CN113150229B - High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof - Google Patents
High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof Download PDFInfo
- Publication number
- CN113150229B CN113150229B CN202110388995.3A CN202110388995A CN113150229B CN 113150229 B CN113150229 B CN 113150229B CN 202110388995 A CN202110388995 A CN 202110388995A CN 113150229 B CN113150229 B CN 113150229B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- containing pyridine
- benzoxazine resin
- type benzoxazine
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a high-carbon-residue fluorine-containing pyridine type benzoxazine resin and a preparation method thereof. Firstly, salicylaldehyde is taken as a phenol source, 2-amino-4- (trifluoromethyl) pyridine and 2-amino-5 (trifluoromethyl) pyridine are respectively taken as amine sources to carry out condensation reaction to generate intermediate Mannich alkali, then the Mannich alkali reacts with paraformaldehyde to synthesize two fluorine-containing pyridine type benzoxazine resins, and the high-performance polybenzoxazine is obtained through thermal curing. The novel benzoxazine resin prepared by the method has the advantages of easily available raw materials and environmental friendliness, and the obtained polybenzoxazine has high thermal stability, high carbon residue rate and good hydrophobic property, and is suitable for high-performance composite materials, electronic insulating materials, electronic packaging materials and the like.
Description
Technical Field
The invention relates to the field of resin synthesis, in particular to high-carbon-residue fluorine-containing pyridine type benzoxazine resin and a preparation method thereof.
Background
The polybenzoxazine inherits the advantages of the traditional phenolic resin and overcomes a plurality of defects of the traditional phenolic resin. Due to the special six-membered heterocyclic ring structure containing O and N and the unique ring-opening curing mechanism thereof, the polybenzoxazine has excellent comprehensive properties of heat resistance, flame retardance and the like, and is expected to replace the traditional phenolic resin, polyester, epoxy resin, cyanate ester, polyimide and the like in many fields. Particularly, the flexible molecular designability is an important characteristic of benzoxazine, and reactive, heat-resistant, flame-retardant and other groups are introduced into the molecular structure to endow the benzoxazine with different performance characteristics so as to meet the requirements of different application fields. Recently, they have been successfully applied to functional carbon precursors for fuel cells, supercapacitors, nanocatalysts and received extensive attention because "in situ" doping of nitrogen results in more uniform doped carbon materials. However, the low nitrogen content of conventional polybenzoxazine carbides may affect their applications. The nitrogen content of carbides is affected by the nitrogen content of polybenzoxazines and coke yield. Therefore, it is necessary to modify it to design a benzoxazine with high nitrogen content and high carbon residue.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a high-carbon-residue fluorine-containing pyridine type benzoxazine resin and a preparation method thereof. The carbon residue rate of the benzoxazine resin is increased from the perspective of molecular design, and good thermal stability is ensured.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the fluorine-containing pyridine type benzoxazine resin with high carbon residue is characterized in that the structural formula is shown in the specification
Wherein R is represented by the following structural formula:
the preparation method of the high-carbon-residue fluorine-containing pyridine type benzoxazine resin comprises the steps of carrying out condensation reaction by taking salicylaldehyde as a phenol source and taking 2-amino-4- (trifluoromethyl) pyridine and 2-amino-5 (trifluoromethyl) pyridine as amine sources respectively to generate intermediate Mannich alkali, then reacting the Mannich alkali with paraformaldehyde to synthesize two fluorine-containing pyridine type benzoxazine resins, and carrying out thermosetting to obtain the high-performance polybenzoxazine.
The pyridine functional group is a six-membered heterocyclic ring structure containing a nitrogen heteroatom, the intramolecular and intermolecular hydrogen bonds of the resin are increased due to the existence of electronegative nitrogen atoms of the pyridine ring, and the flame retardant property of the polymer is also obviously improved due to the increase of the content of nitrogen elements. Therefore, the pyridine structure is introduced into the benzoxazine structure, which is beneficial to improving the heat resistance and the flame retardant property of the cured product. Meanwhile, the fluorine atom has strong electronegativity and strong electron capturing capability, so that the dispersion force caused by the non-overlapping of a positive center and a negative center due to the instantaneous movement of electrons is small.
Further, the method specifically comprises the following steps:
step (1), synthesizing an intermediate Mannich base:
adding salicylaldehyde and fluorine-containing pyridine compound into a certain amount of organic solvent, and introducing N at room temperature2Stirring for 4h, adding sodium borohydride in batches, reacting for 6h, separating out an organic solvent and water, and then drying in vacuum to obtain a product, namely an intermediate Mannich base;
the reaction equation is shown in (I):
wherein R is represented by the structural formula:
and (2) synthesizing fluorine-containing pyridine type benzoxazine resin:
adding the intermediate Mannich alkali and paraformaldehyde into a certain amount of organic solvent, reacting for 5h at 60 ℃, separating the organic solvent and water, and then drying in vacuum to obtain a product, namely fluorine-containing pyridine type benzoxazine;
the reaction equation is shown in (III):
further, in the step (1), the molar ratio of the salicylaldehyde to the fluorine-containing pyridine to the sodium borohydride is 1:1: 1; in the step (2), the molar ratio of the Mannich alkali to the paraformaldehyde is 1: 1.
Further, in the step (1), the amount of the organic solvent is 40ml per 0.1mol of salicylaldehyde; in the step (2), the amount of the organic solvent is 35ml per 0.1mol of paraformaldehyde.
Further, in the steps (1) and (2), the organic solvent is one of ethanol, dioxane and toluene.
Further, in the step (1), the vacuum drying is carried out at 70 ℃ for 3h to obtain a product yield of 72%; in the step (2), the vacuum drying is carried out for 4 hours at the temperature of 80 ℃, so that the yield of the product is 86%.
Further, the temperature gradient is as follows: maintaining at 130 deg.C for 1h, 150 deg.C for 1h, 170 deg.C for 1h, 190 deg.C for 2h, 210 deg.C for 2h, and 230 deg.C for 2 h.
In addition, the invention also provides application of the high-carbon-residue fluorine-containing pyridine type benzoxazine resin or the high-carbon-residue fluorine-containing pyridine type benzoxazine resin obtained by the preparation method in preparation of high-performance polybenzoxazine, and the high-performance polybenzoxazine is obtained by thermosetting.
Further, the preparation method of the polybenzoxazine comprises the following steps:
dissolving benzoxazine resin in an organic solvent, removing the solvent in a vacuum drying oven at 50 ℃, placing the dissolved solution in the drying oven, setting a temperature gradient for solidification, and cooling to obtain polybenzoxazine;
the fluorine-containing pyridine type benzoxazine reaction equation is shown as the formula (IV):
compared with the prior art, the invention has the following beneficial effects:
the resin prepared by the invention introduces fluorine-containing pyridine into benzoxazine, increases the carbon residue rate of the benzoxazine resin, and simultaneously ensures good thermal stability and hydrophobic property.
The resin has the advantages of easily obtained raw materials, simple steps, environmental friendliness, various choices of solvents, optimized preparation process and easy realization of industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of two intermediate Mannich bases of example 1 of the present invention.
Fig. 2 is a nuclear magnetic hydrogen spectrum of the fluorine-containing pyridine type benzoxazine resin according to example 2 of the present invention.
Fig. 3 is an infrared spectrum of the fluorine-containing pyridine type benzoxazine resin according to the present invention.
FIG. 4 is a TGA profile of a polybenzoxazine of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Preparation of intermediate Mannich base by dissolving 2.44g (0.02mol) of salicylaldehyde and 3.24g (0.02mol) of fluorine-containing pyridine in 8ml of ethanol, pouring into a three-neck flask and introducing N2Then, the temperature is set to be 25 ℃ for reaction for 4 hours; and then 0.84g (0.02mol) of sodium borohydride is added in batches to react for 6h, after the reaction is finished, an ethanol solvent and water are evaporated by a rotary evaporator, and then the mixture is dried for 3h under vacuum at 70 ℃ to obtain an intermediate Mannich base with the yield of 72%. The nuclear magnetic spectrum is shown in FIG. 1, and in FIG. 1a, Ar-CH is present at 4.43ppm2Hydrogen atom in-N, 6.56ppm is a H atom in C-NH-Ar, indicating that the intermediate was successfully synthesized. 6.75-8.13ppm is proton absorption peak on benzene ring, 10.98ppm is hydroxyl absorption peak on benzene ring. 7.24ppm is the peak of chloroform as a solvent.
Ar-CH at 4.54ppm in FIG. 1b2Hydrogen atom in-N, 6.49ppm is a H atom in C-NH-Ar, indicating that the intermediate was successfully synthesized. 6.86-8.33ppm is proton absorption peak on benzene ring, 10.87ppm is hydroxyl absorption peak on benzene ring. 7.26ppm is the peak of chloroform as a solvent.
Example 2
Preparation of fluorine-containing pyridine type benzoxazine resin: 4.02g (0.015mol) of intermediate Mannich base and 0.45g (0.015mol) of paraformaldehyde are dissolved in 7ml of toluene and poured into a three-neck flask, and the temperature is set to be 60 ℃ to react for 5 hours. After the solution is cooled, the toluene solvent and water are evaporated by a rotary evaporator, and then the fluorine-containing pyridine type benzoxazine resin is dried for 4 hours at 80 ℃ in vacuum, so that the yield of the fluorine-containing pyridine type benzoxazine resin is 86%.
The nuclear magnetic spectrum chart of the prepared compound is shown in figure 2, and the infrared spectrum chart is shown in figure 3;
as shown in FIG. 2, the single peaks at 4.89 and 5.63ppm in FIG. 2a correspond to Ar-CH in the oxazine ring structure of benzoxazine, respectively2H atoms in-N-and C-NH-Ar indicate that a benzoxazine cyclic structure exists in the product, and the fluorine-containing pyridine type benzoxazine is successfully synthesized. 6.86-8.34ppm is the proton absorption peak on the benzene ring, and 7.24ppm is the peak of chloroform as the solvent.
The single peaks at 4.90 and 5.64ppm in FIG. 2b correspond to Ar-CH in the oxazine ring structure of benzoxazines, respectively2H atoms in-N-and C-NH-Ar indicate that a benzoxazine cyclic structure exists in the product, and the fluorine-containing pyridine type benzoxazine is successfully synthesized. 6.86-8.26ppm is the proton absorption peak on the benzene ring, and 7.25ppm is the peak of chloroform as the solvent.
As shown in FIG. 3, 1570cm in FIG. 3a-11226 and 1165cm as vibration absorption peak of benzene ring skeleton-1Is the absorption peak of C-N-C on the oxazine ring at 1036cm-1Is located at 945cm of symmetric stretching vibration peak of C-O on oxazine ring-1The characteristic absorption peak of the oxazine ring is shown, and the structural characteristics of the fluorine-containing pyridine benzoxazine resin can be basically determined by an infrared spectrogram.
1560cm in FIG. 3b-11227 and 1160cm are vibration absorption peaks of benzene ring skeleton-1Is treated as an absorption peak of C-N-C on the oxazine ring at 1039cm-1Is located at 946cm of symmetric stretching vibration peak of C-O on oxazine ring-1The characteristic absorption peak of the oxazine ring is shown, and the structural characteristics of the fluorine-containing pyridine benzoxazine resin can be basically determined by an infrared spectrogram.
Preparation of polybenzoxazine: dissolving a certain amount of benzoxazine in an ethanol solvent, dripping the benzoxazine onto a glass sheet, then placing the glass sheet in a vacuum drying oven at 50 ℃ to remove the solvent, then placing the glass sheet in a forced air drying oven, setting the temperature gradient to be 130 ℃ (1h) -150 ℃ (1h) -170 ℃ (2h) -190 ℃ (2h) -210 ℃ (2h) -230 ℃ (2h) for solidification, and cooling to obtain the polybenzoxazine. The TGA curve of the resin produced is shown in FIG. 4.
As shown in fig. 4, it can be seen from fig. 4 that the temperature T5% of 4-trifluoromethylpyridine benzoxazine with 5% weight loss is 252.6%, the temperature T10% of 4-trifluoromethylpyridine benzoxazine with 10% weight loss is 277.2 ℃, the carbon residue rate at 800 ℃ is 42.7%, the temperature T5% of 5-trifluoromethylpyridine benzoxazine with 5% weight loss is 277.3%, the temperature T10% of 10% weight loss is 307.6%, and the carbon residue rate at 800 ℃ is 49.8%.
Claims (9)
1. The fluorine-containing pyridine type benzoxazine resin with high carbon residue is characterized in that the structural formula is shown in the specification
wherein-R has the structural formula
2. The preparation method of the high-carbon-residue fluorine-containing pyridine benzoxazine resin according to claim 1, wherein salicylaldehyde is used as a phenol source, 2-amino-4-trifluoromethylpyridine and 2-amino-5-trifluoromethylpyridine are respectively used as amine sources to perform condensation reaction to generate an intermediate Mannich base, and then the Mannich base and paraformaldehyde react to synthesize two fluorine-containing pyridine benzoxazine resins.
3. The preparation method of the high-carbon-residue fluorine-containing pyridine type benzoxazine resin according to claim 2, comprising the following steps:
step (1), synthesizing an intermediate Mannich base:
adding salicylaldehyde and fluorine-containing pyridine compound into a certain amount of organic solvent, and introducing N at room temperature2Stirring for 4h, adding sodium borohydride in batches, reacting for 6h, separating out an organic solvent and water, and then drying in vacuum to obtain a product, namely an intermediate Mannich base;
the reaction equation is shown in (I):
wherein-R has the structural formula
And (2) synthesizing fluorine-containing pyridine type benzoxazine resin:
adding the intermediate Mannich alkali and paraformaldehyde into a certain amount of organic solvent, reacting for 5h at 60 ℃, separating the organic solvent and water, and then drying in vacuum to obtain a product, namely fluorine-containing pyridine type benzoxazine;
the reaction equation is shown in (III):
4. the method for preparing high carbon residue fluorine-containing pyridine type benzoxazine resin according to claim 3,
in the step (1), the molar ratio of the salicylaldehyde to the fluorine-containing pyridine to the sodium borohydride is 1:1: 1; in the step (2), the molar ratio of the Mannich alkali to the paraformaldehyde is 1: 1.
5. The method for preparing high carbon residue fluoropyridine benzoxazine resin according to claim 3, wherein in the step (1), the amount of the organic solvent is 40ml per 0.1mol of salicylaldehyde; in the step (2), the amount of the organic solvent is 35ml per 0.1mol of paraformaldehyde.
6. The method for preparing high-carbon residue fluorine-containing pyridine benzoxazine resin according to claim 3, wherein in the steps (1) and (2), the organic solvent is one of ethanol, dioxane and toluene.
7. The method for preparing high carbon residue fluorine-containing pyridine benzoxazine resin according to claim 3, wherein in the step (1), the vacuum drying is performed at 70 ℃ for 3h, so as to obtain a product yield of 72%; in the step (2), the vacuum drying is carried out for 4 hours at the temperature of 80 ℃, so that the yield of the product is 86%.
8. The application of the high carbon residue fluorine-containing pyridine type benzoxazine resin according to claim 1 or the high carbon residue fluorine-containing pyridine type benzoxazine resin obtained by the preparation method according to any one of claims 2 to 7 in preparation of high-performance polybenzoxazine.
9. Use according to claim 8, characterized in that the preparation method of polybenzoxazines comprises the following steps:
dissolving benzoxazine resin in an organic solvent, removing the solvent from the dissolved solution in a vacuum drying oven at 50 ℃, placing the dissolved solution in the drying oven, setting a temperature gradient for solidification, and cooling to obtain polybenzoxazine;
the fluorine-containing pyridine type benzoxazine reaction equation is shown as the formula (IV):
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110388995.3A CN113150229B (en) | 2021-04-12 | 2021-04-12 | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110388995.3A CN113150229B (en) | 2021-04-12 | 2021-04-12 | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113150229A CN113150229A (en) | 2021-07-23 |
| CN113150229B true CN113150229B (en) | 2022-07-05 |
Family
ID=76889897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110388995.3A Active CN113150229B (en) | 2021-04-12 | 2021-04-12 | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113150229B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090027183A (en) * | 2007-09-11 | 2009-03-16 | 삼성전자주식회사 | Benzooxzine-based monomer, benzooxzine-based polymer, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell using the same |
| WO2013039185A1 (en) * | 2011-09-15 | 2013-03-21 | 住友化学株式会社 | Benzoxazine compound and manufacturing method therefor |
| CN103936686A (en) * | 2014-03-21 | 2014-07-23 | 哈尔滨工程大学 | N-semi aromatic hydrocarbyl diamine-bisphenol tetrafunctional fluorene-based benzoxazine and preparation method thereof |
| CN105315221A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | Aromatic diamine type benzoxazine resin and preparation method thereof |
| CN108658990A (en) * | 2017-03-31 | 2018-10-16 | 南京科技职业学院 | A kind of novel imidazole simultaneously [1,5-a] Pyrazine Bu Ludun kinase inhibitors |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010511050A (en) * | 2006-11-29 | 2010-04-08 | ヘンケル コーポレイション | Method for producing benzoxazine |
| EP2357185B1 (en) * | 2007-11-02 | 2014-04-23 | Samsung Electronics Co., Ltd. | Naphthoxazine Benzoxazine-Based Monomer and Polymer Thereof |
| JP2017186265A (en) * | 2016-04-04 | 2017-10-12 | 日本化薬株式会社 | Benzoxazine compound |
| US11421080B2 (en) * | 2018-12-20 | 2022-08-23 | The Boeing Company | Fluoropolymer adhesives and methods thereof |
-
2021
- 2021-04-12 CN CN202110388995.3A patent/CN113150229B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090027183A (en) * | 2007-09-11 | 2009-03-16 | 삼성전자주식회사 | Benzooxzine-based monomer, benzooxzine-based polymer, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell using the same |
| WO2013039185A1 (en) * | 2011-09-15 | 2013-03-21 | 住友化学株式会社 | Benzoxazine compound and manufacturing method therefor |
| CN103936686A (en) * | 2014-03-21 | 2014-07-23 | 哈尔滨工程大学 | N-semi aromatic hydrocarbyl diamine-bisphenol tetrafunctional fluorene-based benzoxazine and preparation method thereof |
| CN105315221A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | Aromatic diamine type benzoxazine resin and preparation method thereof |
| CN108658990A (en) * | 2017-03-31 | 2018-10-16 | 南京科技职业学院 | A kind of novel imidazole simultaneously [1,5-a] Pyrazine Bu Ludun kinase inhibitors |
Non-Patent Citations (2)
| Title |
|---|
| 3-甲基-7-氧-9-氟-10-烃氧基（或芳氧基）-2,3-二氢-7H-吡啶[ 1,2,3-de]苯并恶嗪-6-羧酸及其类似物（英） 的合成和抗菌以及抗肿瘤活性;周伟澄 等;《Journal of Chinese Pharmaceutical Sciences》;19991231(第1期);第21-25页 * |
| Pyrido[3,2-b][1,4]oxazine and pyrido[2,3-b][1,4]benzoxazine systems from tetrafluoropyridine derivatives;Sandford, G 等;《JOURNAL OF FLUORINE CHEMISTRY》;20141130;第167卷;第91-95页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113150229A (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110240684B (en) | Latent curing benzoxazine resin and preparation method thereof | |
| CN110951018A (en) | Apigenin-based bio-based benzoxazine resin and preparation method thereof | |
| US20230242707A1 (en) | Biomass benzoxazine-based shape memory resin, preparation method therefor, and application thereof | |
| CN103936686B (en) | N-semiaromatic alkyl diamine-bisphenol type four degree of functionality fluorenyl benzoxazine and preparation methods | |
| CN110591091A (en) | Main chain type benzoxazine containing daidzein group and preparation method thereof | |
| CN111100120A (en) | Bio-based bis-benzoxazine monomer and preparation method thereof | |
| Su et al. | The structure and thermal properties of novel DOPO-containing 1, 3-benzoxazines | |
| CN107129493B (en) | Diamine type dibenzoxazine containing alicyclic hydrocarbon imide group and preparation method thereof | |
| CN112341584A (en) | Bio-based benzoxazine resin containing furan amide structure and preparation method thereof | |
| CN103936764B (en) | N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof | |
| CN113150229B (en) | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof | |
| CN114031616B (en) | Benzoxazine containing ethyl acetate and triazole ring structure with high carbon residue and preparation method thereof | |
| CN101659677A (en) | Triphosphazene epoxy resin and preparation method thereof | |
| CN109678880B (en) | Tri-functional benzoxazine monomer based on resveratrol and preparation method thereof | |
| CN113801283B (en) | High heat-resistant Gao Cantan benzoxazine resin and preparation method thereof | |
| CN115260489B (en) | Bio-based difunctional benzoxazine resin and preparation method thereof | |
| CN115403766A (en) | Kaempferol-based bio-based benzoxazine resin and preparation method thereof | |
| CN113004518B (en) | Phthalonitrile resin prepolymer and preparation method thereof | |
| CN115141334A (en) | Sulfur-containing bio-based benzoxazine resin and preparation method thereof | |
| CN113429363B (en) | Benzoxazine and synthetic method thereof | |
| CN108863973B (en) | Novel amide type benzoxazine resin and one-step preparation method thereof | |
| CN112094412A (en) | Cross-linked polybenzoxazole and preparation method thereof | |
| CN116987362B (en) | Benzoxazine resin-based graphene film material and preparation method and application thereof | |
| CN114195803B (en) | Difunctional benzoxazine resin based on coumarin bio-base and preparation method thereof | |
| CN113121772B (en) | Pterostilbene-based benzoxazine resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |