CN107129664B - Preparation method of bio-based network toughened epoxy resin - Google Patents
Preparation method of bio-based network toughened epoxy resin Download PDFInfo
- Publication number
- CN107129664B CN107129664B CN201710448126.9A CN201710448126A CN107129664B CN 107129664 B CN107129664 B CN 107129664B CN 201710448126 A CN201710448126 A CN 201710448126A CN 107129664 B CN107129664 B CN 107129664B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- toughening
- mass
- bio
- curing agent
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims abstract description 7
- LVRCYPYRKNAAMX-UHFFFAOYSA-M bis(triphenylphosphine)iminium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)N=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LVRCYPYRKNAAMX-UHFFFAOYSA-M 0.000 claims abstract description 7
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 9
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 241001494106 Stenotomus chrysops Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparation method for toughening epoxy resin through a network formed based on bio-based dihydrocoumarin, and belongs to the field of epoxy resin composite materials. The method comprises the steps of carrying out alternate copolymerization reaction on polyethylene glycol glycidyl ether, n-butyl glycidyl ether and dihydrocoumarin under the catalysis of bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride to form a network structure, then adding the liquid mixture into an epoxy resin monomer, adding a curing agent and an accelerator, and carrying out curing film formation in a polytetrafluoroethylene mold. The toughness of the epoxy resin modified by the bio-based network is greatly improved.
Description
Technical Field
The invention belongs to the technical field of preparation of epoxy resin composite materials, and relates to a preparation method for forming a double network by using a novel bio-based network and epoxy resin to realize toughening.
Background
The cured epoxy resin has good physical and chemical properties, excellent bonding strength to the surfaces of metal and non-metal materials, good dielectric property, small deformation shrinkage rate, good product dimensional stability, high hardness, good flexibility and stability to alkali and most solvents, so that the cured epoxy resin can be widely applied to various departments of national defense and national economy, and can be used as pouring, dipping, laminating materials, adhesives, coatings and the like. However, the epoxy resin has the disadvantages of large viscosity, poor fluidity, high crosslinking density after curing, poor toughness, large internal stress, brittle quality, poor fatigue resistance, heat resistance, impact resistance, cracking resistance, wet heat resistance and the like, and the application of the epoxy resin in certain high-tech fields is limited to a great extent. So the toughening modification of the epoxy resin is particularly important to meet the application requirements.
The prior toughening modification method of epoxy resin mainly comprises the methods of toughening rubber elastomers (porgy, Ningrongchang, Tangyusheng and the like. aeronautical materials, 2003, 23: 48.), toughening thermoplastic resins (Huakujun, Huchunsheng. high molecular materials science and engineering, 1999, 15: 21.), toughening core-shell structure polymers (Zhangming and the like, applied chemistry, 1996, 13: 113.), toughening interpenetrating polymer networks (Soo-Jin Park, Fan-Long Jin. Mater. Sci. Eng. A, 2008, 478: 402.), toughening nanoparticles (Xusing and the like, CN 104725782A) and the like.
In the method, a bio-based network is formed by reacting polyethylene glycol diglycidyl ether, n-butyl glycidyl ether and dihydrocoumarin to toughen and modify the epoxy resin.
The cross-linked network polymer generated by the reaction is hybridized with the epoxy resin network to form a double-network structure, and the double-network structure is characterized in that a biological network participates in the construction of the epoxy resin network, and besides covalent bonds, ionic bonds also exist in the network. The biological network is randomly hybridized into the epoxy network, and the inherent network structure of the epoxy resin is obviously changed. The structure not only can greatly improve the synergistic effect of the materials, but also can lead the network to generate large deformation under the action of external force, absorb external energy, increase stress transmission, improve the effective amount of chains in the stress concentration and play an obvious toughening effect on the epoxy resin.
Disclosure of Invention
The invention aims to provide a preparation method for toughening an epoxy resin composite material by utilizing a biobased network and an epoxy network to form a double network in a hybrid manner. The preparation method comprises the following steps:
(1) preparing a toughening system:
mixing polyethylene glycol diglycidyl ether, n-butyl glycidyl ether, dihydrocoumarin, bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride according to a molar ratio of X to Y of 1.1 to 0.004, wherein 2X + Y =1.0, and heating at 80 ℃ for 8-10 h to prepare viscous liquid;
(2) toughening and curing of epoxy resin:
firstly, putting an epoxy resin monomer into an oven to enable the epoxy resin monomer to have certain fluidity, then adding the viscous liquid obtained in the step (1) into the epoxy resin monomer, then adding a curing agent and an accelerator, stirring for about 2-5 h at 80-120 ℃, coating in a polytetrafluoroethylene mold, and then putting into the oven to cure for 1-10 h at 100-200 ℃.
Wherein: the epoxy resin monomer is a mixture of diphenol propane epoxy resin containing one or more than two glycidyl groups and homologues thereof or one or more of alicyclic epoxy resin and derivatives thereof.
The curing agent is one or a plurality of dicyandiamide, divinyl triamine, aromatic polyamine and benzoic anhydride, and the mass of the curing agent is 3-10% of that of the epoxy resin monomer.
The accelerant is one or a plurality of aromatic urea, methylimidazole and triphenylphosphine, and the mass of the accelerant is 1-5% of the mass of the epoxy resin monomer.
The toughening system accounts for 10-50% of the total epoxy resin system by mass.
Has the advantages that:
the invention has the advantages that: (1) the toughened epoxy resin has a double-network structure, so that the toughness is greatly improved, and the strength of the material can be effectively maintained; (2) the biological network is derived from dihydrocoumarin, a bio-based chemical raw material which is converted from coumarin and can be obtained in a large scale, and the bio-based chemical raw material has the characteristic of sustainable regeneration from the aspect of raw material acquisition.
Example (b):
the features and advantages of the present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
mixing polyethylene glycol diglycidyl ether, n-butyl glycidyl ether, dihydrocoumarin, bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride according to a molar ratio of 0.025:0.95:1.1:0.004:0.004, and reacting at 80 ℃ for 8 hours to prepare a toughening system; putting bisphenol A diglycidyl ether into an oven at 70 ℃ to ensure that the diglycidyl ether has certain fluidity. Weighing a toughening system, and adding the toughening system into bisphenol A diglycidyl ether, wherein the mass of the toughening system accounts for 10% of the mass of the total system. Meanwhile, adding a curing agent dicyandiamide and an accelerant aromatic urea into an epoxy resin monomer containing a toughening system, wherein the mass of the curing agent and the mass of the accelerant are respectively 5% and 3% of the mass of the epoxy resin, stirring the system at 80 ℃ for 2 h, and pouring the system into a polytetrafluoroethylene mold for coating. And putting the mould into an oven, heating for 2 hours at 120 ℃, and heating for 5 hours at 150 ℃ to completely cure. And demolding the formed cured product, cutting and testing according to the corresponding national standard. The obtained toughened epoxy resin has the tensile strength of 58MPa, the elongation at break of 6.6 percent and the elongation which is 3.3 times of that of an un-toughened system.
Example 2:
mixing polyethylene glycol diglycidyl ether, n-butyl glycidyl ether, dihydrocoumarin, bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride according to a molar ratio of 0.025:0.95:1.1:0.004:0.004, and reacting at 80 ℃ for 8 hours to prepare a toughening system; placing the diglycidyl phthalate into an oven at 70 ℃ to ensure that the diglycidyl phthalate has certain fluidity. Weighing a toughening system, and adding the toughening system into diglycidyl phthalate, wherein the mass of the toughening system accounts for 30% of the total mass of the system. And simultaneously adding a compound curing agent of benzoic anhydride and divinyl triamine and a triphenyl phosphorus accelerator into diglycidyl phthalate containing a toughening system, wherein the mass of the curing agent and the mass of the accelerator are respectively 5% and 3% of the mass of the epoxy resin, stirring the system at 80 ℃ for 2 hours, and pouring the system into a polytetrafluoroethylene mold for coating. And putting the mould into an oven, heating for 2 h at 120 ℃, heating for 2 h at 150 ℃, and heating for 5h at 180 ℃ to completely cure. And demolding the formed cured product, cutting and testing according to the corresponding national standard. The obtained toughened epoxy resin has the tensile strength of 45 MPa, the elongation at break of 8.5 percent and the elongation which is 4 times of that of an un-toughened system.
Example 3:
mixing polyethylene glycol diglycidyl ether, n-butyl glycidyl ether, dihydrocoumarin, bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride according to a molar ratio of 0.25:0.5:1.1:0.004:0.004, and reacting at 80 ℃ for 8 hours to prepare a toughening system; putting bisphenol A diglycidyl ether into an oven at 70 ℃ to ensure that the diglycidyl ether has certain fluidity. Weighing a toughening system, and adding the toughening system into bisphenol A diglycidyl ether, wherein the mass of the toughening system accounts for 50% of the mass of the total system. Meanwhile, adding a curing agent dicyandiamide and an accelerator methylimidazole into bisphenol A diglycidyl ether containing a toughening system, wherein the mass of the curing agent and the mass of the accelerator are respectively 5% and 3% of the mass of the epoxy resin, stirring the system at 80 ℃ for 2 hours, and pouring the system into a polytetrafluoroethylene mold for coating. And putting the mould into an oven, heating for 2 hours at 120 ℃, and heating for 5 hours at 150 ℃ to completely cure. And demolding the formed cured product, cutting and testing according to the corresponding national standard. The obtained toughened epoxy resin has the tensile strength of 50 MPa, the elongation at break of 12.0 percent and the elongation which is 6 times of that of an un-toughened system.
Claims (6)
1. A preparation method of epoxy resin toughened by utilizing a bio-based network is characterized by comprising the following steps:
(1) preparing a toughening system:
mixing polyethylene glycol diglycidyl ether, n-butyl glycidyl ether, dihydrocoumarin, bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride, and reacting at 50-150 ℃ for 5-10 h;
(2) toughening and curing of epoxy resin:
firstly, putting an epoxy resin monomer into an oven to enable the epoxy resin monomer to have certain fluidity, then adding the mixture obtained in the step (1) into the epoxy resin monomer, then adding a proper amount of curing agent and accelerator, heating to 80-120 ℃, stirring for 2-5 h to obtain viscous liquid, coating the viscous liquid in a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into the oven to be cured and molded, and demolding.
2. The method of claim 1, wherein: the molar ratio of polyethylene glycol diglycidyl ether, n-butyl glycidyl ether, dihydrocoumarin, bis (triphenyl phosphoranylidene) ammonium chloride and chromium chloride is X: Y:1.1:0.004:0.004, wherein 2X + Y = 1.0.
3. The method of claim 1, wherein: the epoxy resin monomer comprises diphenol propane epoxy resin containing one or more than two glycidyl groups and a mixture thereof or alicyclic epoxy resin and a derivative thereof.
4. The method of claim 1, wherein: the curing agent is one or a plurality of dicyandiamide, divinyl triamine, aromatic polyamine and benzoic anhydride, and the mass of the curing agent is 3-10% of that of the epoxy resin.
5. The method of claim 1, wherein: the accelerant is one or a plurality of aromatic urea, methylimidazole and triphenylphosphine, and the mass of the accelerant is 1-5% of that of the epoxy resin.
6. The method of claim 1, wherein: the mass content of the toughening system accounts for 10-50% of the total epoxy resin system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710448126.9A CN107129664B (en) | 2017-06-14 | 2017-06-14 | Preparation method of bio-based network toughened epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710448126.9A CN107129664B (en) | 2017-06-14 | 2017-06-14 | Preparation method of bio-based network toughened epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107129664A CN107129664A (en) | 2017-09-05 |
| CN107129664B true CN107129664B (en) | 2022-03-25 |
Family
ID=59734648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710448126.9A Active CN107129664B (en) | 2017-06-14 | 2017-06-14 | Preparation method of bio-based network toughened epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107129664B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574984B (en) * | 2009-10-09 | 2014-09-17 | 汉高股份有限及两合公司 | A latent curing agent and epoxy compositions containing the same |
| CN104356361A (en) * | 2014-10-15 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Bio-based multifunctional silicon-framework epoxy resin as well as preparing method and application thereof |
| CN104448365B (en) * | 2014-12-12 | 2017-07-14 | 江南大学 | It is a kind of prepare epoxidized vegetable oil it is epoxy resin toughened/method of cellulose composite membrane |
| CN105153645A (en) * | 2015-07-24 | 2015-12-16 | 常州大学 | Method for toughened epoxy resin by synergistic effect of epoxidized soybean oil and polyether amine |
-
2017
- 2017-06-14 CN CN201710448126.9A patent/CN107129664B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107129664A (en) | 2017-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104755526B (en) | Epoxy curing agent | |
| CA2743800C (en) | Improved epoxy systems for composites | |
| KR101542338B1 (en) | Epoxy resin composition and fiber-reinforced composite material | |
| KR101846978B1 (en) | Epoxy resin composition for resin transfer molding of fiber-reinforced composite material, fiber-reinforced composite material, and method for producing same | |
| TWI649372B (en) | Fiber reinforced composite | |
| CN109265922B (en) | High-toughness autocatalytic epoxy resin and preparation method thereof | |
| WO2018036506A1 (en) | Epoxy resin composition with rapid curing and low linear shrinkage | |
| CN107709399A (en) | Composition epoxy resin, fibre reinforced composites, products formed and pressure vessel | |
| CN105378019A (en) | Curable compositions | |
| CN100336841C (en) | Epoxy resin roughening and curing agent | |
| US11530288B2 (en) | Anhydrous routes to highly processable covalent network polymers and blends | |
| CN111333817A (en) | Bio-based furan epoxy resin polymer and preparation method and application thereof | |
| CN113061416A (en) | High-strength high-toughness epoxy binder and preparation method thereof | |
| EP3083771A1 (en) | Curable compositions | |
| CN110172228A (en) | A kind of anti-aging composite material of lignin epoxide resin/fibre reinforced | |
| CN106589837A (en) | Heat-resisting epoxy resin and carbon fiber composite cured at medium and low temperature and preparation method of composite | |
| CN113683777A (en) | Preparation method of epoxy-terminated hyperbranched polyether sulfone and application of epoxy-terminated hyperbranched polyether sulfone in salt spray-resistant epoxy resin | |
| CN107778774B (en) | Epoxy resin adhesive film and preparation method thereof | |
| CN105837796A (en) | Preparation of thermosetting polymer high in biological base content | |
| CN109836557B (en) | Toughened hydrophobic epoxy resin and preparation method thereof | |
| CN106117980B (en) | A kind of original position self reinforcing resin system and preparation method thereof | |
| CN107129664B (en) | Preparation method of bio-based network toughened epoxy resin | |
| CN103570937A (en) | Phenolic resin/MC nylon composite material, and preparation method thereof | |
| EP3320013B1 (en) | Stable high glass transition temperature epoxy resin system for making composites | |
| CN105482373B (en) | A kind of method of epoxy terminated polystyrene oligomer Toughening Modification of Epoxy |
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 | ||
| CP03 | Change of name, title or address |
Address after: 3501 Qilu University of technology, Daxue Road, Changqing District, Jinan City, Shandong Province Patentee after: Qilu University of Technology (Shandong Academy of Sciences) Country or region after: China Address before: 3501 Qilu University of technology, Daxue Road, Changqing District, Jinan City, Shandong Province Patentee before: Qilu University of Technology Country or region before: China |
|
| CP03 | Change of name, title or address |