CN114907536A - Multifunctional benzoxazine resin and preparation method thereof - Google Patents
Multifunctional benzoxazine resin and preparation method thereof Download PDFInfo
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- CN114907536A CN114907536A CN202210487802.4A CN202210487802A CN114907536A CN 114907536 A CN114907536 A CN 114907536A CN 202210487802 A CN202210487802 A CN 202210487802A CN 114907536 A CN114907536 A CN 114907536A
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- benzoxazine resin
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- quercetin
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- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 8
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 claims abstract description 21
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229960001285 quercetin Drugs 0.000 claims abstract description 21
- 235000005875 quercetin Nutrition 0.000 claims abstract description 21
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 12
- -1 amine compound Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 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
- 239000000203 mixture Substances 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 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 235000013824 polyphenols Nutrition 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 230000001476 alcoholic effect Effects 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000013035 low temperature curing Methods 0.000 abstract description 4
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 7
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 6
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical group CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 5
- 229960001669 kinetin Drugs 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical group O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of thermosetting resin, and relates to a multifunctional benzoxazine resin and a preparation method thereof, in particular to trifunctional benzoxazine containing phenolic hydroxyl, alcoholic hydroxyl and intramolecular hydrogen bond and a preparation method thereof, wherein the preparation method comprises the following steps: mixing quercetin, amine compound and paraformaldehyde, adding into low-polarity solvent for reaction, reacting at 70-130 deg.C for 2-10 hr, removing organic solvent by rotary evaporation, and drying to obtain the final product. The invention has the advantages that the quercetin is used as the phenol source of the benzoxazine resin, the synthesized benzoxazine resin has a multifunctional structure, and the molecules contain phenolic hydroxyl and alcoholic hydroxyl, so that the resin can be effectively stored and has low-temperature curing characteristics, and meanwhile, the benzoxazine resin has excellent thermodynamic performance. The method has simple synthesis steps, and the cured benzoxazine resin has excellent thermal and mechanical properties and low requirements on production equipment, and is suitable for large-scale production.
Description
Technical Field
The invention is applicable to the technical field of thermosetting resin, and particularly relates to a multifunctional benzoxazine resin and a preparation method thereof.
Background
The benzoxazine is a compound synthesized by taking phenols, aldehydes and primary amine compounds as raw materials. It is a high-performance thermosetting resin, and has the advantages of good thermal stability, low water absorption, high carbon residue rate, easy processing and molding, curing zero volume shrinkage and the like. Benzoxazine resins have been widely used in the aerospace, automotive, electronic and defense industries.
Currently, global economic and social development faces two prominent problems of petroleum resource shortage and environmental pollution. In view of the current situation, a research trend of preparing high polymer materials by using bio-renewable resources instead of petroleum raw materials is promoted all over the world. With the increasing emphasis on the living environment of human beings, the substitution of bio-based polymer materials for petroleum-based polymer materials is a necessary way for green sustainable development.
To improve the thermo-mechanical properties of benzoxazines, petroleum-based groups such as acetylene, allyl, nitrile and maleimide can be incorporated into the benzoxazine structure, with the result that environmental problems caused by petroleum feedstocks remain unavoidable. Compared with the traditional petroleum-based benzoxazine, the benzoxazine produced by taking bio-based materials as raw materials becomes an effective way for sustainable development at the present stage. But the curing temperature of the bio-based benzoxazine is generally higher, so that the processing difficulty of the resin is increased.
Aiming at the problems, the invention designs a quercetin-based bio-based benzoxazine resin and a preparation method thereof. The quercetin is rich in hydroxyl, wherein one phenolic hydroxyl protected by adjacent ketone groups does not participate in oxazine ring cyclization reaction due to the formation of intramolecular hydrogen bonds, and the unreacted phenolic hydroxyl can catalyze the oxazine ring opening reaction after the constraint of the hydrogen bonds is broken. On the other hand, alcoholic hydroxyl on the other side of the ketone group can weaken the strength of hydrogen bonds in molecules, so that the hydrogen bonds are broken at low temperature, and the activity of phenolic hydroxyl is released, so that the resin has the low-temperature curing characteristic.
Disclosure of Invention
Aiming at the problems of environmental and self performance defects of the existing benzoxazine resin, the invention takes the bio-based quercetin as a phenol source, so that the raw materials are environment-friendly, the quercetin can synthesize the bio-based benzoxazine resin with easy storage and low-temperature curing property, and the tri-functional resin structure can promote the cured product to form a high-crosslinking compact structure. Compared with other reported benzoxazine resins, the quercetin-based bio-based benzoxazine resin disclosed by the invention has the characteristics of lower curing temperature, high temperature resistance and the like.
One of the purposes of the invention is to provide a multifunctional benzoxazine resin, the molecular chemical structural formula of which is shown as follows:
the second purpose of the invention is to provide a preparation method for synthesizing the multifunctional biological benzoxazine resin by taking quercetin as a phenol source.
Taking quercetin, amine compounds and paraformaldehyde as raw materials to prepare benzoxazine, wherein 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 quercetin, amine compounds and paraformaldehyde, adding into a reaction flask, adding an organic solvent, reacting at 70-130 ℃ for 2-10h, stopping the reaction, removing the solvent by rotary evaporation, and drying the product to obtain a solid product, namely the quercetin-based bio-benzoxazine resin. The molar ratio of the quercetin to the amine compound to the paraformaldehyde is 1: 3: 6-1: 3: 8.
further, the optimal molar ratio of the quercetin to the amine compound to the paraformaldehyde is 1: 3: 6.5.
the organic solvent is one or a mixture of several of dioxane, toluene and xylene.
Compared with the prior art, the invention has the advantages that:
the bio-based quercetin is used as a phenol source to synthesize the trifunctional benzoxazine resin containing phenolic hydroxyl and alcoholic hydroxyl, one phenolic hydroxyl protected by adjacent ketone groups in the resin structure does not participate in an oxazine ring-opening reaction due to the formation of intramolecular hydrogen bonds, and unreacted phenolic hydroxyl breaks the restriction of the hydrogen bonds and can catalyze the oxazine ring-opening reaction. On the other hand, alcoholic hydroxyl on the other side of the ketone group can weaken the strength of hydrogen bonds in molecules, so that the hydrogen bonds are broken at low temperature, and the activity of phenolic hydroxyl is released, so that the resin has the low-temperature curing characteristic. The benzoxazine has very low curing temperature and excellent thermal property and mechanical property, the curing peak temperature is 150-210 ℃, the glass transition temperature is 250-400 ℃, and the carbon residue rate is 60-80% 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 is a nuclear magnetic resonance hydrogen spectrum of the benzoxazine resin obtained in example 1;
FIG. 2 is an infrared spectrum of the benzoxazine resin obtained in example 1;
FIG. 3 is a DSC spectrum of the benzoxazine resin obtained in example 1;
FIG. 4 is a TGA spectrum of the cured material of benzoxazine resin obtained in example 1.
Detailed Description
The following provides a specific embodiment of a multifunctional benzoxazine resin and a method for preparing the same according to the present invention. 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:
example 1
2-furanmethanamine is used as an amine source. 1g (0.0033mol) of quercetin, 0.974g (0.0101mol) of 2-furanmethanamine, and 0.656g (0.0218mol) of paraformaldehyde were added to the flask, 50ml of a toluene solution was added, a condenser tube was attached, and stirred and reacted at 110 ℃ for 8 hours. After the reaction was stopped, the solvent was removed by rotary evaporation, and dried in a vacuum oven at 50 ℃ for one day to obtain 1.63g of a benzoxazine monomer in a yield of 75%. The chemical reaction equation is as follows:
in this example, the structure of the obtained oxazine product is:
the nuclear magnetic resonance hydrogen spectrogram, Fourier infrared transform spectrogram, DSC curve chart and thermogravimetry curve chart of the product are shown in figure 1, figure 2, figure 3 and figure 4.
FIG. 1 shows a NMR chart. Chemical shifts of 5.09, 5.06, 4.97ppm and 4.25, 4.11, 4.07ppm are characteristic peaks of the oxazine ring upper methylene. FIG. 2 is an infrared spectrum of 929cm -1 And 1241cm -1 The position is a characteristic absorption peak of the benzoxazine ring. FIG. 3 is a DSC graph showing that the peak temperature of the benzoxazine monomer curing exotherm is 189 ℃. FIG. 4 is a TGA graph of the cured resin material, and it can be seen that the temperature of the benzoxazine resin with 5% thermal weight loss is 371 ℃, and the carbon residue rate under the inert gas condition of 800 ℃ is 66%. The glass transition temperature of the cured resin material was 321 ℃.
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: weighing 1g (0.0033mol) of quercetin, 0.9244g (0.0099mol) of aniline and 0.6551g (0.0218mol) of paraformaldehyde. The yield thereof was found to be 81%.
The curing exothermic peak temperature of the polyfunctional benzoxazine resin monomer obtained in the embodiment is 172 ℃, after further curing and crosslinking, the polybenzoxazine resin has a temperature of 366 ℃ when the thermal weight loss is 5%, a carbon residue rate of 60% under an inert gas atmosphere of 800 ℃ and a glass transition temperature of 295 ℃.
Example 3
The amine source compound 2-furanmethanamine in example 1 was replaced with 4-methylaniline. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the 4-methylaniline is as follows:the amounts of reactants were changed to: weighing 1g (0.0033mol) of quercetin, 1.0637g (0.0099mol) of 4-methylaniline and 0.6551g (0.0218mol) of paraformaldehyde. The yield thereof was found to be 83%.
The curing exothermic peak temperature of the polyfunctional benzoxazine resin monomer obtained in the embodiment is 167 ℃, after further curing and crosslinking, the polybenzoxazine resin has the temperature of 358 ℃ when the thermal weight loss is 5%, the carbon residue rate of 61% under the inert gas atmosphere of 800 ℃ and the glass transition temperature of 281 ℃.
Example 4
The amine source compound 2-furanmethanamine in example 1 was replaced with 3-alkynylaniline. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the 3-alkynyl aniline is as follows:the amounts of reactants were changed to: weighing 1g (0.0033mol) of quercetin, 1.1628g (0.0109mol) of 3-alkynyl aniline and 0.6551g (0.0218mol) of paraformaldehyde. The yield thereof was found to be 76%.
The curing exothermic peak temperature of the polyfunctional benzoxazine resin monomer obtained in the embodiment is 162 ℃, after further curing and crosslinking, the polybenzoxazine resin has a temperature of 410 ℃ when the thermal weight loss is 5%, a carbon residue rate of 72% under an inert gas atmosphere of 800 ℃ and a glass transition temperature of 385 ℃.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
2. the multifunctional benzoxazine resin according to claim 1, wherein the curing peak temperature is 150-210 ℃, the multifunctional benzoxazine resin is further cured and crosslinked to obtain the polybenzoxazine resin, the glass transition temperature is 250-400 ℃, and the carbon residue rate is 60-80% under the condition of an inert gas atmosphere of 800 ℃.
3. A method for preparing the multifunctional benzoxazine resin according to any one of claims 1 to 2, comprising the steps of:
mixing quercetin, amine compounds and paraformaldehyde, adding an organic solvent, reacting at 70-130 ℃ for 2-10h, stopping the reaction, removing the solvent by rotary evaporation, and drying the product to obtain a solid product, namely the multifunctional biological benzoxazine resin.
5. the method for preparing the multifunctional benzoxazine resin according to claim 3, wherein the molar ratio of quercetin to the amine compound to paraformaldehyde is 1: 3: 6-1: 3: 8.
6. the method for preparing the multifunctional benzoxazine resin according to claim 5, wherein the optimal molar ratio of quercetin to the amine compound to paraformaldehyde is 1: 3: 6.5.
7. the method for preparing the multifunctional benzoxazine resin according to claim 3, wherein the organic solvent is one or a mixture of dioxane, toluene and xylene.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN113121772A (en) * | 2021-03-26 | 2021-07-16 | 江苏大学 | Pterostilbene benzoxazine-based resin and preparation method thereof |
CN113845638A (en) * | 2021-07-29 | 2021-12-28 | 镇江利德尔复合材料有限公司 | Bio-based water-soluble benzoxazine resin and preparation method thereof |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN113121772A (en) * | 2021-03-26 | 2021-07-16 | 江苏大学 | Pterostilbene benzoxazine-based resin and preparation method thereof |
CN113845638A (en) * | 2021-07-29 | 2021-12-28 | 镇江利德尔复合材料有限公司 | Bio-based water-soluble benzoxazine resin and preparation method thereof |
Non-Patent Citations (1)
Title |
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李常风: "《典型天然药物的化学成分及其研究开发新探》", vol. 1, 31 March 2019, 吉林大学出版社, pages: 97 - 99 * |
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