CN115044076A - Surface-modified milled fiber and preparation method thereof, high-toughness modified epoxy resin prepared from same and preparation method thereof - Google Patents
Surface-modified milled fiber and preparation method thereof, high-toughness modified epoxy resin prepared from same and preparation method thereof Download PDFInfo
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- CN115044076A CN115044076A CN202210710804.5A CN202210710804A CN115044076A CN 115044076 A CN115044076 A CN 115044076A CN 202210710804 A CN202210710804 A CN 202210710804A CN 115044076 A CN115044076 A CN 115044076A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
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- 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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention discloses a surface modified milled fiber and a preparation method thereof, a high-toughness modified epoxy resin prepared from the surface modified milled fiber and a preparation method of the high-toughness modified epoxy resin. The surface-modified milled fibers include milled fibers and an epoxy resin attached to the surface of the milled fibers, wherein the milled fibers have the epoxy resin in the epoxy emulsion attached to the surface of the milled fibers by a silane coupling agent. The modified epoxy resin comprises the following raw materials in parts by weight: 80-100 parts of epoxy resin raw material, 5-15 parts of diluent, 0.1-2.5 parts of modified milled fiber, 70-90 parts of curing agent and 1-5 parts of accelerator. According to the invention, the coupling agent and the epoxy resin in the epoxy emulsion are introduced to the surface of the milled fiber to realize the surface modification of the milled fiber, so that the modified milled fiber surface has a structure similar to a resin matrix and a large number of active functional groups, and the modified milled fiber surface is uniformly dispersed in the epoxy resin by stirring and ultrasonic methods, so that the tensile strength and the elongation at break of the modified epoxy resin are obviously improved.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to surface-modified milled fibers and a preparation method thereof, and high-toughness and high-strength modified epoxy resin prepared from the surface-modified milled fibers and a preparation method thereof.
Background
The epoxy resin is a thermosetting resin which is widely applied, has the advantages of excellent mechanical property, corrosion resistance, electric insulation property and the like, and is widely applied to the industrial fields of aerospace, wind power, insulating materials, coatings and the like. However, due to the high degree of crosslinking in the system, especially in anhydride-cured systems, the toughness of epoxy resins is inadequate.
Currently, increasing the toughness of epoxy resins of anhydride-cured systems is often achieved by adding plasticizers, such as polyurethane terminated plasticizers and some thermoplastic rubber particles, but such toughened resin systems reduce the strength, hardness, modulus, etc. of the resin system. For example, patent CN 107109176B adds a butadiene-acrylonitrile copolymer terminated by carboxyl group to epoxy resin to form a resin system of rubber particles with core/shell structure, which significantly improves the toughness of the epoxy resin system and also lowers the glass transition temperature and modulus of the resin system. In addition, some methods for reducing the crosslinking density of epoxy curing systems by using mixed alcohols to improve the toughness are proposed, for example, in patent CN 112552486A, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, polyethylene glycol, etc. are added into the epoxy resin system of anhydride curing system, so as to improve the toughness of the original resin and reduce the glass transition problem of the resin.
In recent years, for example, thermotropic liquid crystal toughening modes such as thermotropic liquid crystal toughening, interpenetrating network polymer toughening, hyperbranched polymer toughening and nano-particles toughening can improve the toughness of a resin system, but the modulus strength cannot be reduced, even the modulus strength is slightly increased, but the preparation methods are often characterized by complex process, difficult production conditions and the like, so that the method has very important practical significance for finding a new method which is simple to operate, easy for large-scale production and good in manufacturability.
Disclosure of Invention
Aiming at the problems in the background art, the surface modified milled fiber and the preparation method thereof, the epoxy resin reinforced by the modified milled fiber and the preparation method thereof are provided, so that the toughness of the epoxy resin can be obviously improved, and the strength and the modulus of an epoxy resin system can be increased.
The invention provides a surface modified milled fiber, which is characterized in that: the surface-modified milled fibers include milled fibers and an organic substance attached to the surface of the milled fibers, the organic substance including a silane coupling agent and an epoxy resin. The weight ratio of the organic matter on the surface to the milled fiber is 1-2.5:100, and the epoxy resin is the epoxy resin in the epoxy emulsion.
Further, the milled fibers have a diameter of 10 to 22 microns and a length of 10 to 400 microns.
Further, the silane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane and aminoethylaminopropyltriethoxysilane.
Further, the epoxy emulsion is preferably prepared according to the following steps: and mixing the epoxy resin and the nonionic emulsifier, and then mixing the mixed system obtained by mixing with water to obtain the epoxy emulsion.
Furthermore, the epoxy resin in the epoxy emulsion is one or more of bisphenol A epoxy, bisphenol F epoxy, hydrogenated bisphenol A epoxy and novolac epoxy.
Furthermore, the nonionic emulsifier in the epoxy emulsion is any one or a mixture of more than two of polyoxyethylene ether, polyoxypropylene ether and block copolymer of ethylene oxide and propylene oxide.
Furthermore, the proportion of the nonionic emulsifier in the epoxy emulsion is 7.5-22.5% of the weight ratio of the epoxy resin.
Further, the solid content of the epoxy emulsion is preferably 40-70 wt%, and specifically can be 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt% or 70 wt%; the content of the emulsifier in the epoxy emulsion is preferably 7.5-22.5 wt% of the mass of the epoxy resin, and specifically can be 8.3 wt%, 8.5 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 22.5 wt%.
Further, in the preparation step of the epoxy emulsion provided by the invention, the mixing temperature of the epoxy resin and the emulsifier is preferably 95-100 ℃, and specifically can be 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃; the rotation speed for mixing the epoxy resin and the emulsifier is preferably 800-1300 r/min, and specifically can be 800r/min, 850r/min, 900r/min, 950r/min, 1000r/min, 1050r/min, 1100r/min, 1150r/min, 1200r/min, 1250r/min or 1300 r/min; the mixing system is preferably mixed with water in such a manner that water is added dropwise to the mixing system.
The invention provides a preparation method of surface modified milled fiber, which comprises the following steps:
step 1: adding acetone into a reaction vessel, heating to 50-70 ℃, adding the milled fiber into the acetone, uniformly stirring and dissolving for 1-4h, filtering and airing, wherein the weight ratio of the solvent to the milled fiber is (2-4): 1.
step 2: adding the silane coupling agent into the deionized water solution of ethanol, stirring at room temperature, adding acetic acid, and adjusting the pH value to 4-5 to form hydrolysate of the silane coupling agent. Wherein the weight ratio of various substances is deionized water: anhydrous ethanol: silane 70-80: 10-15: 5-10.
And step 3: and adding the epoxy emulsion into the hydrolysate of the silane coupling agent, and uniformly stirring for 30-90min at room temperature. The weight ratio of the solid matter of the epoxy emulsion to the coupling agent is 2-5: 1.
and 4, step 4: adding the dried milled fiber into the emulsion, uniformly stirring at room temperature for 1-4h, and filtering under reduced pressure. Putting into a 120 ℃ oven, drying, grinding, sealing and storing.
The invention provides a modified epoxy resin, which is characterized in that: the modified epoxy resin consists of epoxy resin raw material, diluent, curing agent, modified milled fiber and accelerator.
The modified epoxy resin comprises the following raw materials in parts by weight:
80-100 parts of epoxy resin raw material
5-15 parts of diluent
0.1-2.5 parts of modified milled fiber
70-90 parts of curing agent
1-5 parts of accelerator
Further, the epoxy resin raw material is bisphenol A epoxy with a structural formula as follows:
Further, the diluent is one or more of ethylene glycol diglycidyl ether, 1, 4-hexanedimethanol diglycidyl ether, glycidyl laurate, n-butyl glycidyl ether and glycerol triglycidyl ether.
Further, the curing agent is one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, trimellitic anhydride, dodecenyl succinic anhydride and poly adipic anhydride.
Further, the accelerator is one or more of imidazole compounds, benzylamine compounds and quaternary ammonium salts.
The invention also provides a preparation method of the modified epoxy resin, which comprises the following steps:
step 1: mixing the epoxy resin raw material and the diluent in proportion, stirring for 1-2h to obtain a mixture, and then removing bubbles for 1-4h under the condition of vacuum pressure of 0-1kPa to form the material A.
Step 2: mixing the modified milled fiber, the curing agent and the accelerator according to a ratio, stirring for 1-4h, then carrying out ultrasonic treatment for 1-3h, and removing bubbles to form a material B.
And step 3: mixing and stirring the material A and the material B for 30min-2h, vacuumizing for 1-4h, pouring into a mold, curing at 160-180 ℃ for 1-4h, and naturally cooling and demolding.
The invention has the beneficial effects that: the invention coats the coupling agent and the epoxy emulsion on the surface of the milled fiber, so that the milled fiber is combined with the epoxy resin in the epoxy emulsion through the coupling agent, the surface modification of the milled fiber is realized, the modified milled fiber can be more easily mixed with the epoxy resin according to the principle of similar compatibility because the modified milled fiber has a structure similar to a resin matrix and a large amount of active functional groups, and the modified milled fiber is uniformly dispersed in the epoxy resin through stirring and ultrasonic methods, and the tensile strength and the elongation at break of a modified epoxy resin system are obviously improved. The modified milled fiber is adopted to toughen and strengthen the epoxy resin, so that the tensile strength of the modified epoxy resin is improved by 9-13% compared with the epoxy resin, the elongation at break is improved by 5-7%, and the modulus is hardly influenced.
Drawings
FIG. 1 scanning electron micrograph of the surface topography of the modified milled fiber of example 3 of the present invention.
FIG. 2 scanning electron micrographs of tensile sections of the modified milled fiber-reinforced epoxy resin of example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, wherein the present embodiment is based on the technical solution, and detailed embodiments and specific operation processes are provided, but the present invention is not limited to the present embodiment.
Example one
The modified epoxy resin comprises the following components:
example two
The modified epoxy resin comprises the following components:
EXAMPLE III
The modified epoxy resin comprises the following components:
the modified milled fibers of the above examples include milled fibers having epoxy resin adhered to the surface thereof by a silane coupling agent, and organic substances such as epoxy resin adhered to the surface of the milled fibers, wherein the weight ratio of the organic substances to the milled fibers on the surface is 1-2.5:100,
the milled fibers are 10-22 microns in diameter and 10-400 microns in length.
The silane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane and aminoethylaminopropyltriethoxysilane.
The epoxy emulsion is preferably prepared according to the following steps: and mixing the epoxy resin and the nonionic emulsifier, and then mixing the mixed system obtained by mixing with water to obtain the epoxy emulsion.
The epoxy resin in the epoxy emulsion is one or more of bisphenol A epoxy, bisphenol F epoxy, hydrogenated bisphenol A epoxy and novolac epoxy.
The nonionic emulsifier in the epoxy emulsion is any one or a mixture of more than two of polyoxyethylene ether, polyoxypropylene ether and segmented copolymer of ethylene oxide and propylene oxide.
The proportion of the nonionic emulsifier in the epoxy emulsion is 7.5-22.5% of the weight ratio of the epoxy resin.
The solid content of the epoxy emulsion is preferably 40-70 wt%, and specifically can be 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt% or 70 wt%; the content of the emulsifier in the epoxy emulsion is preferably 7.5 to 22.5 wt% of the mass of the epoxy resin, and specifically may be 8.3 wt%, 8.5 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 22.5 wt%.
In the preparation step of the epoxy emulsion provided by the invention, the mixing temperature of the epoxy resin and the emulsifier is preferably 95-100 ℃, and specifically can be 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃; the rotation speed for mixing the epoxy resin and the emulsifier is preferably 800-1300 r/min, and specifically can be 800r/min, 850r/min, 900r/min, 950r/min, 1000r/min, 1050r/min, 1100r/min, 1150r/min, 1200r/min, 1250r/min or 1300 r/min; the mixing system is preferably mixed with water in such a manner that water is added dropwise to the mixing system.
The preparation method of the modified milled fiber comprises the following steps:
step 1: adding acetone into a reaction vessel, heating to 50 ℃, adding the milled fiber into the reaction vessel, uniformly stirring and dissolving for 2 hours, filtering and airing, wherein the weight ratio of the solvent to the milled fiber is 2: 1.
step 2: adding the silane coupling agent into the deionized water solution of ethanol, stirring at room temperature, adding acetic acid, and adjusting the pH value to 4.6 to form hydrolysate of the silane coupling agent. Wherein the weight ratio of various substances is deionized water: anhydrous ethanol: silane 80:10: 10.
And step 3: and adding the epoxy emulsion with the solid content of 55% into the hydrolysate of the silane coupling agent, and uniformly stirring for 60min at room temperature. The weight ratio of the solid matter of the epoxy emulsion to the coupling agent is 4: 1.
And 4, step 4: adding the dried milled fiber into the emulsion, uniformly stirring for 2h at room temperature, washing with deionized water, filtering under reduced pressure until the filtrate is clear, putting the obtained modified milled fiber into an oven at 120 ℃, drying for 4h, grinding, and sealing for storage to obtain the modified milled fiber.
The preparation method of the modified epoxy resin in the above embodiment comprises the following steps:
step 1: epoxy resin E51 and ethylene glycol diglycidyl ether were stirred in a reactor at a speed of 600r/m for 2h, and then bubbles were evacuated under a vacuum pressure of 1kPa for 3h to form a material A.
Step 2: mixing the modified milled fiber, methyl tetrahydrophthalic anhydride, poly adipic anhydride and imidazole according to a ratio, stirring for 1h, then carrying out ultrasonic treatment for 1h, and removing bubbles to form a material B.
And step 3: mixing the material A and the material B, stirring for 30min, vacuumizing for 1h, pouring into a mold, curing at 160 ℃ for 4h, naturally cooling and demolding.
Comparative example 1
The epoxy resin comprises the following components:
step 1: epoxy resin E51 and ethylene glycol diglycidyl ether were stirred in a reactor at a speed of 600r/m for 2h, and then bubbles were evacuated under a vacuum pressure of 1kPa for 3h to form a material A.
Step 2: mixing methyl tetrahydrophthalic anhydride, poly adipic anhydride and imidazole according to a ratio, stirring for 1h, then carrying out ultrasonic treatment for 1h, and removing bubbles to form a material B.
And step 3: mixing the material A and the material B, stirring for 30min, vacuumizing for 1h, pouring into a mold, curing at 160 ℃ for 4h, naturally cooling and demolding.
Comparative example 2
The epoxy resin comprises the following components:
step 1: epoxy resin E51 and ethylene glycol diglycidyl ether were stirred in a reactor at a speed of 600r/m for 2h, and then bubbles were evacuated under a vacuum pressure of 1kPa for 3h to form a material A.
Step 2: mixing the milled fiber, the methyl tetrahydrophthalic anhydride, the poly adipic anhydride and the imidazole according to a ratio, stirring for 1h, then carrying out ultrasonic treatment for 1h, and removing bubbles to form a material B.
And step 3: mixing the material A and the material B, stirring for 30min, vacuumizing for 1h, pouring into a mold, curing at 160 ℃ for 4h, naturally cooling and demolding.
The resins prepared in examples 1 to 5 were tested according to ISO-527-1 and DSC for their properties, and the results were as follows:
in the comparative example, the unmodified milled fibers have small toughening and reinforcing effects on the epoxy resin, and the modified milled fibers have obvious improvement on the strength, the elongation at break and the Tg, so that the tensile strength of the modified epoxy resin is improved by 9-13 percent, the elongation at break is improved by 5-7 percent, and the modulus is hardly influenced.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited thereto, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (12)
1. A surface-modified milled fiber characterized by: the surface-modified milled fibers include milled fibers and organic substances such as epoxy resin attached to the surface of the milled fibers, and the epoxy resin in the epoxy emulsion is attached to the surface of the milled fibers by a silane coupling agent.
2. The surface-modified milled fibers according to claim 1, characterized in that the weight ratio of the organic matter on the surface to the milled fibers is 1-2.5: 100.
3. Surface-modified milled fibres according to claim 1 or 2, characterised in that the milled fibres have a diameter of 10-22 microns and a length of 10-400 microns.
4. The surface-modified milled fibers according to claim 1 or 2, wherein an epoxy emulsion comprising an epoxy resin, an emulsifier and water is mixed, and then the mixed system obtained by mixing the epoxy resin and the emulsifier is mixed with water to obtain the epoxy emulsion.
5. Surface-modified milled fibres according to claim 1 or 2, characterised in that the proportion of nonionic emulsifier in the epoxy emulsion is 7.5-22.5% by weight of the resin.
6. A process for preparing surface-modified milled fibers according to claims 1 to 5, comprising the steps of:
step 1: adding acetone into a reaction vessel, heating to 50-70 ℃, adding milled fibers into the acetone, uniformly stirring and dissolving for 1-4h, filtering and airing, wherein the weight ratio of the solvent to the milled fibers is (2-4): 1;
step 2: adding a silane coupling agent into a deionized water solution of ethanol, stirring at room temperature, adding acetic acid, and adjusting the pH value to 4-5; wherein the weight ratio of various substances is deionized water: absolute ethanol: silane 70-80: 10-15: 5-10;
and step 3: adding the epoxy emulsion into the hydrolysate of the silane coupling agent, and uniformly stirring for 30-90min at room temperature; the weight ratio of the solid matter of the epoxy emulsion to the coupling agent is 2-5: 1;
and 4, step 4: adding the dried milled fiber into the emulsion, uniformly stirring at room temperature for 1-4h, and filtering under reduced pressure; putting into a 120 ℃ oven, drying, grinding, sealing and storing.
7. A modified epoxy resin is characterized in that: the modified epoxy resin comprises epoxy resin raw materials, a diluent, a curing agent, the modified milled fiber of claims 1-5 and an accelerator.
8. The modified epoxy resin as claimed in claim 7, wherein the raw materials comprise, by weight: 80-100 parts of epoxy resin raw material, 5-15 parts of diluent, 70-90 parts of curing agent, 0.1-2.5 parts of modified milled fiber and 1-5 parts of accelerator.
9. The modified epoxy resin as claimed in claim 7 or 8, wherein the epoxy resin is bisphenol A epoxy resin, and the diluent is one or more selected from ethylene glycol diglycidyl ether, 1, 4-hexanedimethanol diglycidyl ether, glycidyl laurate, n-butyl glycidyl ether, and glycerol triglycidyl ether.
10. The modified epoxy resin according to claim 7 or 8, wherein the curing agent is one or more selected from phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, trimellitic anhydride, dodecenylsuccinic anhydride and polyhexamic anhydride.
11. The modified epoxy resin as claimed in claim 7 or 8, wherein the accelerator is one or more of imidazole compounds, benzylamine compounds and quaternary ammonium salts.
12. A process for preparing a modified epoxy resin according to claims 7 to 11, comprising the steps of:
step 1: mixing an epoxy resin raw material and a diluent in proportion, stirring for 1-2h to obtain a mixture, and then removing bubbles for 1-4h under the condition of vacuum pressure of 0-1kPa to form a material A;
step 2: mixing the modified milled fiber, the curing agent and the accelerator according to a ratio, stirring for 1-4h, then carrying out ultrasonic treatment for 1-3h, and removing bubbles to form a material B;
and step 3: mixing and stirring the material A and the material B for 30min-2h, vacuumizing for 1-4h, pouring into a mold, curing at 160-180 ℃ for 1-4h, and naturally cooling and demolding.
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Citations (3)
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|---|---|---|---|---|
| WO2013123648A1 (en) * | 2012-02-22 | 2013-08-29 | Abb Technology Ltd. | Curable epoxy composition with milled glass fiber |
| CN106758242A (en) * | 2016-12-20 | 2017-05-31 | 盐城工学院 | A kind of surface modified castor fiber and its preparation method and application |
| JP2017119733A (en) * | 2015-12-28 | 2017-07-06 | セントラル硝子株式会社 | Glass powder granule |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013123648A1 (en) * | 2012-02-22 | 2013-08-29 | Abb Technology Ltd. | Curable epoxy composition with milled glass fiber |
| JP2017119733A (en) * | 2015-12-28 | 2017-07-06 | セントラル硝子株式会社 | Glass powder granule |
| CN106758242A (en) * | 2016-12-20 | 2017-05-31 | 盐城工学院 | A kind of surface modified castor fiber and its preparation method and application |
Non-Patent Citations (1)
| Title |
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| 李丰恺等: "磨碎玻璃纤维增强环氧树脂复合材料的制备及力学性能研究", 《材料发开与应用》, vol. 32, no. 6, pages 101 - 109 * |
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