polybenzoxazine. The obtained polybenzoxazine resin generally has excellent performances of low flammability, low dielectric constant, high thermal stability, excellent thermodynamic property, low surface energy and the like, and therefore has wide development prospects in the fields of buildings, electronics, aerospace and the like.
With the rise of green chemistry and the morphological change of people in environmental awareness, the research prospect of the traditional organic chemistry is limited, and researchers have to aim at the biological-based raw materials with huge reserves. The emergence of green chemistry is probably the trigger for rapid development for benzoxazines. Compared to the simple functional group and limited reserves of petroleum-based raw materials, bio-based materials exhibit complex and diverse functional systems and can be supplied continuously, and these functional structures and renewable advantages are not possessed by petroleum-based raw materials. In addition, it is worth noting that the current reports on bio-based benzoxazines are single, mainly adopt single oxazine ring or local modification, and are slightly insufficient in mechanics, ablation resistance and weather resistance; few reports are reported about the systematic study of bio-based multifunctional benzoxazine.
Based on the problems, the invention designs the kaempferol bio-based benzoxazine resin and the preparation method thereof. The method takes kaempferol as a phenol source to synthesize a bifunctional benzoxazine monomer containing phenolic hydroxyl and alcoholic hydroxyl simultaneously, and the phenolic hydroxyl protected by hydrogen bonds in the monomer can lose activity at room temperature, so that the storability of the resin is ensured. And the other alcoholic hydroxyl in the molecular structure can weaken the strength of hydrogen bonds in molecules, so that the phenolic hydroxyl can excite the catalytic activity at a lower temperature, and the polymerization temperature of the resin is obviously reduced. In addition, the existence of abundant intermolecular hydrogen bonds in the synthesized benzoxazine resin can enable the resin to have higher thermal stability and mechanical properties. The development of the novel bio-based benzoxazine resin has important significance for new materials capable of being developed sustainably.
Disclosure of Invention
In view of some problems of the existing benzoxazine resin and the current research situation of the bio-based high-performance resin, the invention synthesizes the benzoxazine resin with the characteristics of easy storage and low-temperature curing by taking bio-based kaempferol as a phenol source. The benzoxazine resin has very low curing temperature due to the existence of hydrogen bonds, and the completely cured benzoxazine resin also has very excellent thermal stability and mechanical properties.
The invention aims to provide benzoxazine taking bio-based kaempferol as a phenol source and a preparation method thereof, wherein the bio-based benzoxazine resin is prepared, so that the curing temperature of the benzoxazine resin is greatly reduced, and the thermal property and the mechanical property of the benzoxazine resin are improved.
The purpose of the invention is realized by the following technical scheme:
one of the purposes of the invention is to provide a kaempferol bio-based benzoxazine resin, the molecular chemical structural formula of which is as follows:
wherein,
is one of the following structures:
the second purpose of the invention is to provide a preparation method of bio-based benzoxazine resin with kaempferol as a phenol source.
The method is characterized in that kaempferol, amine compounds and paraformaldehyde are used as raw materials to prepare benzoxazine, and the chemical reaction equation is as follows:
the structural formula of the amine compound is R-NH 2 Is one of the following structures:
the method specifically comprises the following steps:
mixing kaempferol, an amine compound and paraformaldehyde, adding into a round-bottom flask, adding a proper amount of organic solvent, reacting at 80-120 ℃ for 6-12h, filtering to remove unreacted raw materials after the reaction is finished, washing the filtrate with deionized water for three times, performing rotary evaporation, and drying to obtain a solid product, namely the kaempferol-based bio-based benzoxazine resin.
The molar ratio of the kaempferol to the amine compound to the paraformaldehyde is 1:2: (4-5), preferably in a ratio of 1:2:4.4.
the organic solvent is one or a mixture of several of toluene, xylene and 1,4 dioxane.
Compared with the prior art, the invention has the advantages that:
the bio-based kaempferol is used as a phenol source to synthesize the bifunctional benzoxazine resin containing phenolic hydroxyl and alcoholic hydroxyl, and the phenolic hydroxyl protected by hydrogen bonds can lose activity at room temperature, so that the storability of the resin is ensured. The other alcoholic hydroxyl in the molecular structure can weaken the strength of hydrogen bonds in molecules, so that the phenolic hydroxyl can excite the catalytic activity at a lower temperature, and the polymerization temperature of the resin is obviously reduced; in addition, abundant intermolecular hydrogen bonds of the cured polybenzoxazine resin improve the thermal stability and the mechanical property of the resin to different degrees; the resin has a curing peak temperature of 150-200 ℃ and a carbon residue rate of 65-80% at 800 ℃ in an inert gas atmosphere; the synthesis process is simple, the yield is high, the requirement on equipment is low, and the method is suitable for large-scale production.
Drawings
FIG. 1 nuclear magnetic resonance hydrogen spectrum of benzoxazine resin obtained in example 1;
FIG. 2 is an infrared spectrum of the benzoxazine resin obtained in example 1;
FIG. 3 DSC spectrum of benzoxazine resin obtained in example 1;
FIG. 4 TGA spectrum of cured benzoxazine resin obtained in example 1.
Detailed Description
The following provides a specific embodiment of the kaempferol bio-based benzoxazine resin and the preparation method thereof. It is to be noted that: the following examples are intended only to illustrate the present invention in more detail, and do not narrow the scope of the present invention. Modifications and adaptations of the present invention may occur to those skilled in the art after reading the present invention and may be made without departing from the spirit and scope of the present invention as defined by the appended claims.
Example 1:
2-furanmethylamine is used as an amine source; 1g (0.0035 mol) of kaempferol, 0.678g (0.007 mol) of 2-furanmethanamine and 0.462g (0.0154 mol) of paraformaldehyde are added into a 100mL round-bottom flask, then 50mL of toluene solution is added, a condenser tube is connected, and the mixture is stirred for 6 hours at 120 ℃; after the reaction was stopped, the reaction mixture was cooled to room temperature, filtered to remove precipitates, the filtrate was washed with deionized water, then rotary-evaporated, and dried in a vacuum oven at 50 ℃ for one day to obtain 1.57g of benzoxazine monomer, with a yield of 85%. The chemical reaction equation is as follows:
in this example, the structure of the obtained oxazine product is:
the nuclear magnetic resonance hydrogen spectrum, fourier infrared transform spectrum, DSC curve chart and thermal weight loss curve chart of the product are shown in figure 1, figure 2, figure 3 and figure 4.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum, and from the graph, chemical shifts of 5.00 ppm and 4.99ppm and chemical shifts of 4.22 ppm and 4.11ppm are the characteristic peaks of methylene on the oxazine ring.
FIG. 2 is an infrared spectrum showing 923cm -1 And 1239cm -1 The position is a characteristic absorption peak of the benzoxazine ring.
FIG. 3 is a DSC chart showing the exothermic peak temperature of the benzoxazine monomer curing at 184 ℃.
Fig. 4 is a TGA graph of the cured resin material, and it can be seen that the temperature of the benzoxazine resin at 5% weight loss by heat was 329 deg.c and the carbon residue rate at 800 deg.c was 64%.
Example 2:
the amine source compound 2-furanmethanamine in example 1 was replaced with aniline. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the aniline is as follows:
the amounts of reactants were changed to: 1g (0.0035 mol) of kaempferol, 0.651g (0.007 mol) of aniline, and 0.462g (0.0154 mol) of paraformaldehyde were weighed out, and the yield was 88%.
The monomer of the bio-based benzoxazine resin obtained in the embodiment has a curing exothermic peak temperature of 175 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a temperature of 372 ℃ when the thermal weight loss is 5%, and a carbon residue rate of 65% when the temperature is 800 ℃ under an inert gas atmosphere.
Example 3:
the amine source compound 2-furanmethanamine in example 1 was replaced with 3-aminophenylacetylene. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the 3-aminophenylacetylene is shown as
The amounts of reactants were changed to: weighing 1g (0.0035 mol) of kaempferol and 3-ammoniaPhenylacetylene 0.819g (0.007 mol), paraformaldehyde 0.462g (0.0154 mol) yield 80%.
The curing exothermic peak temperature of the bio-based benzoxazine resin monomer obtained in the embodiment is 164 ℃, after further curing and crosslinking, the temperature of the polybenzoxazine resin is 386% when the thermal weight loss is 5%, and the carbon residue rate is 72% when the polybenzoxazine resin is in an inert gas atmosphere of 800 ℃.
Example 4:
the amine source compound 2-furanmethanamine in example 1 was replaced with 3-aminobenzonitrile. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the 3-aminobenzonitrile is as follows:
the amounts of reactants were changed to: 1g (0.0035 mol) of kaempferol, 0.826g (0.007 mol) of 3-aminobenzonitrile and 0.462g (0.0154 mol) of paraformaldehyde were weighed out in a yield of 83%.
The curing exothermic peak temperature of the bio-based benzoxazine resin monomer obtained in the embodiment is 198 ℃, after further curing and crosslinking, the temperature of the polybenzoxazine resin is 412 ℃ when the thermal weight loss is 5%, and the carbon residue rate is 71% when the polybenzoxazine resin is in an inert gas atmosphere of 800 ℃.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the various embodiments thereof, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and within the scope of the following claims.
Claims (7)
1. A bio-based benzoxazine resin based on kaempferol is characterized in that the molecular formula is as follows:
wherein,
is one of the following structures:
2. the kaempferol-based bio-based benzoxazine resin according to claim 1, wherein the curing peak temperature is 150-200 ℃, and the bio-based benzoxazine resin is further cured and crosslinked to obtain a polybenzoxazine resin, and the char yield is 60-80% under the inert atmosphere condition of 800 ℃.
3. A method for preparing a kaempferol-based bio-based benzoxazine resin as claimed in any one of claims 1-2, comprising the following steps:
mixing kaempferol, an amine compound and paraformaldehyde, adding an organic solvent, reacting at 80-120 ℃ for 6-12h, filtering to remove unreacted raw materials after the reaction is finished, washing with water, performing rotary evaporation, and drying to obtain a solid product, namely the kaempferol-based bio-based benzoxazine resin.
4. The method for preparing the kaempferol bio-based benzoxazine-based resin according to claim 3, wherein the amine compound has a structural formula of R-NH 2 Is one of the following structures:
5. the method for preparing the kaempferol bio-based benzoxazine-based resin according to claim 3, wherein the molar ratio of kaempferol, the amine compound and paraformaldehyde is 1:2:4 to 5.
6. The method for preparing the kaempferol bio-based benzoxazine-based resin according to claim 5, wherein the molar ratio of kaempferol, the amine compound and paraformaldehyde is 1:2:4.4.
7. the method for preparing the kaempferol bio-based benzoxazine resin according to claim 3, wherein the organic solvent is one or a mixture of toluene, xylene and 1, 4-dioxane.
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| CN117050271A (en) * | 2023-09-19 | 2023-11-14 | 常州宏巨电子科技有限公司 | Amide-containing bio-based benzoxazine/epoxy resin copolymer and preparation method thereof |
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| CN111269395A (en) * | 2020-04-14 | 2020-06-12 | 镇江利德尔复合材料有限公司 | Benzoxazine epoxy resin copolymer containing phenolic hydroxyl and preparation method thereof |
| CN115386059A (en) * | 2021-05-24 | 2022-11-25 | 中国科学院宁波材料技术与工程研究所 | Bio-based benzoxazine precursor and preparation method and application thereof |
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|---|---|---|---|---|
| CN110240684A (en) * | 2019-05-29 | 2019-09-17 | 江苏大学 | A kind of latent curing type benzoxazine resin and preparation method thereof |
| CN110951018A (en) * | 2019-12-30 | 2020-04-03 | 江苏大学 | Apigenin-based bio-based benzoxazine resin and preparation method thereof |
| CN111269395A (en) * | 2020-04-14 | 2020-06-12 | 镇江利德尔复合材料有限公司 | Benzoxazine epoxy resin copolymer containing phenolic hydroxyl and preparation method thereof |
| CN115386059A (en) * | 2021-05-24 | 2022-11-25 | 中国科学院宁波材料技术与工程研究所 | Bio-based benzoxazine precursor and preparation method and application thereof |
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| CN117050271A (en) * | 2023-09-19 | 2023-11-14 | 常州宏巨电子科技有限公司 | Amide-containing bio-based benzoxazine/epoxy resin copolymer and preparation method thereof |
| CN117050271B (en) * | 2023-09-19 | 2024-05-07 | 常州宏巨电子科技有限公司 | Amide-containing bio-based benzoxazine/epoxy resin copolymer and preparation method thereof |
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Application publication date: 20221129 |