CN113861362A - Method for rapidly curing and simultaneously toughening benzoxazine resin - Google Patents
Method for rapidly curing and simultaneously toughening benzoxazine resin Download PDFInfo
- Publication number
- CN113861362A CN113861362A CN202111156327.4A CN202111156327A CN113861362A CN 113861362 A CN113861362 A CN 113861362A CN 202111156327 A CN202111156327 A CN 202111156327A CN 113861362 A CN113861362 A CN 113861362A
- Authority
- CN
- China
- Prior art keywords
- curing
- benzoxazine
- toughening
- solvent
- benzoxazine resin
- 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.)
- Granted
Links
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000001723 curing Methods 0.000 claims abstract description 61
- 239000010954 inorganic particle Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000011415 microwave curing Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000010881 fly ash Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- -1 primary amine compound Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- XGCCXKOSCKUFIF-UHFFFAOYSA-N O1NC=CC2=C1C=CC=C2.O2NC=CC1=C2C=CC=C1 Chemical compound O1NC=CC2=C1C=CC=C2.O2NC=CC1=C2C=CC=C1 XGCCXKOSCKUFIF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to the field of thermosetting resin curing, in particular to a method for rapidly curing and simultaneously toughening benzoxazine resin; the method comprises the following steps: firstly, dispersing inorganic particles in a proper amount of solvent, then ultrasonically mixing the inorganic particles with benzoxazine dissolved in the proper amount of solvent to prepare a uniform solution, and then removing the solvent in a vacuum oven; the benzoxazine resin is toughened while fast curing is realized by adopting a mode of combining microwave curing and heating curing. The benzoxazine resin obtained by the curing method has good mechanical property, the curing time is shortened to 45min from 8h of hot curing, the impact property is improved by 107% to the maximum extent compared with that of the pure benzoxazine resin, and the carbon residue rate at 800 ℃ is up to 46.9%. The invention is mainly used for manufacturing large resin base materials, shortens the curing time, improves the production efficiency of workpieces, reduces the manufacturing cost and has important significance for improving the rapid forming level of aviation equipment in China.
Description
Technical Field
The invention relates to the field of thermosetting resin curing, in particular to a method for rapidly curing and simultaneously toughening benzoxazine resin.
Background
Benzoxazine (Benzoxazine) is a benzo six-membered heterocyclic compound containing nitrogen and oxygen atoms, which is obtained by condensation reaction of a phenolic compound, a primary amine compound and formaldehyde. The synthetic method of the benzoxazine resin is simple, the melt viscosity is low, no micromolecular by-product is released during polymerization, the product porosity is low, the volume shrinkage rate is zero during curing, and the product precision is high; meanwhile, the flame retardant has excellent thermal stability and flame retardance; good mechanical properties, as well as higher glass transition temperature (Tg) and modulus; meanwhile, the method also has the advantages of flexible molecular design and the like. Benzoxazine resin has been widely used in various fields such as electronic packaging materials, aerospace industry, composite materials, flame retardant materials, high temperature resistant electrical insulation materials, coatings and the like. However, like other thermosetting resins, benzoxazine has the disadvantages of high brittleness, high curing temperature, long curing time and the like of a cured product. The defects greatly limit the popularization and the application of the high-performance structural material in high and new technical fields such as aerospace and the like.
The traditional curing mode of benzoxazine resin is heating curing, and heat is transferred from the outside of the material to the inside of the material during heating curing, so that the temperature gradient exists in the material, the curing degree in the thickness direction is different, the resin curing is difficult to be uniform and complete, larger internal stress is easy to generate, the curing speed is slow, the period is long, and the production cost is increased. Microwave curing is an 'intramolecular' uniform curing mode, utilizes microwave radiation to generate heat, raises the temperature and generates curing reaction, has the advantages of uniform curing, high speed, easy control, energy conservation and low equipment investment, and has become the key point of the research on the curing aspect of thermosetting resin.
The toughening modification of the benzoxazine resin comprises methods such as blending modification of rubber elastomers, blending modification of other thermosetting resins, molecular design modification, inorganic particle modification and the like. For example: zhao et al use imidazole (MZ) as catalyst to prepare a novel Benzoxazine (BOZ)/Epoxy Resin (ER) blending structure with sea-island structure, compared with homogeneous PBOZ and PBOZ/ER blending, the toughness and thermal performance of phase separation blending system are greatly improved, wherein the impact strength of PBOZ/ER/MZ system reaches 33.8kJ/m2, and is improved by nearly two times compared with PBOZ system; liu and the like uniformly disperse nano silicon nitride in benzoxazine resin, the nano silicon nitride reinforced benzoxazine composite material is prepared by curing for 8 hours at 180 ℃, and DMA test results show that the initial storage modulus and Tg of the nano composite material are respectively improved to 2GPa and 47 ℃ compared with unmodified PBA-a resin under the condition of the maximum nano silicon nitride content (30wt%), and meanwhile, the tensile strength and the tensile modulus are both obviously improved. Although the toughness of the benzoxazine resin can be effectively improved through the toughening modification, the problems of high curing temperature, long curing time of 6-8 h, complex operation, high processing cost and the like still exist. Therefore, the design of a curing mode which is rapid and efficient, simple to operate, low in processing cost and capable of toughening benzoxazine resin is of great significance.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a method for shortening the curing time and toughening benzoxazine resin. The idea of the invention is derived from microwave curing technology, which can cure inorganic particles by using microwave to act on the inorganic particles to generate heat. Inorganic particles are introduced into benzoxazine, the inorganic particles are utilized to absorb microwave energy and convert the internal energy into heat energy, the heat energy is transferred to a resin matrix through heat conduction, the resin matrix is cured from inside to outside, the internal stress is reduced, the curing time of the resin is shortened, and meanwhile, the inorganic particle fly ash is used as a toughening phase to toughen the benzoxazine resin. The purpose of toughening the benzoxazine while shortening the curing time of the benzoxazine is realized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for rapidly curing and simultaneously toughening benzoxazine resin comprises the following steps: dispersing inorganic particles with microwave absorption performance in a proper amount of solvent, and ultrasonically mixing the inorganic particles with benzoxazine dissolved in the proper amount of solvent to prepare uniform mixed solution; and then removing the solvent from the mixed solution in a vacuum oven to obtain a benzoxazine prepolymer, and finally preparing a casting body by adopting microwave curing and heating curing processes.
Further, the benzoxazine is one or a combination of bisphenol A type benzoxazine, naphthol type benzoxazine and diamine type benzoxazine.
Further, the inorganic particles are one or a combination of more of fly ash, silicon dioxide and aluminum oxide.
Further, the solvent is one or more of N, N-dimethylformamide, acetone, tetrahydrofuran and chloroform.
Further, the mass ratio of the inorganic particles to the benzoxazine is 1:100 to 5: 100.
Furthermore, the dosage ratio of the inorganic particles to the solvent is 0.5g/mL, and the dosage ratio of the benzoxazine to the solvent is 0.1-0.5 g/mL (the resin is required to be completely dissolved).
Preferably, the specific process of curing is as follows: after curing with microwave at 440W/5min and 600W/10min, heating and curing at 200 deg.C/30 min.
Compared with the prior art, the invention has the following beneficial effects:
the curing method provided by the invention is simple to operate and short in curing time, and the benzoxazine resin obtained by the curing method provided by the invention is good in mechanical property, the curing time is shortened to 45min from 8h of hot curing, the impact property is improved by 107% at most compared with that of pure benzoxazine resin, and the carbon residue rate at 800 ℃ is up to 46.9%. The invention provides a novel method for rapidly curing and simultaneously toughening benzoxazine resin, which is characterized in that microwave curing is introduced to shorten the curing time of benzoxazine, and inorganic particles are introduced to serve as toughening phases to toughen the benzoxazine. The method has the advantages of saving energy, improving the production efficiency of the parts and reducing the cost. In addition, the composite material prepared by the method has good mechanical properties, and the method is mainly used for manufacturing large resin base materials.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) profile of example 1 and comparative example 1, wherein CV (thermal curing) is a DSC curve of 1% by mass in comparative example 1, MW (microwave curing) is a DSC curve of example 1, and No curing is a DSC curve of an uncured sample.
FIG. 2 is an infrared spectrum of example 1 and comparative example 1, wherein CV curing is comparative example 1, MW 15min is a sample microwave cured for 15 minutes, MW 10min is a sample microwave cured for 10 minutes, and No curing is an uncured sample.
FIG. 3 is a graph of impact strength for examples 1 to 3, where the abscissa values are the mass ratio of fly ash to bisphenol A benzoxazine.
Fig. 4 is a graph of impact strength of comparative example 1, in which the abscissa value is the mass ratio of fly ash to bisphenol a type benzoxazine.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Dispersing a certain amount of fly ash in N, N-dimethylformamide, and carrying out ultrasonic treatment for 10min to uniformly mix the fly ash and the N, N-dimethylformamide to prepare a solution; dissolving bisphenol A benzoxazine in a proper amount of N, N-dimethylformamide, and performing ultrasonic treatment for 10min to prepare a solution. And ultrasonically mixing the two solutions for 0.5h to obtain a uniform solution. The mass ratio of the fly ash to the bisphenol A benzoxazine is 1: 100. The dosage ratio of the inorganic particle fly ash to the solvent is 0.1 g/mL. The dosage ratio of the benzoxazine to the solvent is 0.1-0.5 g/mL (the resin is required to be completely dissolved).
Firstly, pouring the solution into a polytetrafluoroethylene mold, and then removing the solvent in a vacuum oven at 140 ℃/1 h.
Secondly, the sample strips from which the solvent was removed were cured by the following steps: after curing with microwave at 440W/5min and 600W/10min, heating and curing at 200 deg.C/30 min.
Finally, the impact strength of the obtained polybenzoxazine composite material (marked as FA/BA-a) reaches 16.85KJ/m2Is higher than pure resin92.1%。
Example 2
The present embodiment differs from embodiment 1 in that: the mass ratio of the fly ash to the bisphenol A benzoxazine in the step one is 3: 100. The other steps and parameters were the same as in example 1. Finally, the impact strength of the obtained polybenzoxazine composite material reaches 18.18KJ/m2The yield is improved by 107.3 percent compared with the pure resin.
Example 3
The present embodiment differs from embodiment 1 in that: the mass ratio of the fly ash to the bisphenol A benzoxazine in the step one is 5: 100. The other steps and parameters were the same as in example 1. Finally, the impact strength of the obtained polybenzoxazine composite material reaches 15.52KJ/m2The yield is improved by 76.9 percent compared with pure resin.
Comparative example 1
The mass ratio of the fly ash to the benzoxazine is the same as that in the examples 1 to 3, only the composite material is prepared into sample strips by the hot curing process of 140 ℃/2h, 160 ℃/2h, 180 ℃/2h and 200 ℃/2h, and the impact strength of the composite material obtained after curing reaches 15.37KJ/m2、16.92KJ/m2、14.82KJ/m2。
Claims (7)
1. A method for rapidly curing and simultaneously toughening benzoxazine resin is characterized by comprising the following steps: dispersing inorganic particles with microwave absorption performance in a proper amount of solvent, and ultrasonically mixing the inorganic particles with benzoxazine dissolved in the proper amount of solvent to prepare uniform mixed solution; and then removing the solvent from the mixed solution in a vacuum oven to obtain a benzoxazine prepolymer, and finally preparing a casting body by adopting microwave curing and heating curing processes.
2. The method for rapidly curing and simultaneously toughening benzoxazine resin according to claim 1, wherein the benzoxazine is one or a combination of bisphenol A type benzoxazine, naphthol type benzoxazine and diamine type benzoxazine.
3. The method for rapidly curing and simultaneously toughening benzoxazine resin according to claim 1, wherein the inorganic particles are one or a combination of fly ash, silicon dioxide and aluminum oxide.
4. The method for rapidly curing and simultaneously toughening benzoxazine resin according to claim 1, wherein the solvent is one or more of N, N-dimethylformamide, acetone, tetrahydrofuran and chloroform.
5. The method for rapidly curing and simultaneously toughening benzoxazine resin according to claim 1, wherein the mass ratio of the inorganic particles to the benzoxazine is between 1:100 and 5: 100.
6. The method for rapidly curing and simultaneously toughening benzoxazine resin according to claim 1, wherein the dosage ratio of the inorganic particles to the solvent is 0.5g/mL, and the dosage ratio of the benzoxazine to the solvent is 0.1-0.5 g/mL.
7. The method for rapidly curing and simultaneously toughening benzoxazine resin according to any one of claims 1-6, wherein the curing process is as follows: after curing with microwave at 440W/5min and 600W/10min, heating and curing at 200 deg.C/30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111156327.4A CN113861362B (en) | 2021-09-30 | 2021-09-30 | Method for rapidly curing and toughening benzoxazine resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111156327.4A CN113861362B (en) | 2021-09-30 | 2021-09-30 | Method for rapidly curing and toughening benzoxazine resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113861362A true CN113861362A (en) | 2021-12-31 |
| CN113861362B CN113861362B (en) | 2024-01-23 |
Family
ID=79000943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111156327.4A Active CN113861362B (en) | 2021-09-30 | 2021-09-30 | Method for rapidly curing and toughening benzoxazine resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113861362B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395308A (en) * | 2022-01-21 | 2022-04-26 | 中北大学 | Preparation method and application of environment-friendly super-hydrophobic anti-corrosion composite coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4785073A (en) * | 1983-08-16 | 1988-11-15 | Polymer Tectonics Limited | Melamine-phenol-formaldehyde resole modified by glycols moulding composition |
| JP2001174946A (en) * | 1999-10-05 | 2001-06-29 | Konica Corp | Photosensitive emulsion, heat developable photosensitive material, image recording method and image forming method |
| CN108587060A (en) * | 2018-05-02 | 2018-09-28 | 江苏恒神股份有限公司 | A kind of benzoxazine colophony constituent and its prepreg suitable for microwave curing process |
| CN113248865A (en) * | 2021-05-10 | 2021-08-13 | 泰安市中研复合材料科技有限公司 | Benzoxazine resin system capable of being rapidly cured and composite material |
-
2021
- 2021-09-30 CN CN202111156327.4A patent/CN113861362B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4785073A (en) * | 1983-08-16 | 1988-11-15 | Polymer Tectonics Limited | Melamine-phenol-formaldehyde resole modified by glycols moulding composition |
| JP2001174946A (en) * | 1999-10-05 | 2001-06-29 | Konica Corp | Photosensitive emulsion, heat developable photosensitive material, image recording method and image forming method |
| CN108587060A (en) * | 2018-05-02 | 2018-09-28 | 江苏恒神股份有限公司 | A kind of benzoxazine colophony constituent and its prepreg suitable for microwave curing process |
| CN113248865A (en) * | 2021-05-10 | 2021-08-13 | 泰安市中研复合材料科技有限公司 | Benzoxazine resin system capable of being rapidly cured and composite material |
Non-Patent Citations (1)
| Title |
|---|
| RIMDUSIT ET AL: "Characterization of SiC Whisker-Filled Polybenzoxazine Cured by Microwave Radiation and Heat", 《INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION》, no. 11, pages 441 - 453 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395308A (en) * | 2022-01-21 | 2022-04-26 | 中北大学 | Preparation method and application of environment-friendly super-hydrophobic anti-corrosion composite coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113861362B (en) | 2024-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105838086B (en) | Preparation method of sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material | |
| CN102181140A (en) | Carbon fiber silk waste reinforced polycarbonate composite material and preparation method of the carbon fiber silk waste reinforced polycarbonate composite material | |
| CN113861362B (en) | Method for rapidly curing and toughening benzoxazine resin | |
| CN1884376A (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| WO2023179260A1 (en) | Natural plant fiber/water-borne epoxy resin composite material and manufacturing method therefor | |
| CN112961468B (en) | Modified epoxy resin composite material and preparation method thereof | |
| CN110818932A (en) | Norbornene-based end-capped benzoxazine oligomer prepreg composition, and preparation method and application method thereof | |
| CN109880298A (en) | A kind of high insulating epoxy composite material of high thermal conductivity and its preparation and application | |
| CN103524691B (en) | Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof | |
| CN115196982B (en) | Boiler lining heat-insulating material and preparation method thereof | |
| CN114015198B (en) | Preparation method of intermediate-temperature curing prepreg epoxy resin with optimized process | |
| CN107365498B (en) | high-temperature forming insulating material for superconducting magnet and preparation method thereof | |
| CN113462154B (en) | High-heat-resistance cyanate resin and preparation method thereof | |
| CN113788697A (en) | Ceramic precursor slurry applicable to winding process and preparation method thereof | |
| CN109553929B (en) | Nano flame-retardant epoxy resin composite material and preparation method thereof | |
| CN112694340A (en) | Preparation method of high-temperature-resistant carbon fiber composite material | |
| CN111793193A (en) | Solvent-free type 180-DEG C-resistant ultralow-viscosity epoxy resin matrix and preparation method thereof | |
| CN114250050B (en) | Epoxy resin composition, preparation thereof and application thereof in IGBT semiconductor packaging | |
| CN108587060A (en) | A kind of benzoxazine colophony constituent and its prepreg suitable for microwave curing process | |
| CN108129801A (en) | A kind of carbon fibre composite and preparation method thereof | |
| CN111454562B (en) | Light low-loss fiber-reinforced aromatic nitrile-based resin composite material and preparation method thereof | |
| CN117069987B (en) | Carbon fiber prepreg and preparation method thereof | |
| CN113429546A (en) | High-fracture-toughness low-viscosity epoxy resin composition | |
| CN111019073A (en) | Preparation method of toughened and modified dual-curing benzoxazine resin | |
| CN117645709A (en) | Organosilicon modified epoxy resin, thermal repair epoxy resin composition 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 |