CN113845638A - Bio-based water-soluble benzoxazine resin and preparation method thereof - Google Patents
Bio-based water-soluble benzoxazine resin and preparation method thereof Download PDFInfo
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- CN113845638A CN113845638A CN202110863205.2A CN202110863205A CN113845638A CN 113845638 A CN113845638 A CN 113845638A CN 202110863205 A CN202110863205 A CN 202110863205A CN 113845638 A CN113845638 A CN 113845638A
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- 239000011347 resin Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 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 57
- 238000002360 preparation method Methods 0.000 title abstract description 8
- HSTZMXCBWJGKHG-UHFFFAOYSA-N (E)-piceid Natural products OC1C(O)C(O)C(CO)OC1OC1=CC(O)=CC(C=CC=2C=CC(O)=CC=2)=C1 HSTZMXCBWJGKHG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960003764 polydatin Drugs 0.000 claims abstract description 22
- HSTZMXCBWJGKHG-CUYWLFDKSA-N trans-piceid Polymers O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(\C=C\C=2C=CC(O)=CC=2)=C1 HSTZMXCBWJGKHG-CUYWLFDKSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- -1 amine compound Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 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
- 238000001704 evaporation Methods 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 125000001483 monosaccharide substituent group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 9
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical group CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 6
- 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
- 229960001669 kinetin Drugs 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical group CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing 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
- 244000153955 Reynoutria sachalinensis Species 0.000 description 1
- 235000003202 Reynoutria sachalinensis Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000011825 aerospace material Substances 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
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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 discloses a bio-based water-soluble benzoxazine resin and a preparation method thereof. The invention takes the bio-based polydatin as a phenol source, reduces the pollution to the environment in the sense of raw materials, and the polydatin contains a monosaccharide structure, so that the benzoxazine resin monomer can be dissolved in water, thereby greatly widening the application field of the benzoxazine resin.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin, and particularly relates to green environment-friendly bio-based water-soluble benzoxazine resin and a preparation method thereof
Background
Benzoxazine resin has many advantages of the conventional phenol resin such as excellent heat resistance, chemical resistance, flame retardancy, low dielectric constant, good dynamic mechanical properties and low cost as a new ring-opening polymerization resin, and benzoxazine overcomes some disadvantages of the conventional phenol resin due to its unique ring-opening mechanism, and has other desirable properties including near-zero shrinkage curing, low water absorption, good dimensional stability, excellent FST (fire, smoke, toxicity) properties and ultra-high molecular design flexibility. Due to the unique properties, the adhesive can be applied to the aspects of high-performance adhesives, composite material matrix resins and the like. In addition, the benzoxazine has low water absorption, good moisture resistance and excellent dielectric property, and can replace the traditional epoxy resin and phenolic resin to be used as a burning-resistant material, a corrosion-resistant material, an electronic packaging material, a mechanical manufacturing part, an aerospace material, an adhesive, a circuit board substrate, a vacuum pump rotary vane, an insulating material and other related fields under special requirements.
With the expansion of the application field, people pursue high-performance polybenzoxazine materials, and meanwhile, environmental influence also becomes a key factor. The development of materials with both high performance and environmental friendliness has become the direction of researchers and researchers in the industry. A bio-based double bond-containing active bifunctional benzoxazine resin prepared in the patent No. (CN107459512A) and the patent No. (CN 111205421A). Although the resin has excellent thermal performance, the monomer of the resin does not have the characteristic of water solubility, the realization of a water-based construction environment is difficult, and the wide application of the resin is obviously limited. Chinese patent CN201410026770.3 discloses a water-soluble benzoxazine resin and a preparation method thereof, but the raw materials used in the scheme are not environment-friendly, and the added water-soluble functional monomer is salt, and can remain in the resin material in the application process to influence the use performance.
Disclosure of Invention
In view of some defects of the prior thermosetting resin material, the invention uses the bio-based polydatin as a phenol source by utilizing the flexible molecular design of the benzoxazine resin, reduces the pollution to the environment in the sense of raw materials, and the polydatin contains a monosaccharide structure, so that the benzoxazine resin monomer can be dissolved in water, thereby greatly widening the application field of the benzoxazine resin monomer.
The invention aims to overcome the problem that the traditional benzoxazine resin is difficult to dissolve in water by preparing the bio-based water-soluble benzoxazine resin, and simultaneously keep the resin to have good thermal property, mechanical property and interface property. The invention also provides a method for preparing the novel water-soluble benzoxazine by taking the bio-based polydatin as a phenol source.
The purpose of the invention is realized by the following technical scheme:
one of the purposes of the invention is to provide a bio-based water-soluble benzoxazine resin, the molecular chemical structural formula of which is shown as follows:
wherein the content of the first and second substances,
is one of the following structures:
the benzoxazine resin can be dissolved in water, the curing peak temperature is 180-220 ℃, the bio-based benzoxazine resin is further cured and crosslinked to obtain the polybenzoxazine resin, and the carbon residue rate is 20-80% at the inert atmosphere of 800 ℃.
The second purpose of the invention is to provide a preparation method of a water-soluble benzoxazine resin monomer.
The method is characterized in that the benzoxazine is prepared by taking polydatin, amine compounds and paraformaldehyde as raw materials, and the chemical reaction equation is as follows:
the structural formula of the amine compound is R-NH2Is one of the following structures:
the method specifically comprises the following steps:
adding polydatin, an amine compound and paraformaldehyde into a flask, adding an organic solvent, reacting at the temperature of 100 ℃ and 130 ℃ for 6-20h, filtering the reactant after the reaction is stopped, performing rotary evaporation, and drying to obtain a solid product, namely the water-soluble benzoxazine monomer.
Preferably, the molar ratio of the polydatin to the amine compound to the paraformaldehyde is 1: 2: 4-1: 2: 6.
preferably, the molar ratio of the polydatin to the amine compound to the paraformaldehyde is 1: 2: 4.14.
preferably, the organic solvent is one or a mixture of toluene, xylene and dioxane.
Compared with the prior art, the invention has the advantages that:
(1) according to the invention, the bio-based polydatin is used as a phenol source to synthesize the benzoxazine resin containing double bonds, so that the curing degree of ring opening of the benzoxazine can be improved, the obtained benzoxazine has good thermal stability, mechanical property and surface property, the curing peak temperature is 180-220 ℃, the residue rate is 20-80% at 800 ℃ in an inert gas atmosphere, the bio-based benzoxazine resin synthesized by the method can be dissolved in water, and the application occasions of the resin are greatly expanded;
(2) the polydatin used in the invention is extracted from giant knotweed rhizome, and is a substance with extremely high biological activity, widely applied to the field of medicine, and also a substance with extremely high development potential; because the existing medical field and the material preparation field of the saxitin do not have intersection, no researchers use the saxitin as a raw material of thermosetting resin to synthesize the resin at present; from the aspect of molecular structure, a single molecule of the saxitin contains two phenolic hydroxyl groups, and the saxitin can be used for synthesizing a bifunctional benzoxazine monomer; because the polydatin has a monosaccharide structure, the water-soluble group is creatively introduced into the benzoxazine monomer by synthesizing the benzoxazine by using the polydatin as a phenol source compound, so that the aqueous processing condition of the benzoxazine monomer is realized; meanwhile, experiments prove that the resin material has excellent performance, particularly the heat resistance is greatly improved.
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 a water-soluble benzoxazine-based resin and a preparation method thereof 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 which may occur to those skilled in the art after reading the present invention are within the scope of the following claims and are intended to be protected by the present invention.
Example 1
2-furanmethanamine is used as an amine source. 1g (0.00256mol) of polydatin, 0.492g (0.00512mol) of 2-furanmethanamine and 0.338g (0.01127mol) of paraformaldehyde are put into a flask, 50ml of dioxane solution is added, a condensing tube is connected, and stirring and reaction are carried out at 120 ℃ for 12 hours. After the reaction was stopped, the reaction was filtered, rotary evaporated and dried in a vacuum oven at 50 ℃ for one day to give 1.48g of benzoxazine monomer in 80% yield. 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, thermogravimetry graph and coating and water contact angle chart of the product are shown in figure 1, figure 2, figure 3 and figure 4.
FIG. 1 NMR spectrum of hydrogenFigure (a). Chemical shifts of about 4.77ppm and 3.57ppm are characteristic peaks of methylene on the oxazine ring. FIG. 2 is an infrared spectrum in which 919cm is-1And 1218cm-1The position is a characteristic absorption peak of the benzoxazine ring. FIG. 3 is a DSC graph, and the exothermic peak temperature of the benzoxazine monomer curing is 183 ℃. FIG. 4 is a TGA graph of the cured resin material, and it can be seen that the temperature of the benzoxazine resin is 306 ℃ when the thermal weight loss is 5%, and the carbon residue rate is 61% at 800 ℃. In addition, the benzoxazine resin was soluble in water at 50 ℃.
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 (0.00256mol) of polydatin, 0.477g (0.00512mol) of aniline, and 0.338g (0.01127mol) of paraformaldehyde were weighed out, and the yield was 81%.
The latent curing benzoxazine resin monomer obtained in the embodiment has a curing exothermic peak temperature of 189 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a residual carbon rate of 58% at a temperature of 293 ℃ under a thermal weight loss of 5% and an inert gas atmosphere of 800 ℃, and the benzoxazine can be dissolved in water at a temperature of 65 ℃.
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 (0.00256mol) of polydatin, 0.551g (0.00256mol) of 4-methylaniline and 0.338g (0.0112 mol) of paraformaldehyde7 mol). The yield thereof was found to be 75%.
The latent curing type benzoxazine resin monomer obtained in the embodiment has a curing exothermic peak temperature of 190 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a temperature of 300 ℃ when the thermal weight loss is 5%, and a carbon residue rate of 60% when the temperature is 800 ℃ in an inert gas atmosphere, and the benzoxazine resin can be dissolved in water at 70 ℃.
Example 4
The amine source compound 2-furanmethanamine in example 1 was replaced with octadecylamine. The other steps were the same as in example 1.
The specific chemical structural formula of the octadecyl amine is as follows:
the amounts of reactants were changed to: weighing 1g (0.00256mol) of polydatin, 1.380g (0.00256mol) of octadecyl amine and 0.338g (0.01127mol) of paraformaldehyde. The yield thereof was found to be 30%.
The latent curing benzoxazine resin monomer obtained in the embodiment has a curing exothermic peak temperature of 201 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a temperature of 274 ℃ when the thermal weight loss is 5%, and a carbon residue rate of 32% when the temperature is 800 ℃ in an inert gas atmosphere, and the benzoxazine can be dissolved in water at 70 ℃.
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)
1. A bio-based water-soluble benzoxazine resin is characterized in that: the molecular formula is as follows:
wherein the content of the first and second substances,
is one of the following structures:
2. the bio-based water-soluble benzoxazine resin according to claim 1, wherein the bio-based benzoxazine resin is soluble in water, the curing peak temperature is 180-220 ℃, the bio-based benzoxazine resin is further cured and crosslinked to obtain the polybenzoxazine resin, and the carbon residue rate is 20-80% at 800 ℃ in an inert atmosphere.
3. A method for preparing a bio-based water-soluble benzoxazine resin according to any one of claims 1-2, comprising the steps of:
mixing polydatin, amine compound and paraformaldehyde, adding an organic solvent, reacting at the temperature of 100 ℃ and 130 ℃ for 6-20h, filtering, rotary evaporating and drying reactants after the reaction is stopped to obtain a solid product, namely the water-soluble benzoxazine monomer.
4. The method for preparing polydatin-based benzoxazine resin according to claim 3, wherein the organic solvent is one or a mixture of toluene, xylene and dioxane.
5. The method for preparing the bio-based water-soluble benzoxazine resin according to claim 3, wherein the molar ratio of polydatin, the amine compound and the paraformaldehyde is 1: 2: 4-1: 2: 6.
6. the method for preparing polydatin-based benzoxazine resin according to claim 5, wherein the molar ratio of polydatin to amine compound to paraformaldehyde is 1: 2: 4.14.
7. the method for preparing bio-based water-soluble benzoxazine resin according to claim 5 or 6, wherein the amine compound has a structural formula of R-NH2Is one of the following structures:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907536A (en) * | 2022-05-06 | 2022-08-16 | 镇江利德尔复合材料有限公司 | Multifunctional benzoxazine resin and preparation method thereof |
| CN115260425A (en) * | 2022-07-18 | 2022-11-01 | 镇江利德尔复合材料有限公司 | Main chain type bio-based benzoxazine resin and preparation method thereof |
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| US20030023007A1 (en) * | 2001-07-27 | 2003-01-30 | Hycomp, Inc. | Enhancement of thermal properties of benzoxazine polymers by use of aromatic polyamines to incorporate internal benzoxazine groups within the monomer |
| JP2009196946A (en) * | 2008-02-22 | 2009-09-03 | Sekisui Chem Co Ltd | Method for producing benzoxazine |
| US20100210787A1 (en) * | 2007-12-06 | 2010-08-19 | Henkel Ag & Co. Kgaa | Curable benzoxazine macromonomers, their preparation and cured products |
| CN110951018A (en) * | 2019-12-30 | 2020-04-03 | 江苏大学 | Apigenin-based bio-based benzoxazine resin and preparation method thereof |
-
2021
- 2021-07-29 CN CN202110863205.2A patent/CN113845638A/en active Pending
Patent Citations (4)
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| US20030023007A1 (en) * | 2001-07-27 | 2003-01-30 | Hycomp, Inc. | Enhancement of thermal properties of benzoxazine polymers by use of aromatic polyamines to incorporate internal benzoxazine groups within the monomer |
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Non-Patent Citations (1)
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| LUDOVIC DUMAS ET AL.: ""Arbutin-based benzoxazine: en route to an intrinsic water soluble biobased resin"", 《GREEN CHEMISTRY》, pages 4954 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907536A (en) * | 2022-05-06 | 2022-08-16 | 镇江利德尔复合材料有限公司 | Multifunctional benzoxazine resin and preparation method thereof |
| CN115260425A (en) * | 2022-07-18 | 2022-11-01 | 镇江利德尔复合材料有限公司 | Main chain type bio-based benzoxazine resin and preparation method thereof |
| CN115260425B (en) * | 2022-07-18 | 2024-01-26 | 镇江利德尔复合材料有限公司 | Main chain type bio-based benzoxazine resin and preparation method thereof |
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